CN1817837B - Carbonyl compound and method for preparing the same - Google Patents

Carbonyl compound and method for preparing the same Download PDF

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Publication number
CN1817837B
CN1817837B CN 200610004608 CN200610004608A CN1817837B CN 1817837 B CN1817837 B CN 1817837B CN 200610004608 CN200610004608 CN 200610004608 CN 200610004608 A CN200610004608 A CN 200610004608A CN 1817837 B CN1817837 B CN 1817837B
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cyclopentadienyl
phenyl
methyl
dichloride
close titanium
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CN1817837A (en
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花冈秀典
吉川荣二
今本有香
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Priority claimed from JP2001337582A external-priority patent/JP3928408B2/en
Priority claimed from JP2001354234A external-priority patent/JP3960018B2/en
Priority claimed from JP2001366248A external-priority patent/JP3960027B2/en
Priority claimed from JP2001368236A external-priority patent/JP3960028B2/en
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Abstract

The present invention relates to a transition metal complex represented by the formula (I): wherein M represents a Group 4 transition metal; -Y- represents (a): -C(R<1>)(R<20>)-A-, (b): -C(R<1>)(R<20>)-A<1>(R<30>)-, (c): -C(R<1>)=A<1>-, or (d): -C(R<1>)=A<1>-A<2>-R<30> (A represents a Group 16 element and A<1> and A<2> each represents a Group 15 element); R<1 >to R<9>, R<20>, and R<30> are the same or different and each represents an optionally substituted hydrocarbon group, etc.; and X<1> and X<2> are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted C1-10 alkyl group, etc., and an intermediate product thereof, and a catalyst for olefin polymerization which comprises the transition metal complex as a component.

Description

Carbonyl compound and preparation method thereof
The application is dividing an application of asking in following: application number: 02822222.9 (PCT/JP02/09314); The applying date: on September 12nd, 2002; Denomination of invention: " transition metal complex and catalyst for olefines polymerizing and prepare the method for olefin polymer with it ".
Technical field
The present invention relates to transition metal complex and comprise the catalyst for olefines polymerizing of described complex compound and prepare the method for olefin polymer with it.
Background technology
As for olefines polymerization semi-metallocene catalyst, disclose respectively that dichloride dimetylsilyl (tetramethyl-ring pentadienyl) (the 3-tertiary butyl-5-methyl-2-phenoxy group) is closed titanium (spy opens flat 3-163088 communique) and dichloride dimetylsilyl (tetramethyl-ring pentadienyl) (TERTIARY BUTYL AMINE) is closed titanium (spy opens flat 9-87313 number).But, need to use silicon compound as key intermediate in the production process of these transition metal complexes, and silicon compound is difficult to manipulation to moisture-sensitive.Therefore, need to handle more easily and can provide the catalyzer of various olefin polymers.
Summary of the invention
According to the present invention, available energy prepares the part intermediate of handling more easily and obtains transition metal complex, and need not to use to moisture-sensitive, be difficult to the silicon compound handled as key intermediate, can obtain to produce the catalyzer of various olefin polymers as catalyst component with described transition metal complex.
That is, the invention provides following invention:
1. formula (I):
Figure G2006100046087D00021
Wherein M represents 4 group 4 transition metals;
-Y-represents
(a)：-C(R 1)＝(R 20)-A-、
(b)：-C(R 1)＝(R 20)-A 1(R 30)-、
(c) :-C (R 1)=A 1, or
(d)：
Figure G2006100046087D00022
Here A 1And A 2Form coordinate bond with M;
A represents 16 family's elements, A 1And A 2Represent 15 family's elements separately;
R 1And R 20Identical or different, represent separately hydrogen atom,
The optional C that replaces 1-10Alkyl,
The optional C that replaces 6-20Aryl or
The optional C that replaces 7-20Aralkyl;
R 30The expression hydrogen atom,
The optional C that replaces 1-10Alkyl,
The optional C that replaces 6-20Aryl,
The optional C that replaces 7-20Aralkyl or
The optional C that is optionally substituted 1-20The silyl that alkyl replaces;
R 2, R 3, R 4And R 5Identical or different, represent separately hydrogen atom,
The optional C that replaces 1-10Alkyl,
The optional C that replaces 1-10Alkoxyl group,
The optional C that replaces 6-20Aryl,
The optional C that replaces 6-20Aryloxy,
The optional C that replaces 7-20Aralkyl,
The optional C that replaces 7-20Aralkoxy,
The C that is optionally substituted 1-20The silyl that alkyl replaces or
C 1-20The amino that alkyl replaces;
R 6, R 7, R 8And R 9Identical or different, represent separately hydrogen atom, halogen atom,
The optional C that replaces 1-10Alkyl,
The optional C that replaces 1-10Alkoxyl group,
The optional C that replaces 6-20Aryl,
The optional C that replaces 6-20Aryloxy,
The optional C that replaces 7-20Aralkyl,
The optional C that replaces 7-20Aralkoxy,
The C that is optionally substituted 1-20The silyl that alkyl replaces or
C 1-20The amino that alkyl replaces; And
X 1And X 2Identical or different, represent separately hydrogen atom, halogen atom,
The optional C that replaces 1-10Alkyl,
The optional C that replaces 1-10Alkoxyl group,
The optional C that replaces 6-20Aryl,
The optional C that replaces 6-20Aryloxy,
The optional C that replaces 7-20Aralkyl,
The optional C that replaces 7-20Aralkoxy or
C 1-20The amino that alkyl replaces, perhaps
X 1And X 2, R 1And R 20, adjacent R 2, R 3, R 4And R 5Perhaps adjacent R 6, R 7, R 8And R 9Can be interconnected to form ring;
Condition be when-when Y-represented (a), R can not appear 1And R 20All represent hydrogen atom and R 2, R 3, R 4And R 5Form the situation of 2-methyl indenes-1-base with the cyclopentadiene ring;
2. the catalyst for olefines polymerizing that comprises above-mentioned transition metal complex and following compound (A):
Wherein (A) represents at least a compound that is selected from following compounds (A1) to (A3):
(A1): likes E1 aAl (Z) (3-a)Shown in organo-aluminium compound,
(A2): have formula { Al (E2)-O-} bShown in structure the ring-type aikyiaiurnirsoxan beta and
(A3): have formula E3{-Al (E3)-O-} cAl (E3) 2Shown in the line style aikyiaiurnirsoxan beta of structure,
Wherein E1 is identical or different to E3, represents the C1-8 alkyl separately;
Z is identical or different, represents hydrogen atom or halogen atom separately; And
A is 1,2 or 3, and b is not less than 2 integer, and c is not less than 1 integer;
3. comprise the catalyst for olefines polymerizing that above-mentioned transition metal complex and compound (A) also have (B):
Wherein (B) represents at least a compound that is selected from following compounds (B1) to (B3):
(B1): likes BQ 1Q 2Q 3Shown in boron compound,
(B2): likes Z +(BQ 1Q 2Q 3Q 4) -Shown in boron compound and
(B3): formula (L-H) +(BQ 1Q 2Q 3Q 4) -Shown in boron compound,
Wherein B is the boron atom of triad valence state;
Q 1To Q 4Identical or different, represent separately halogen atom,
C 1-20Alkyl,
C 1-20The halo alkyl,
By C 1-20The silyl that alkyl replaces,
C 1-20Alkoxyl group or
By two C 2-20The amino that alkyl replaces;
L-H represents Bronsted acid; And
Z is identical or different, represents inorganic separately or organic cation (for example hydrogen atom, halogen atom or trityl positively charged ion);
4. method for preparing olefin polymer, this method comprises with above-mentioned catalyst for olefines polymerizing olefin polymerization;
5. product in the middle of substituted cyclopentadiene part shown in the following formula (II) or its:
Figure G2006100046087D00051
Wherein-Y ' expression
(a’)：-C(R 1)(R 20)-A-H
(b’)：-C(R 1)(R 20)-A 1(R 30)-H
(c’)：-C(R 1)＝A 1-H
(d’)：
Figure G2006100046087D00052
(e)：-C(R 1)＝A 1-R 30
(f) :-CH=A 1-OR 30Or
(g) :-CN; And
R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 20, R 30, A, A 1And A 2Have the definition identical with foregoing;
Condition is:
1) when-Y ' expression (a '), R 2And R 3Perhaps R 4And R 5Can not combine and cyclopentadiene ring formation fluorenes ring or indenes ring; With
2) when-Y ' expression (g), R 2And R 3Perhaps R 4And R 5Can not combine and cyclopentadiene ring formation fluorenes ring, and compound shown in the formula (II) can not be 2-(4-methoxyl group indenes-1-yl) benzonitrile;
In addition, for two keys of cyclopentadiene ring, its position is not limited to the position shown in the formula, can be any position, and perhaps this cyclopentadiene ring is illustrated in the mixture of isomers that any position has two keys;
6. the method for transition metal complex shown in the preparation formula (I), this method comprise makes the reaction of transistion metal compound shown in substituted cyclopentadiene shown in the formula (II) and the formula (III), in the formula (II)-
Y ' expression (a ') in (d ') any,
MX 1X 2X 3X 4 (III)
Wherein M represents 4 group 4 transition metals; And
X 1, X 2, X 3And X 4Identical or different, represent separately hydrogen atom, halogen atom,
C 1-10Alkyl,
C 1-10Alkoxyl group,
C 6-20Aryl,
C 6-20Aryloxy,
C 7-20Aralkyl,
C 7-20Aralkoxy or
C 1-20The amino that alkyl replaces;
7. carbonyl compound shown in the formula (1):
Figure G2006100046087D00061
R wherein 1The expression hydrogen atom,
The optional C that replaces 1-10Alkyl,
The optional C that replaces 6-20Aryl or
The optional C that replaces 7-20Aralkyl;
R 2, R 3, R 4And R 5Identical or different, represent separately hydrogen atom,
The optional C that replaces 1-10Alkyl,
The optional C that replaces 1-10Alkoxyl group,
The optional C that replaces 6-20Aryl,
The optional C that replaces 6-20Aryloxy,
The optional C that replaces 7-20Aralkyl,
The optional C that replaces 7-20Aralkoxy,
The C that is optionally substituted 1-20The silyl that alkyl replaces or
C 1-20The amino that alkyl replaces; And
R 6, R 7, R 8And R 9Identical or different, represent separately hydrogen atom, halogen atom,
The optional C that replaces 1-10Alkyl,
The optional C that replaces 1-10Alkoxyl group,
The optional C that replaces 6-20Aryl,
The optional C that replaces 6-20Aryloxy,
The optional C that replaces 7-20Aralkyl,
The optional C that replaces 7-20Aralkoxy,
The C that is optionally substituted 1-20The silyl that alkyl replaces or
C 1-20The amino that alkyl replaces, perhaps
Adjacent R 2, R 3, R 4And R 5With adjacent R 6, R 7, R 8And R 9Can be interconnected to form phenyl ring or cycloalkylidene (cycloalkylene) ring;
Condition is
1) position of two keys is arbitrarily in the cyclopentadiene ring, perhaps this cyclopentadiene ring be illustrated in the optional position have two keys compound mixture and
2) R 2And R 3Perhaps R 4And R 5Can not combine and cyclopentadiene ring formation fluorenes ring or indenes ring;
Shown in the preferred formula (1) in the carbonyl compound, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8And R 9Be C 1-10Alkyl; In the preferred carbonyl compound, R 2, R 3, R 4And R 5Identical or different, independent separately expression hydrogen atom or C 1-5Alkyl; In the further preferred carbonyl compound, R 1Be hydrogen atom, C 1-5Alkyl or C 6-10Aryl.
8. the method for substituted cyclopentadiene compound shown in the preparation formula (1), this method is included in magnesium compound or organolithium compound exists down, make the reaction of cyclopentenone shown in halogen compounds shown in the formula (2) and the formula (3), obtain cyclopentenol shown in the formula (4), and with the described compound of acid treatment:
Figure G2006100046087D00081
R wherein 1, R 6, R 7, R 8And R 9Have and following identical connotation,
R 10And R 11Identical or different, the C that replaces is chosen in expression wantonly separately 1-10Alkyl, perhaps they are connected with each other at its end, and the carbon atom that is connected with described Sauerstoffatom with Sauerstoffatom forms 5 or 6 yuan of rings, and
X represents chlorine, bromine or iodine atom;
Figure G2006100046087D00082
R wherein 2, R 3, R 4And R 5Have and following identical connotation;
Figure G2006100046087D00083
R wherein 1The expression hydrogen atom,
The optional C that replaces 1-10Alkyl,
The optional C that replaces 6-20Aryl or
The optional C that replaces 7-20Aralkyl,
R 2, R 3, R 4And R 5Identical or different, represent separately hydrogen atom,
The optional C that replaces 1-10Alkyl,
The optional C that replaces 1-10Alkoxyl group,
The optional C that replaces 6-20Aryl,
The optional C that replaces 6-20Aryloxy,
The optional C that replaces 7-20Aralkyl,
The optional C that replaces 7-20Aralkoxy,
The C that is optionally substituted 1-20The silyl that alkyl replaces or
C 1-20The amino that alkyl replaces,
R 6, R 7, R 8And R 9Identical or different, independent separately expression hydrogen atom, halogen atom,
The optional C that replaces 1-10Alkyl,
The optional C that replaces 1-10Alkoxyl group,
The optional C that replaces 6-20Aryl,
The optional C that replaces 6-20Aryloxy,
The optional C that replaces 7-20Aralkyl,
The optional C that replaces 7-20Aralkoxy,
The C that is optionally substituted 1-20The silyl that alkyl replaces or
C 1-20The amino that alkyl replaces, perhaps
Adjacent R 2, R 3, R 4And R 5With adjacent R 6, R 7, R 8And R 9Can be interconnected to form phenyl ring or cycloalkylidene ring; With
R 10And R 11Has definition same as described above;
9. cyclopentenol shown in the formula (4).
Implement mode of the present invention
Exemplify compound shown in above-mentioned formula (I), (II) and (1) to (4) and following compound (5) substituent R below to (13) 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 20And R 30
Substituent R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 20, R 30And X 1To X 4The C of optional replacement 1-10The object lesson of alkyl comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, neo-pentyl, amyl group, n-hexyl, n-octyl, positive decyl.The above-mentioned substituent object lesson that is replaced by halogen atom (particularly fluorine atom) comprises methyl fluoride, difluoromethyl, trifluoromethyl, fluoro ethyl, two fluoro ethyls, trifluoroethyl, tetrafluoro ethyl, pentafluoroethyl group, perfluoro propyl, perfluoro butyl, perfluor amyl group, perfluoro hexyl, perfluoro capryl, perfluor decyl, trichloromethyl etc.Wherein preferable methyl, ethyl, sec.-propyl, the tertiary butyl, amyl group etc.
R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 20, R 30And X 1To X 4The C of optional replacement 6-20Aryl comprises phenyl, naphthyl, anthryl etc., its object lesson comprises for example phenyl, the 2-tolyl, the 3-tolyl, the 4-tolyl, 2, the 3-xylyl, 2, the 4-xylyl, 2, the 5-xylyl, 2, the 6-xylyl, 3, the 4-xylyl, 3, the 5-xylyl, 2,3, the 4-trimethylphenyl, 2,3, the 5-trimethylphenyl, 2,3, the 6-trimethylphenyl, 2,4, the 6-trimethylphenyl, 3,4, the 5-trimethylphenyl, 2,3,4, the 5-tetramethylphenyl, 2,3,4, the 6-tetramethylphenyl, 2,3,5, the 6-tetramethylphenyl, the pentamethyl-phenyl, ethylphenyl, the n-propyl phenyl, isopropyl phenyl, n-butylphenyl, secondary butyl phenenyl, tert-butyl-phenyl, the n-pentyl phenyl, the neo-pentyl phenyl, the n-hexyl phenyl, the n-octyl phenyl, positive decyl phenyl, the dodecyl phenyl, n-tetradecane base phenyl, naphthyl, anthryl.In addition, can also exemplify out, more particularly the above-mentioned substituting group that is replaced by fluorine atom by halogen atom.Preferred aryl groups, for example phenyl.
The optional C that replaces 7-20Aralkyl comprises benzyl, naphthyl methyl, the anthryl methyl, diphenyl methyl etc., its object lesson comprises for example benzyl, (2-aminomethyl phenyl) methyl, (3-aminomethyl phenyl) methyl, (4-aminomethyl phenyl) methyl, (2, the 3-3,5-dimethylphenyl) methyl, (2, the 4-3,5-dimethylphenyl) methyl, (2, the 5-3,5-dimethylphenyl) methyl, (2, the 6-3,5-dimethylphenyl) methyl, (3, the 4-3,5-dimethylphenyl) methyl, (2,3, the 4-trimethylphenyl) methyl, (2,3, the 5-trimethylphenyl) methyl, (2,3, the 6-trimethylphenyl) methyl, (3,4, the 5-trimethylphenyl) methyl, (2,4, the 6-trimethylphenyl) methyl, (2,3,4, the 5-tetramethylphenyl) methyl, (2,3,4, the 6-tetramethylphenyl) methyl, (2,3,5, the 6-tetramethylphenyl) methyl, (pentamethyl-phenyl) methyl, (ethylphenyl) methyl, (n-propyl phenyl) methyl, (isopropyl phenyl) methyl, (n-butylphenyl) methyl, (secondary butyl phenenyl) methyl, (tert-butyl-phenyl) methyl, (n-pentyl phenyl) methyl, (neo-pentyl phenyl) methyl, (n-hexyl phenyl) methyl, (n-octyl phenyl) methyl, (positive decyl phenyl) methyl, (dodecyl phenyl) methyl, naphthyl methyl, the anthryl methyl, diphenyl methyl and by the above-mentioned substituting group that halogen replaces, the fluoro aralkyl of more specifically saying so.Benzyl is a preferred substituted.
Substituent R 2, R 3, R 4, R 5, R 6, R 7, R 8And R 9The C of optional replacement 1-10The object lesson of alkoxyl group comprises methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert.-butoxy, n-pentyloxy, neopentyl oxygen, positive hexyloxy, n-octyloxy, positive ninth of the ten Heavenly Stems oxygen base, n-decyloxy.The fluorine atom substituted alkoxy that the example more specifically of the alkoxyl group that is replaced by halogen has alkoxyl group wherein to be replaced by fluorine atom.Preferred methoxyl group, oxyethyl group, tert.-butoxy.
Substituent R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9And X 1To X 4The C of optional replacement 6-20Aryloxy comprises phenoxy group, naphthyloxy, anthracene oxygen base.Its object lesson comprises phenoxy group, the 2-methylphenoxy, the 3-methylphenoxy, the 4-methylphenoxy, 2, the 3-dimethyl phenoxy, 2, the 4-dimethyl phenoxy, 2, the 5-dimethyl phenoxy, 2, the 6-dimethyl phenoxy, 3, the 4-dimethyl phenoxy, 3, the 5-dimethyl phenoxy, 2,3,4-trimethylammonium phenoxy group, 2,3,5-trimethylammonium phenoxy group, 2,3,6-trimethylammonium phenoxy group, 2,4,5-trimethylammonium phenoxy group, 2,4,6-trimethylammonium phenoxy group, 3,4,5-trimethylammonium phenoxy group, 2,3,4,5-tetramethyl-phenoxy group, 2,3,4,6-tetramethyl-phenoxy group, 2,3,5,6-tetramethyl-phenoxy group, the pentamethyl-phenoxy group, the ethyl phenoxy group, the n-propyl phenoxy group, the sec.-propyl phenoxy group, the normal-butyl phenoxy group, the sec-butyl phenoxy group, tertiary butyl phenoxy group, the n-hexyl phenoxy group, the n-octyl phenoxy group, positive decyl phenoxy group, the n-tetradecane phenoxyl, naphthyloxy, anthracene oxygen base and by the above-mentioned substituting group that halogen atom replaces more specifically has the fluoro aryloxy.
Substituent R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9And X 1To X 4The C of optional replacement 7-20Aralkoxy comprises benzyloxy, naphthyl methoxyl group, anthryl methoxyl group and phenylbenzene methoxy base.Its object lesson comprises benzyloxy, (2-aminomethyl phenyl) methoxyl group, (3-aminomethyl phenyl) methoxyl group, (4-aminomethyl phenyl) methoxyl group, (2, the 3-3,5-dimethylphenyl) methoxyl group, (2, the 4-3,5-dimethylphenyl) methoxyl group, (2, the 5-3,5-dimethylphenyl) methoxyl group, (2, the 6-3,5-dimethylphenyl) methoxyl group, (3, the 4-3,5-dimethylphenyl) methoxyl group, (2,3, the 4-trimethylphenyl) methoxyl group, (2,3, the 5-trimethylphenyl) methoxyl group, (2,3, the 6-trimethylphenyl) methoxyl group, (3,4, the 5-trimethylphenyl) methoxyl group, (2,4, the 6-trimethylphenyl) methoxyl group, (2,3,4, the 5-tetramethylphenyl) methoxyl group, (2,3,4, the 6-tetramethylphenyl) methoxyl group, (2,3,5, the 6-tetramethylphenyl) methoxyl group, (pentamethyl-phenyl) methoxyl group, (ethylphenyl) methoxyl group, (n-propyl phenyl) methoxyl group, (isopropyl phenyl) methoxyl group, (n-butylphenyl) methoxyl group, (secondary butyl phenenyl) methoxyl group, (tert-butyl-phenyl) methoxyl group, (n-pentyl phenyl) methoxyl group, (neo-pentyl phenyl) methoxyl group, (n-hexyl phenyl) methoxyl group, (n-octyl phenyl) methoxyl group, (positive decyl phenyl) methoxyl group, (dodecyl phenyl) methoxyl group, the naphthyl methoxyl group, the anthryl methoxyl group, phenylbenzene methoxy base and by the above-mentioned substituting group that halogen replaces, the aralkoxy that the fluorine atom of more specifically saying so replaces.Benzyloxy is a preferred substituted.
Substituent R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9And R 30C 1-20The example that alkyl replaces silyl has by C 1-20The silyl that alkyl replaces.Here used alkyl comprises for example C such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, neo-pentyl, amyl group, n-hexyl, cyclohexyl, n-octyl, positive decyl 1-10Alkyl, C such as phenyl, tolyl, xylyl, naphthyl, anthryl 6-20Aryl.Such C 1-20Alkyl replaces silyl and comprises for example methyl-silicane base, the ethyl silicane base, monosubstitution silyls such as phenyl silyl, dimetylsilyl, the diethylsilane base, two silyls that replace such as diphenylmethyl silylation, trimethyl silyl, triethylsilyl, three n-propyl silyls, the triisopropyl silyl, three normal-butyl silyls, three sec-butyl silyls, the tri-tert silyl, tri-iso-butylsilyl, t-butyldimethylsilyl, three n-pentyl silyls, three n-hexyl silyls, the thricyclohexyl silyl, triphenyl silyls etc. three replace silyl, preferred trimethyl silyl, t-butyldimethylsilyl and triphenyl silyl.The above-mentioned replacement silyl that also has alkyl wherein to be replaced by halogen atom such as fluorine atom.
Substituent R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9And X 1To X 4C 1-20The example of alkyl substituted-amino has the amino that is replaced by two alkyl.Here used alkyl comprises for example C such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, neo-pentyl, amyl group, n-hexyl, cyclohexyl, n-octyl, positive decyl 1-10Alkyl, C such as phenyl, tolyl, xylyl, naphthyl, anthryl 6-20Aryl.Such C 1-20The example of alkyl substituted-amino comprises for example dimethylamino, diethylamino, di amino, diisopropylaminoethyl, di-n-butyl amino, two sec-butyl amino, di-t-butyl amino, diisobutyl amino, tertiary butyl sec.-propyl amino, di-n-hexyl amino, di-n-octyl amino, two positive decyl amino, diphenyl amino etc., preferred dimethylamino and diethylamino.
Substituent R 6, R 7, R 8, R 9And X 1To X 4Halogen atom comprise fluorine atom, chlorine atom, bromine atoms and iodine atom, preferred fluorine atom and chlorine atom.
In formula (I), R 20Expression and R 1Identical substituting group, its object lesson comprises R 1In those groups of exemplifying.R 30Expression and R 1Identical substituting group, its object lesson comprises R 1In those groups of exemplifying.R 30Also comprise and R 2To R 5In the C that is optionally substituted 1-20The identical group of silyl that alkyl replaces.
Exemplify transition metal complex shown in the formula (I) below.
4 group 4 transition metals shown in the M comprise the transition metal (IUPAC inorganic chemistry nomenclature revised edition, 1989) of 4 families in the periodic table of elements, for example titanium atom, zirconium atom, hafnium atom etc., preferably titanium atom and zirconium atom.
16 family's elements of A representative comprise for example Sauerstoffatom, sulphur atom, selenium atom etc., preferred oxygen atom.
A 1And A 215 family's atoms comprise for example nitrogen-atoms, phosphorus atom, arsenic atom etc., preferred nitrogen atom in the periodic table of elements of representative.
In the transition metal complex of formula (I), preferred R 2, R 3, R 4And R 5Be respectively hydrogen atom or C 1-5Alkyl.
X 1And X 2Preferably include halogen atom, C 1-10Alkyl, C 7-20Aralkyl, C 6-20Aryl or C 1-20The amino that alkyl replaces, more preferably halogen atom and C 1-10The amino that alkyl replaces.
As the transition metal complex of formula (I), preferred X wherein 1And X 2Be respectively halogen atom or C 1-10The amino that alkyl replaces, R 2, R 3, R 4And R 5Be respectively methyl and R 6, R 7, R 8And R 9Be respectively the complex compound of hydrogen atom.
As the transition metal complex of formula (I), can exemplify following formula (I-1), (I-2), (I-3) and (I-4) shown in transition metal complex.
Exemplify below in formula (I) transition metal complex-Y-is the formula (1-1) of (a):
R wherein 1To R 9, R 20, X 1, X 2, M and A have the synonymous of definition in the above-mentioned formula (I).
In Chem.Commun. 1405-1406 page or leaf in 1999, disclose two (diethylins) and changed [1-(2-methyl indenes-1-yl)-2-naphthyl methoxyl group] and close zirconium, but unexposed, do not point out its function as polymerizing catalyst yet.
In described transition metal complex, preferred R 1To R 20In the optional C that replaces of at least one expression 1-10Alkyl, the optional C that replaces 6-20Aryl or the optional C that replaces 7-20Aralkyl.
Compound comprises following compounds shown in the concrete formula (I-1):
(1) dichloride 2-(cyclopentadienyl) benzyloxy root (benzyloxy) close titanium,
(2) dichloride 2-(2-methyl cyclopentadienyl) benzyloxy root close titanium,
(3) dichloride 2-(3-methyl cyclopentadienyl) benzyloxy root close titanium,
(4) dichloride 2-(2,3-dimethyl cyclopentadienyl) benzyloxy root close titanium,
(5) dichloride 2-(2,4-dimethyl cyclopentadienyl) benzyloxy root close titanium,
(6) dichloride 2-(2,3,4-trimethylammonium cyclopentadienyl) benzyloxy root close titanium,
(7) dichloride 2-(2,3,5-trimethylammonium cyclopentadienyl) benzyloxy root close titanium,
(8) dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl) benzyloxy root close titanium,
(9) dichloride 2-(2-dimethylaminomethyl cyclopentadienyl) benzyloxy root close titanium,
(10) dichloride 2-(3-dimethylaminomethyl cyclopentadienyl) benzyloxy root close titanium,
(11) dichloride 2-(indenes-1-yl) benzyloxy root close titanium,
(12) dichloride 2-(2-phenylindan-1-yl) benzyloxy root close titanium,
(13) dichloride 2-(fluorenes-9-yl) benzyloxy root close titanium,
(14) dichloride 2-(cyclopentadienyl)-1-naphthyl methoxy root (methyloxy) close titanium,
(15) dichloride 2-(2-methyl cyclopentadienyl)-1-naphthyl methoxy root close titanium,
(16) dichloride 2-(3-methyl cyclopentadienyl)-1-naphthyl methoxy root close titanium,
(17) dichloride 2-(2,3-dimethyl cyclopentadienyl)-1-naphthyl methoxy root close titanium,
(18) dichloride 2-(2,4-dimethyl cyclopentadienyl)-1-naphthyl methoxy root close titanium,
(19) dichloride 2-(2,3,4-trimethylammonium cyclopentadienyl)-1-naphthyl methoxy root close titanium,
(20) dichloride 2-(2,3,5-trimethylammonium cyclopentadienyl)-1-naphthyl methoxy root close titanium,
(21) dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-naphthyl methoxy root close titanium,
(22) dichloride 2-(2-dimethylaminomethyl cyclopentadienyl)-1-naphthyl methoxy root close titanium,
(23) dichloride 2-(3-dimethylaminomethyl cyclopentadienyl)-1-naphthyl methoxy root close titanium,
(24) dichloride 2-(indenes-1-yl)-1-naphthyl methoxy root close titanium,
(25) dichloride 2-(2-phenylindan-1-yl)-1-naphthyl methoxy root close titanium,
(26) dichloride 2-(fluorenes-9-yl)-1-naphthyl methoxy root close titanium,
(27) dichloride 1-[2-(cyclopentadienyl) phenyl] ethoxy root (ethyloxy) close titanium,
(28) dichloride 1-[2-(2-methyl cyclopentadienyl) phenyl] the ethoxy root close titanium,
(29) dichloride 1-[2-(3-methyl cyclopentadienyl) phenyl] the ethoxy root close titanium,
(30) dichloride 1-[2-(2,3-dimethyl cyclopentadienyl) phenyl] the ethoxy root close titanium,
(31) dichloride 1-[2-(2,4-dimethyl cyclopentadienyl) phenyl] the ethoxy root close titanium,
(32) dichloride 1-[2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl] the ethoxy root close titanium,
(33) dichloride 1-[2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl] the ethoxy root close titanium,
(34) dichloride 1-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl] the ethoxy root close titanium,
(35) dichloride 1-[2-(2-dimethylaminomethyl cyclopentadienyl) phenyl] the ethoxy root close titanium,
(36) dichloride 1-[2-(3-dimethylaminomethyl cyclopentadienyl) phenyl] the ethoxy root close titanium,
(37) dichloride 1-[2-(indenes-1-yl) phenyl] the ethoxy root close titanium,
(38) dichloride 1-[2-(2-phenylindan-1-yl) phenyl] the ethoxy root close titanium,
(39) dichloride 1-[2-(fluorenes-9-yl) phenyl] the ethoxy root close titanium,
(40) dichloride 1-[2-(cyclopentadienyl)-1-naphthyl] the ethoxy root close titanium,
(41) dichloride 1-[2-(2-methyl cyclopentadienyl)-1-naphthyl] the ethoxy root close titanium,
(42) dichloride 1-[2-(3-methyl cyclopentadienyl)-1-naphthyl] the ethoxy root close titanium,
(43) dichloride 1-[2-(2,3-dimethyl cyclopentadienyl)-1-naphthyl] the ethoxy root close titanium,
(44) dichloride 1-[2-(2,4-dimethyl cyclopentadienyl)-1-naphthyl] the ethoxy root close titanium,
(45) dichloride 1-[2-(2,3,4-trimethylammonium cyclopentadienyl)-1-naphthyl] the ethoxy root close titanium,
(46) dichloride 1-[2-(2,3,5-trimethylammonium cyclopentadienyl)-1-naphthyl] the ethoxy root close titanium,
(47) dichloride 1-[2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-naphthyl] the ethoxy root close titanium,
(48) dichloride 1-[2-(2-dimethylaminomethyl cyclopentadienyl)-1-naphthyl] the ethoxy root close titanium,
(49) dichloride 1-[2-(3-dimethylaminomethyl cyclopentadienyl)-1-naphthyl] the ethoxy root close titanium,
(50) dichloride 1-[2-(indenes-1-yl)-1-naphthyl] the ethoxy root close titanium,
(51) dichloride 1-[2-(2-phenylindan-1-yl)-1-naphthyl] the ethoxy root close titanium,
(52) dichloride 1-[2-(fluorenes-9-yl)-1-naphthyl] the ethoxy root close titanium,
(53) dichloride 1-[2-(cyclopentadienyl) phenyl]-1-methyl-ethoxy root close titanium,
(54) dichloride 1-[2-(2-methyl cyclopentadienyl) phenyl]-1-methyl-ethoxy root close titanium,
(55) dichloride 1-[2-(3-methyl cyclopentadienyl) phenyl]-1-methyl-ethoxy root close titanium,
(56) dichloride 1-[2-(2,3-dimethyl cyclopentadienyl) phenyl]-1-methyl-ethoxy root close titanium,
(57) dichloride 1-[2-(2,4-dimethyl cyclopentadienyl) phenyl]-1-methyl-ethoxy root close titanium,
(58) dichloride 1-[2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl]-1-methyl-ethoxy root close titanium,
(59) dichloride 1-[2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl]-1-methyl-ethoxy root close titanium,
(60) dichloride 1-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl]-1-methyl-ethoxy root close titanium,
(61) dichloride 1-[2-(2-dimethylaminomethyl cyclopentadienyl) phenyl]-1-methyl-ethoxy root close titanium,
(62) dichloride 1-[2-(3-dimethylaminomethyl cyclopentadienyl) phenyl]-1-methyl-ethoxy root close titanium,
(63) dichloride 1-[2-(indenes-1-yl) phenyl]-1-methyl-ethoxy root close titanium,
(64) dichloride 1-[2-(2-phenylindan-1-yl) phenyl]-1-methyl-ethoxy root close titanium,
(65) dichloride 1-[2-(fluorenes-9-yl) phenyl]-1-methyl-ethoxy root close titanium,
(66) dichloride 1-[2-(cyclopentadienyl)-1-naphthyl]-1-methyl-ethoxy root close titanium,
(67) dichloride 1-[2-(2-methyl cyclopentadienyl)-1-naphthyl]-1-methyl-ethoxy root close titanium,
(68) dichloride 1-[2-(3-methyl cyclopentadienyl)-1-naphthyl]-1-methyl-ethoxy root close titanium,
(69) dichloride 1-[2-(2,3-dimethyl cyclopentadienyl)-1-naphthyl]-1-methyl-ethoxy root close titanium,
(70) dichloride 1-[2-(2,4-dimethyl cyclopentadienyl)-1-naphthyl]-1-methyl-ethoxy root close titanium,
(71) dichloride 1-[2-(2,3,4-trimethylammonium cyclopentadienyl)-1-naphthyl]-1-methyl-ethoxy root close titanium,
(72) dichloride 1-[2-(2,3,5-trimethylammonium cyclopentadienyl)-1-naphthyl]-1-methyl-ethoxy root close titanium,
(73) dichloride 1-[2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-naphthyl]-1-methyl-ethoxy root close titanium,
(74) dichloride 1-[2-(2-dimethylaminomethyl cyclopentadienyl)-1-naphthyl]-1-methyl-ethoxy root close titanium,
(75) dichloride 1-[2-(3-dimethylaminomethyl cyclopentadienyl)-1-naphthyl]-1-methyl-ethoxy root close titanium,
(76) dichloride 1-[2-(indenes-1-yl)-1-naphthyl]-1-methyl-ethoxy root close titanium,
(77) dichloride 1-[2-(2-phenylindan-1-yl)-1-naphthyl]-1-methyl-ethoxy root close titanium,
(78) dichloride 1-[2-(fluorenes-9-yl)-1-naphthyl]-1-methyl-ethoxy root close titanium,
(79) dichloride [2-(cyclopentadienyl) the phenyl]-tertiary butyl-methoxy root close titanium,
(80) dichloride [2-(2-methyl cyclopentadienyl) the phenyl]-tertiary butyl-methoxy root close titanium,
(81) dichloride [2-(3-methyl cyclopentadienyl) the phenyl]-tertiary butyl-methoxy root close titanium,
(82) dichloride [2-(2,3-dimethyl cyclopentadienyl) the phenyl]-tertiary butyl-methoxy root close titanium,
(83) dichloride [2-(2,4-dimethyl cyclopentadienyl) the phenyl]-tertiary butyl-methoxy root close titanium,
(84) dichloride [2-(2,3,4-trimethylammonium cyclopentadienyl) the phenyl]-tertiary butyl-methoxy root close titanium,
(85) dichloride [2-(2,3,5-trimethylammonium cyclopentadienyl) the phenyl]-tertiary butyl-methoxy root close titanium,
(86) dichloride [2-(2,3,4,5-tetramethyl-ring pentadienyl) the phenyl]-tertiary butyl-methoxy root close titanium,
(87) dichloride [2-(2-dimethylaminomethyl cyclopentadienyl) the phenyl]-tertiary butyl-methoxyl group oxygenate titanium,
(88) dichloride [2-(3-dimethylaminomethyl cyclopentadienyl) the phenyl]-tertiary butyl-methoxy root close titanium,
(89) dichloride [2-(indenes-1-yl) the phenyl]-tertiary butyl-methoxy root close titanium,
(90) dichloride [2-(2-phenylindan-1-yl) the phenyl]-tertiary butyl-methoxy root close titanium,
(91) dichloride [2-(fluorenes-9-yl) the phenyl]-tertiary butyl-methoxy root close titanium,
(92) dichloride [2-(cyclopentadienyl)-1-the naphthyl]-tertiary butyl-methoxy root close titanium,
(93) dichloride [2-(2-methyl cyclopentadienyl)-1-the naphthyl]-tertiary butyl-methoxy root close titanium,
(94) dichloride [2-(3-methyl cyclopentadienyl)-1-the naphthyl]-tertiary butyl-methoxy root close titanium,
(95) dichloride [2-(2,3-dimethyl cyclopentadienyl)-1-the naphthyl]-tertiary butyl-methoxy root close titanium,
(96) dichloride [2-(2,4-dimethyl cyclopentadienyl)-1-the naphthyl]-tertiary butyl-methoxy root close titanium,
(97) dichloride [2-(2,3,4-trimethylammonium cyclopentadienyl)-1-the naphthyl]-tertiary butyl-methoxy root close titanium,
(98) dichloride [2-(2,3,5-trimethylammonium cyclopentadienyl)-1-the naphthyl]-tertiary butyl-methoxy root close titanium,
(99) dichloride [2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-the naphthyl]-tertiary butyl-methoxy root close titanium,
(100) dichloride [2-(2-dimethylaminomethyl cyclopentadienyl)-1-the naphthyl]-tertiary butyl-methoxy root close titanium,
(101) dichloride [2-(3-dimethylaminomethyl cyclopentadienyl)-1-the naphthyl]-tertiary butyl-methoxy root close titanium,
(102) dichloride [2-(indenes-1-yl)-1-the naphthyl]-tertiary butyl-methoxy root close titanium,
(103) dichloride [2-(2-phenylindan-1-yl)-1-the naphthyl]-tertiary butyl-methoxy root close titanium,
(104) dichloride [2-(fluorenes-9-yl)-1-the naphthyl]-tertiary butyl-methoxy root closes titanium
(105) dichloride [2-(cyclopentadienyl) phenyl] phenyl methoxy root close titanium,
(106) dichloride [2-(2-methyl cyclopentadienyl) phenyl] phenyl methoxy root close titanium,
(107) dichloride [2-(3-methyl cyclopentadienyl) phenyl] phenyl methoxy root close titanium,
(108) dichloride [2-(2,3-dimethyl cyclopentadienyl) phenyl] phenyl methoxy root close titanium,
(109) dichloride [2-(2,4-dimethyl cyclopentadienyl) phenyl] phenyl methoxy root close titanium,
(110) dichloride [2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl] phenyl methoxy root close titanium,
(111) dichloride [2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl] phenyl methoxy root close titanium,
(112) dichloride [2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl] phenyl methoxy root close titanium,
(113) dichloride [2-(2-dimethylaminomethyl cyclopentadienyl) phenyl] phenyl methoxy root close titanium,
(114) dichloride [2-(3-dimethylaminomethyl cyclopentadienyl) phenyl] phenyl methoxy root close titanium,
(115) dichloride [2-(indenes-1-yl) phenyl] phenyl methoxy root close titanium,
(116) dichloride [2-(2-phenylindan-1-yl) phenyl] phenyl methoxy root close titanium,
(117) dichloride [2-(fluorenes-9-yl) phenyl] phenyl methoxy root close titanium,
(118) dichloride [2-(cyclopentadienyl)-1-naphthyl] phenyl methoxy root close titanium,
(119) dichloride [2-(2-methyl cyclopentadienyl)-1-naphthyl] phenyl methoxy root close titanium,
(120) dichloride [2-(3-methyl cyclopentadienyl)-1-naphthyl] phenyl methoxy root close titanium,
(121) dichloride [2-(2,3-dimethyl cyclopentadienyl)-1-naphthyl] benzene oxygen root (phenyloxy) close titanium,
(122) dichloride [2-(2,4-dimethyl cyclopentadienyl)-1-naphthyl] phenyl methoxy root close titanium,
(123) dichloride [2-(2,3,4-trimethylammonium cyclopentadienyl)-1-naphthyl] phenyl methoxy root close titanium,
(124) dichloride [2-(2,3,5-trimethylammonium cyclopentadienyl)-1-naphthyl] phenyl methoxy root close titanium,
(125) dichloride [2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-naphthyl] phenyl methoxy root close titanium,
(126) dichloride [2-(2-dimethylaminomethyl cyclopentadienyl)-1-naphthyl] phenyl methoxy root close titanium,
(127) dichloride [2-(3-dimethylaminomethyl cyclopentadienyl)-1-naphthyl] phenyl methoxy root close titanium,
(128) dichloride [2-(indenes-1-yl)-1-naphthyl] phenyl methoxy root close titanium,
(129) dichloride [2-(2-phenylindan-1-yl)-1-naphthyl] phenyl methoxy root close titanium,
(130) dichloride [2-(fluorenes-9-yl)-1-naphthyl] phenyl methoxy root close titanium,
(131) dichloride [2-(cyclopentadienyl) phenyl] phenylbenzene methoxy root close titanium,
(132) dichloride [2-(2-methyl cyclopentadienyl) phenyl] phenylbenzene methoxy root close titanium,
(133) dichloride [2-(3-methyl cyclopentadienyl) phenyl] phenylbenzene methoxy root close titanium,
(134) dichloride [2-(2,3-dimethyl cyclopentadienyl) phenyl] phenylbenzene methoxy root close titanium,
(135) dichloride [2-(2,4-dimethyl cyclopentadienyl) phenyl] phenylbenzene methoxy root close titanium,
(136) dichloride [2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl] phenylbenzene methoxy root close titanium,
(137) dichloride [2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl] phenylbenzene methoxy root close titanium,
(138) dichloride [2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl] phenylbenzene methoxy root close titanium,
(139) dichloride [2-(2-dimethylaminomethyl cyclopentadienyl) phenyl] phenylbenzene methoxy base oxygenate titanium,
(140) dichloride [2-(3-dimethylaminomethyl cyclopentadienyl) phenyl] phenylbenzene methoxy root close titanium,
(141) dichloride [2-(indenes-1-yl) phenyl] phenylbenzene methoxy root close titanium,
(142) dichloride [2-(2-phenylindan-1-yl) phenyl] phenylbenzene methoxy root close titanium,
(143) dichloride [2-(fluorenes-9-yl) phenyl] phenylbenzene methoxy root close titanium,
(144) dichloride [2-(cyclopentadienyl)-1-naphthyl] phenylbenzene methoxy root close titanium,
(145) dichloride [2-(2-methyl cyclopentadienyl)-1-naphthyl] phenylbenzene methoxy root close titanium,
(146) dichloride [2-(3-methyl cyclopentadienyl)-1-naphthyl] phenylbenzene methoxy root close titanium,
(147) dichloride [2-(2,3-dimethyl cyclopentadienyl)-1-naphthyl] hexichol oxygen root close titanium,
(148) dichloride [2-(2,4-dimethyl cyclopentadienyl)-1-naphthyl] phenylbenzene methoxy root close titanium,
(149) dichloride [2-(2,3,4-trimethylammonium cyclopentadienyl)-1-naphthyl] phenylbenzene methoxy root close titanium,
(150) dichloride [2-(2,3,5-trimethylammonium cyclopentadienyl)-1-naphthyl] phenylbenzene methoxy root close titanium,
(151) dichloride [2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-naphthyl] phenylbenzene methoxy root close titanium,
(152) dichloride [2-(2-dimethylaminomethyl cyclopentadienyl)-1-naphthyl] phenylbenzene methoxy root close titanium,
(153) dichloride [2-(3-dimethylaminomethyl cyclopentadienyl)-1-naphthyl] phenylbenzene methoxy root close titanium,
(154) dichloride [2-(indenes-1-yl)-1-naphthyl] phenylbenzene methoxy root close titanium,
(155) dichloride [2-(2-phenylindan-1-yl)-1-naphthyl] phenylbenzene methoxy root close titanium,
(156) dichloride [2-(fluorenes-9-yl)-1-naphthyl] phenylbenzene methoxy root closes titanium etc.
Equally, also can exemplify out the compound that (2-cyclopentadienyl-1-naphthyl) in the above-claimed cpd changes (2-cyclopentadienyl-3-naphthyl) into, (indenes-1-yl) changes the compound of (indenes-2-yl) into, titanium changes the compound of zirconium or hafnium into, and perhaps dichloride changes the compound of dibrominated, two iodate, diformazan alcoholization, diisopropyl alcoholization, two butanolsization, two dimethylaminoization, two diethylinization, dimethyl or two trimethyl silyl methyl etc. into.
Exemplify below shown in the formula (I) in the transition metal complex-Y-is compound shown in the formula (I-2) of (b):
In the formula (I-2), A 1Be preferably nitrogen-atoms.
R 2, R 3, R 4And R 5Be preferably hydrogen atom or C respectively 1-5Alkyl.
The object lesson of transition metal complex comprises following compounds shown in the formula (I-2):
(1) methyl dichloride N-[(2-(cyclopentadienyl) phenyl)]-N-phenyl amine (amido) close titanium,
(2) methyl dichloride N-[(2-(2-methyl cyclopentadienyl) phenyl)]-the N-phenyl amine close titanium,
(3) methyl dichloride N-[(2-(3-methyl cyclopentadienyl) phenyl)]-the N-phenyl amine close titanium,
(4) methyl dichloride N-[(2-(2,3-dimethyl cyclopentadienyl) phenyl)]-the N-phenyl amine close titanium,
(5) methyl dichloride N-[(2-(2,4-dimethyl cyclopentadienyl) phenyl)]-the N-phenyl amine close titanium,
(6) methyl dichloride N-[(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl)]-the N-phenyl amine close titanium,
(7) methyl N-[(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl)]-the N-phenyl amine,
(8) methyl dichloride N-[(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl)]-the N-phenyl amine close titanium,
(9) methyl dichloride N-[(2-(2-dimethylaminomethyl cyclopentadienyl) phenyl)]-the N-phenyl amine close titanium,
(10) methyl dichloride N-[(2-(3-dimethylaminomethyl cyclopentadienyl) phenyl)]-the N-phenyl amine close titanium,
(11) methyl dichloride N-[(2-(indenes-1-yl) phenyl)]-the N-phenyl amine close titanium,
(12) methyl dichloride N-[(2-(2-methyl indenes-1-yl) phenyl)]-the N-phenyl amine close titanium,
(13) methyl dichloride N-[(2-(2-phenylindan-1-yl) phenyl)]-the N-phenyl amine close titanium,
(14) methyl dichloride N-[(2-(fluorenes-9-yl) phenyl)]-the N-phenyl amine close titanium,
(15) methyl dichloride N-[(2-(cyclopentadienyl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(16) methyl dichloride N-[(2-(2-methyl cyclopentadienyl) phenyl)]-N-(2,4, the 6-trimethylphenyl) close titanium,
(17) methyl dichloride N-[(2-(3-methyl cyclopentadienyl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(18) methyl dichloride N-[(2-(2,3-dimethyl cyclopentadienyl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(19) methyl dichloride N-[(2-(2,4-dimethyl cyclopentadienyl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(20) methyl dichloride N-[(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(21) methyl dichloride N-[(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(22) methyl dichloride N-[(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(23) methyl dichloride N-[(2-(2-dimethylaminomethyl cyclopentadienyl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(24) methyl dichloride N-[(2-(3-dimethylaminomethyl cyclopentadienyl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(25) methyl dichloride N-[(2-(indenes-1-yl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(26) methyl dichloride N-[(2-(2-methyl indenes-1-yl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(27) methyl dichloride N-[(2-(2-phenylindan-1-yl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(28) methyl dichloride N-[(2-(fluorenes-9-yl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(29) methyl dichloride N-[(2-(cyclopentadienyl) phenyl)]-the N-tert-butylamine close titanium,
(30) methyl dichloride N-[(2-(2-methyl cyclopentadienyl) phenyl)]-the N-tert-butylamine close titanium,
(31) methyl dichloride N-[(2-(3-methyl cyclopentadienyl) phenyl)]-the N-tert-butylamine close titanium,
(32) methyl dichloride N-[(2-(2,3-dimethyl cyclopentadienyl) phenyl)]-the N-tert-butylamine close titanium,
(33) methyl dichloride N-[(2-(2,4-dimethyl cyclopentadienyl) phenyl)]-the N-tert-butylamine close titanium,
(34) methyl dichloride N-[(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl)]-the N-tert-butylamine close titanium,
(35) methyl dichloride N-[(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl)]-the N-tert-butylamine close titanium,
(36) methyl dichloride N-[(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl)]-the N-tert-butylamine close titanium,
(37) methyl dichloride N-[(2-(2-dimethylaminomethyl cyclopentadienyl) phenyl)]-the N-tert-butylamine close titanium,
(38) methyl dichloride N-[(2-(3-dimethylaminomethyl cyclopentadienyl) phenyl)]-the N-tert-butylamine close titanium,
(39) methyl dichloride N-[(2-(indenes-1-yl) phenyl)]-the N-tert-butylamine close titanium,
(40) methyl dichloride N-[(2-(2-methyl indenes-1-yl) phenyl)]-the N-tert-butylamine close titanium,
(41) methyl dichloride N-[(2-(2-phenylindan-1-yl) phenyl)]-the N-tert-butylamine close titanium,
(42) methyl dichloride N-[(2-(fluorenes-9-yl) phenyl)]-the N-tert-butylamine close titanium,
(43) methyl dichloride N-[(2-(cyclopentadienyl) phenyl)]-the N-n-butylamine close titanium,
(44) methyl dichloride N-[(2-(2-methyl cyclopentadienyl) phenyl)]-the N-n-butylamine close titanium,
(45) methyl dichloride N-[(2-(3-methyl cyclopentadienyl) phenyl)]-the N-n-butylamine close titanium,
(46) methyl dichloride N-[(2-(2,3-dimethyl cyclopentadienyl) phenyl)]-the N-n-butylamine close titanium,
(47) methyl dichloride N-[(2-(2,4-dimethyl cyclopentadienyl) phenyl)]-the N-n-butylamine close titanium,
(48) methyl dichloride N-[(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl)]-the N-n-butylamine close titanium,
(49) methyl dichloride N-[(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl)]-the N-n-butylamine close titanium,
(50) methyl dichloride N-[(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl)]-the N-n-butylamine close titanium,
(51) methyl dichloride N-[(2-(2-dimethylaminomethyl cyclopentadienyl) phenyl)]-the N-n-butylamine close titanium,
(52) methyl dichloride N-[(2-(3-dimethylaminomethyl cyclopentadienyl) phenyl)]-the N-n-butylamine close titanium,
(53) methyl dichloride N-[(2-(indenes-1-yl) phenyl)]-the N-n-butylamine close titanium,
(54) methyl dichloride N-[(2-(2-methyl indenes-1-yl) phenyl)]-the N-n-butylamine close titanium,
(55) methyl dichloride N-[(2-(2-phenylindan-1-yl) phenyl)]-the N-n-butylamine close titanium,
(56) methyl dichloride N-[(2-(fluorenes-9-yl) phenyl)]-the N-n-butylamine close titanium,
(57) dichloride N-[1-(2-(cyclopentadienyl) phenyl) ethyl]-the N-phenyl amine close titanium,
(58) dichloride N-[1-(2-(2-methyl cyclopentadienyl) phenyl) ethyl]-the N-phenyl amine close titanium,
(59) dichloride N-[1-(2-(3-methyl cyclopentadienyl) phenyl) ethyl]-the N-phenyl amine close titanium,
(60) dichloride N-[1-(2-(2,3-dimethyl cyclopentadienyl) phenyl) ethyl]-the N-phenyl amine close titanium,
(61) dichloride N-[1-(2-(2,4-dimethyl cyclopentadienyl) phenyl) ethyl]-the N-phenyl amine close titanium,
(62) dichloride N-[1-(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl) ethyl]-the N-phenyl amine close titanium,
(63) dichloride N-[1-(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl) ethyl]-the N-phenyl amine close titanium,
(64) dichloride N-[1-(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl) ethyl]-the N-phenyl amine close titanium,
(65) dichloride N-[1-(2-(2-dimethylaminomethyl cyclopentadienyl) phenyl) ethyl]-the N-phenyl amine close titanium,
(66) dichloride N-[1-(2-(3-dimethylaminomethyl cyclopentadienyl) phenyl) ethyl]-the N-phenyl amine close titanium,
(67) dichloride N-[1-(2-(indenes-1-yl) phenyl) ethyl]-the N-phenyl amine close titanium,
(68) dichloride N-[1-(2-(2-methyl indenes-1-yl) phenyl) ethyl]-the N-phenyl amine close titanium,
(69) dichloride N-[1-(2-(2-phenylindan-1-yl) phenyl) ethyl]-the N-phenyl amine close titanium,
(70) dichloride N-[1-(2-(fluorenes-9-yl) phenyl) ethyl]-the N-phenyl amine close titanium,
(71) dichloride N-[1-(2-(cyclopentadienyl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(72) dichloride N-[1-(2-(2-methyl cyclopentadienyl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(73) dichloride N-[1-(2-(3-methyl cyclopentadienyl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(74) dichloride N-[1-(2-(2,3-dimethyl cyclopentadienyl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(75) dichloride N-[1-(2-(2,4-dimethyl cyclopentadienyl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(76) dichloride N-[1-(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(77) dichloride N-[1-(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(78) dichloride N-[1-(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(79) dichloride N-[1-(2-(2-dimethylaminomethyl cyclopentadienyl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(80) dichloride N-[1-(2-(3-dimethylaminomethyl cyclopentadienyl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(81) dichloride N-[1-(2-(indenes-1-yl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(82) dichloride N-[1-(2-(2-methyl indenes-1-yl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(83) dichloride N-[1-(2-(2-phenylindan-1-yl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(84) dichloride N-[1-(2-(fluorenes-9-yl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine closes titanium
(85) dichloride N-[1-(2-(cyclopentadienyl) phenyl) ethyl]-the N-tert-butylamine close titanium,
(86) dichloride N-[1-(2-(2-methyl cyclopentadienyl) phenyl) ethyl]-the N-tert-butylamine close titanium,
(87) dichloride N-[1-(2-(3-methyl cyclopentadienyl) phenyl) ethyl]-the N-tert-butylamine close titanium,
(88) dichloride N-[1-(2-(2,3-dimethyl cyclopentadienyl) phenyl) ethyl]-the N-tert-butylamine close titanium,
(89) dichloride N-[1-(2-(2,4-dimethyl cyclopentadienyl) phenyl) ethyl]-the N-tert-butylamine close titanium,
(90) dichloride N-[1-(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl) ethyl]-the N-tert-butylamine close titanium,
(91) dichloride N-[1-(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl) ethyl]-the N-tert-butylamine close titanium,
(92) dichloride N-[1-(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl) ethyl]-the N-tert-butylamine close titanium,
(93) dichloride N-[1-(2-(2-dimethylaminomethyl cyclopentadienyl) phenyl) ethyl]-the N-tert-butylamine close titanium,
(94) dichloride N-[1-(2-(3-dimethylaminomethyl cyclopentadienyl) phenyl) ethyl]-the N-tert-butylamine close titanium,
(95) dichloride N-[1-(2-(indenes-1-yl) phenyl) ethyl]-the N-tert-butylamine close titanium,
(96) dichloride N-[1-(2-(2-methyl indenes-1-yl) phenyl) ethyl]-the N-tert-butylamine close titanium,
(97) dichloride N-[1-(2-(2-phenylindan-1-yl) phenyl) ethyl]-the N-tert-butylamine close titanium,
(98) dichloride N-[1-(2-(fluorenes-9-yl) phenyl) ethyl]-the N-tert-butylamine close titanium,
(99) dichloride N-[1-(2-(cyclopentadienyl) phenyl) ethyl]-the N-n-butylamine close titanium,
(100) dichloride N-[1-(2-(2-methyl cyclopentadienyl) phenyl) ethyl]-the N-n-butylamine close titanium,
(101) dichloride N-[1-(2-(3-methyl cyclopentadienyl) phenyl) ethyl]-the N-n-butylamine close titanium,
(102) dichloride N-[1-(2-(2,3-dimethyl cyclopentadienyl) phenyl) ethyl]-the N-n-butylamine close titanium,
(103) dichloride N-[1-(2-(2,4-dimethyl cyclopentadienyl) phenyl) ethyl]-the N-n-butylamine close titanium,
(104) dichloride N-[1-(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl) ethyl]-the N-n-butylamine close titanium,
(105) dichloride N-[1-(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl) ethyl]-the N-n-butylamine close titanium,
(106) dichloride N-[1-(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl) ethyl]-the N-n-butylamine close titanium,
(107) dichloride N-[1-(2-(2-dimethylaminomethyl cyclopentadienyl) phenyl) ethyl]-the N-n-butylamine close titanium,
(108) dichloride N-[1-(2-(3-dimethylaminomethyl cyclopentadienyl) phenyl) ethyl]-the N-n-butylamine close titanium,
(109) dichloride N-[1-(2-(indenes-1-yl) phenyl) ethyl]-the N-n-butylamine close titanium,
(110) dichloride N-[1-(2-(2-methyl indenes-1-yl) phenyl) ethyl]-the N-n-butylamine close titanium,
(111) dichloride N-[1-(2-(2-phenylindan-1-yl) phenyl) ethyl]-the N-n-butylamine close titanium,
(112) dichloride N-[1-(2-(fluorenes-9-yl) phenyl) ethyl]-the N-n-butylamine close titanium,
(113) dichloride N-[1-(2-(cyclopentadienyl) phenyl)-1-methylethyl]-the N-phenyl amine close titanium,
(114) dichloride N-[1-(2-(2-methyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-phenyl amine close titanium,
(115) dichloride N-[1-(2-(3-methyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-phenyl amine close titanium,
(116) dichloride N-[1-(2-(2,3-dimethyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-phenyl amine close titanium,
(117) dichloride N-[1-(2-(2,4-dimethyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-phenyl amine close titanium,
(118) dichloride N-[1-(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl)-1-methylethyl]-the N-phenyl amine close titanium,
(119) dichloride N-[1-(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl)-1-methylethyl]-the N-phenyl amine close titanium,
(120) dichloride N-[1-(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl)-1-methylethyl]-the N-phenyl amine close titanium,
(121) dichloride N-[1-(2-(2-dimethylaminomethyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-phenyl amine close titanium,
(122) dichloride N-[1-(2-(3-dimethylaminomethyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-phenyl amine close titanium,
(123) dichloride N-[1-(2-(indenes-1-yl) phenyl)-1-methylethyl]-the N-phenyl amine close titanium,
(124) dichloride N-[1-(2-(2-methyl indenes-1-yl) phenyl)-1-methylethyl]-the N-phenyl amine close titanium,
(125) dichloride N-[1-(2-(2-phenylindan-1-yl) phenyl)-1-methylethyl]-the N-phenyl amine close titanium,
(126) dichloride N-[1-(2-(fluorenes-9-yl) phenyl)-1-methylethyl]-the N-phenyl amine close titanium,
(127) dichloride N-[1-(2-(cyclopentadienyl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(128) dichloride N-[1-(2-(2-methyl cyclopentadienyl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(129) dichloride N-[1-(2-(3-methyl cyclopentadienyl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(130) dichloride N-[1-(2-(2,3-dimethyl cyclopentadienyl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(131) dichloride N-[1-(2-(2,4-dimethyl cyclopentadienyl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(132) dichloride N-[1-(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(133) dichloride N-[1-(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(134) dichloride N-[1-(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(135) dichloride N-[1-(2-(2-dimethylaminomethyl cyclopentadienyl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(136) dichloride N-[1-(2-(3-dimethylaminomethyl cyclopentadienyl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(137) dichloride N-[1-(2-(indenes-1-yl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(138) dichloride N-[1-(2-(2-methyl indenes-1-yl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(139) dichloride N-[1-(2-(2-phenylindan-1-yl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(140) dichloride N-[1-(2-(fluorenes-9-yl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(141) dichloride N-[1-(2-(cyclopentadienyl) phenyl)-1-methylethyl]-the N-tert-butylamine close titanium,
(142) dichloride N-[1-(2-(2-methyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-tert-butylamine close titanium,
(143) dichloride N-[1-(2-(3-methyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-tert-butylamine close titanium,
(144) dichloride N-[1-(2-(2,3-dimethyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-tert-butylamine close titanium,
(145) dichloride N-[1-(2-(2,4-dimethyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-tert-butylamine close titanium,
(146) dichloride N-[1-(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl)-1-methylethyl]-the N-tert-butylamine close titanium,
(147) dichloride N-[1-(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl)-1-methylethyl]-the N-tert-butylamine close titanium,
(148) dichloride N-[1-(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl)-1-methylethyl]-the N-tert-butylamine close titanium,
(149) dichloride N-[1-(2-(2-dimethylaminomethyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-tert-butylamine close titanium,
(150) dichloride N-[1-(2-(3-dimethylaminomethyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-tert-butylamine close titanium,
(151) dichloride N-[1-(2-(indenes-1-yl) phenyl)-1-methylethyl]-the N-tert-butylamine close titanium,
(152) dichloride N-[1-(2-(2-methyl indenes-1-yl) phenyl)-1-methylethyl]-the N-tert-butylamine close titanium,
(153) dichloride N-[1-(2-(2-phenylindan-1-yl) phenyl)-1-methylethyl]-the N-tert-butylamine close titanium,
(154) dichloride N-[1-(2-(fluorenes-9-yl) phenyl)-1-methylethyl]-the N-tert-butylamine close titanium,
(155) dichloride N-[1-(2-(cyclopentadienyl) phenyl)-1-methylethyl]-the N-n-butylamine close titanium,
(156) dichloride N-[1-(2-(2-methyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-n-butylamine close titanium,
(157) dichloride N-[1-(2-(3-methyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-n-butylamine close titanium,
(158) dichloride N-[1-(2-(2,3-dimethyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-n-butylamine close titanium,
(159) dichloride N-[1-(2-(2,4-dimethyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-n-butylamine close titanium,
(160) dichloride N-[1-(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl)-1-methylethyl]-the N-n-butylamine close titanium,
(161) dichloride N-[1-(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl)-1-methylethyl]-the N-n-butylamine close titanium,
(162) dichloride N-[1-(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl)-1-methylethyl]-the N-n-butylamine close titanium,
(163) dichloride N-[1-(2-(2-dimethylaminomethyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-n-butylamine close titanium,
(164) dichloride N-[1-(2-(3-dimethylaminomethyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-n-butylamine close titanium,
(165) dichloride N-[1-(2-(indenes-1-yl) phenyl)-1-methylethyl]-the N-n-butylamine close titanium,
(166) dichloride N-[1-(2-(2-methyl indenes-1-yl) phenyl)-1-methylethyl]-the N-n-butylamine close titanium,
(167) dichloride N-[1-(2-(2-phenylindan-1-yl) phenyl)-1-methylethyl]-the N-n-butylamine close titanium,
(168) dichloride N-[1-(2-(fluorenes-9-yl) phenyl)-1-methylethyl]-the N-n-butylamine close titanium,
(169) methyl dichloride N-[(2-(cyclopentadienyl)-1-naphthyl)]-the N-phenyl amine close titanium,
(170) methyl dichloride N-[(2-(2-methyl cyclopentadienyl)-1-naphthyl)]-the N-phenyl amine close titanium,
(171) methyl dichloride N-[(2-(3-methyl cyclopentadienyl)-1-naphthyl)]-the N-phenyl amine close titanium,
(172) methyl dichloride N-[(2-(2,3-dimethyl cyclopentadienyl)-1-naphthyl)]-the N-phenyl amine close titanium,
(173) methyl dichloride N-[(2-(2,4-dimethyl cyclopentadienyl)-1-naphthyl)]-the N-phenyl amine close titanium,
(174) methyl dichloride N-[(2-(2,3,4-trimethylammonium cyclopentadienyl)-1-naphthyl)]-the N-phenyl amine close titanium,
(175) methyl dichloride N-[(2-(2,3,5-trimethylammonium cyclopentadienyl)-1-naphthyl)]-the N-phenyl amine close titanium,
(176) methyl dichloride N-[(2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-naphthyl)]-the N-phenyl amine close titanium,
(177) methyl dichloride N-[(2-(2-dimethylaminomethyl cyclopentadienyl)-1-naphthyl)]-the N-phenyl amine close titanium,
(178) methyl dichloride N-[(2-(3-dimethylaminomethyl cyclopentadienyl)-1-naphthyl)]-the N-phenyl amine close titanium,
(179) methyl dichloride N-[(2-(indenes-1-yl)-1-naphthyl)]-the N-phenyl amine close titanium,
(180) methyl dichloride N-[(2-(2-methyl indenes-1-yl)-1-naphthyl)]-the N-phenyl amine close titanium,
(181) methyl dichloride N-[(2-(2-phenylindan-1-yl)-1-naphthyl)]-the N-phenyl amine close titanium,
(182) methyl dichloride N-[(2-(fluorenes-9-yl)-1-naphthyl)]-the N-phenyl amine close titanium,
(183) methyl dichloride N-[(2-(cyclopentadienyl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(184) methyl dichloride N-[(2-(2-methyl cyclopentadienyl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(185) methyl dichloride N-[(2-(3-methyl cyclopentadienyl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(186) methyl dichloride N-[(2-(2,3-dimethyl cyclopentadienyl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(187) methyl dichloride N-[(2-(2,4-dimethyl cyclopentadienyl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(188) methyl dichloride N-[(2-(2,3,4-trimethylammonium cyclopentadienyl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(189) methyl dichloride N-[(2-(2,3,5-trimethylammonium cyclopentadienyl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(190) methyl dichloride N-[(2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(191) methyl dichloride N-[(2-(2-dimethylaminomethyl cyclopentadienyl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(192) methyl dichloride N-[(2-(3-dimethylaminomethyl cyclopentadienyl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(193) methyl dichloride N-[(2-(indenes-1-yl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(194) methyl dichloride N-[(2-(2-methyl indenes-1-yl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(195) methyl dichloride N-[(2-(2-phenylindan-1-yl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(196) methyl dichloride N-[(2-(fluorenes-9-yl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine close titanium,
(197) methyl dichloride N-[(2-(cyclopentadienyl)-1-naphthyl)]-the N-tert-butylamine close titanium,
(198) methyl dichloride N-[(2-(2-methyl cyclopentadienyl)-1-naphthyl)]-the N-tert-butylamine close titanium,
(199) methyl dichloride N-[(2-(3-methyl cyclopentadienyl)-1-naphthyl)]-the N-tert-butylamine close titanium,
(200) methyl dichloride N-[(2-(2,3-dimethyl cyclopentadienyl)-1-naphthyl)]-the N-tert-butylamine close titanium,
(201) methyl dichloride N-[(2-(2,4-dimethyl cyclopentadienyl)-1-naphthyl)]-the N-tert-butylamine close titanium,
(202) methyl dichloride N-[(2-(2,3,4-trimethylammonium cyclopentadienyl)-1-naphthyl)]-the N-tert-butylamine close titanium,
(203) methyl dichloride N-[(2-(2,3,5-trimethylammonium cyclopentadienyl)-1-naphthyl)]-the N-tert-butylamine close titanium,
(204) methyl dichloride N-[(2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-naphthyl)]-the N-tert-butylamine close titanium,
(205) methyl dichloride N-[(2-(2-dimethylaminomethyl cyclopentadienyl)-1-naphthyl)]-the N-tert-butylamine close titanium,
(206) methyl dichloride N-[(2-(3-dimethylaminomethyl cyclopentadienyl)-1-naphthyl)]-the N-tert-butylamine close titanium,
(207) methyl dichloride N-[(2-(indenes-1-yl)-1-naphthyl)]-the N-tert-butylamine close titanium,
(208) methyl dichloride N-[(2-(2-methyl indenes-1-yl)-1-naphthyl)]-the N-tert-butylamine close titanium,
(209) methyl dichloride N-[(2-(2-phenylindan-1-yl)-1-naphthyl)]-the N-tert-butylamine close titanium,
(210) methyl dichloride N-[(2-(fluorenes-9-yl)-1-naphthyl)]-the N-tert-butylamine close titanium,
(211) methyl dichloride N-[(2-(cyclopentadienyl)-1-naphthyl)]-the N-n-butylamine close titanium,
(212) methyl dichloride N-[(2-(2-methyl cyclopentadienyl)-1-naphthyl)]-the N-n-butylamine close titanium,
(213) methyl dichloride N-[(2-(3-methyl cyclopentadienyl)-1-naphthyl)]-the N-n-butylamine close titanium,
(214) methyl dichloride N-[(2-(2,3-dimethyl cyclopentadienyl)-1-naphthyl)]-the N-n-butylamine close titanium,
(215) methyl dichloride N-[(2-(2,4-dimethyl cyclopentadienyl)-1-naphthyl)]-the N-n-butylamine close titanium,
(216) methyl dichloride N-[(2-(2,3,4-trimethylammonium cyclopentadienyl)-1-naphthyl)]-the N-n-butylamine close titanium,
(217) methyl dichloride N-[(2-(2,3,5-trimethylammonium cyclopentadienyl)-1-naphthyl)]-the N-n-butylamine close titanium,
(218) methyl dichloride N-[(2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-naphthyl)]-the N-n-butylamine close titanium,
(219) methyl dichloride N-[(2-(2-dimethylaminomethyl cyclopentadienyl)-1-naphthyl)]-the N-n-butylamine close titanium,
(220) methyl dichloride N-[(2-(3-dimethylaminomethyl cyclopentadienyl)-1-naphthyl)]-the N-n-butylamine close titanium,
(221) methyl dichloride N-[(2-(indenes-1-yl)-1-naphthyl)]-the N-n-butylamine close titanium,
(222) methyl dichloride N-[(2-(2-methyl indenes-1-yl)-1-naphthyl)]-the N-n-butylamine close titanium,
(223) methyl dichloride N-[(2-(2-phenylindan-1-yl)-1-naphthyl)]-the N-n-butylamine close titanium,
(224) methyl dichloride N-[(2-(fluorenes-9-yl)-1-naphthyl)]-the N-n-butylamine closes titanium etc.
Equally, also can exemplify out the compound that (indenes-1-yl) in the above-claimed cpd changes (indenes-2-yl) into, titanium changes the compound of zirconium or hafnium into, and perhaps dichloride changes the compound of dibrominated, two iodate, diformazan alcoholization, diisopropyl alcoholization, two butanolsization, two dimethylaminoization, two diethylinization, dimethyl or two trimethyl silyl methyl etc. into.
The following describes shown in the formula (I) in the transition metal complex-Y-is the formula (I-3) of (d):
In formula (I-3), A 1And A 2All be preferably nitrogen-atoms.
The object lesson of transition metal complex comprises shown in the formula (I-3): transistion metal compound reacts resulting compound shown in the compound that exemplifies as hydrazone compound shown in the following formula (7) and the formula (III) by making.
The following describes shown in the formula (I) in the transition metal complex-Y-is the formula (I-4) of (c):
In formula (I-4), A is preferably nitrogen-atoms.
The object lesson of transition metal complex comprises following compounds shown in the formula (I-4):
(1) dichloride 2-(cyclopentadienyl)-α-tertiary butyl-benzimide (methanimido) close titanium,
(2) dichloride 2-(2-methyl cyclopentadienyl)-α-tertiary butyl-benzimide close titanium,
(3) dichloride 2-(3-methyl cyclopentadienyl)-α-tertiary butyl-benzimide close titanium,
(4) dichloride 2-(2,3-dimethyl cyclopentadienyl)-α-tertiary butyl-benzimide close titanium,
(5) dichloride 2-(2,4-dimethyl cyclopentadienyl)-α-tertiary butyl-benzimide close titanium,
(6) dichloride 2-(2,3,4-trimethylammonium cyclopentadienyl)-α-tertiary butyl-benzimide close titanium,
(7) dichloride 2-(2,3,5-trimethylammonium cyclopentadienyl)-α-tertiary butyl-benzimide close titanium,
(8) dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-benzimide close titanium,
(9) dichloride 2-(2-dimethylaminomethyl cyclopentadienyl)-α-tertiary butyl-benzimide close titanium,
(10) dichloride 2-(3-dimethylaminomethyl cyclopentadienyl)-α-tertiary butyl-benzimide close titanium,
(11) dichloride 2-(indenes-1-yl)-α-tertiary butyl-benzimide close titanium,
(12) dichloride 2-(2-methyl indenes-1-yl)-α-tertiary butyl-benzimide close titanium,
(13) dichloride 2-(2-phenylindan-1-yl)-α-tertiary butyl-benzimide close titanium,
(14) dichloride 2-(fluorenes-9-yl)-α-tertiary butyl-benzimide close titanium,
(15) dichloride 2-(cyclopentadienyl)-α-normal-butyl-benzimide close titanium,
(16) dichloride 2-(2-methyl cyclopentadienyl)-α-normal-butyl-benzimide close titanium,
(17) dichloride 2-(3-methyl cyclopentadienyl)-α-normal-butyl-benzimide close titanium,
(18) dichloride 2-(2,3-dimethyl cyclopentadienyl)-α-normal-butyl-benzimide close titanium,
(19) dichloride 2-(2,4-dimethyl cyclopentadienyl)-α-normal-butyl-benzimide close titanium,
(20) dichloride 2-(2,3,4-trimethylammonium cyclopentadienyl)-α-normal-butyl-benzimide close titanium,
(21) dichloride 2-(2,3,5-trimethylammonium cyclopentadienyl)-α-normal-butyl-benzimide close titanium,
(22) dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-normal-butyl-benzimide close titanium,
(23) dichloride 2-(2-dimethylaminomethyl cyclopentadienyl)-α-normal-butyl-benzimide close titanium,
(24) dichloride 2-(3-dimethylaminomethyl cyclopentadienyl)-α-normal-butyl-benzimide close titanium,
(25) dichloride 2-(indenes-1-yl)-α-normal-butyl-benzimide close titanium,
(26) dichloride 2-(2-methyl indenes-1-yl)-α-normal-butyl-benzimide close titanium,
(27) dichloride 2-(2-phenylindan-1-yl)-α-normal-butyl-benzimide close titanium,
(28) dichloride 2-(fluorenes-9-yl)-α-normal-butyl-benzimide close titanium,
(29) dichloride 2-(cyclopentadienyl)-α-phenyl-benzimide close titanium,
(30) dichloride 2-(2-methyl cyclopentadienyl)-α-phenyl-benzimide close titanium,
(31) dichloride 2-(3-methyl cyclopentadienyl)-α-phenyl-benzimide close titanium,
(32) dichloride 2-(2,3-dimethyl cyclopentadienyl)-α-phenyl-benzimide close titanium,
(33) dichloride 2-(2,4-dimethyl cyclopentadienyl)-α-phenyl-benzimide close titanium,
(34) dichloride 2-(2,3,4-trimethylammonium cyclopentadienyl)-α-phenyl-benzimide close titanium,
(35) dichloride 2-(2,3,5-trimethylammonium cyclopentadienyl)-α-phenyl-benzimide close titanium,
(36) dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-benzimide close titanium,
(37) dichloride 2-(2-dimethylaminomethyl cyclopentadienyl)-α-phenyl-benzimide close titanium,
(38) dichloride 2-(3-dimethylaminomethyl cyclopentadienyl)-α-phenyl-benzimide close titanium,
(39) dichloride 2-(indenes-1-yl)-α-phenyl-benzimide close titanium,
(40) dichloride 2-(2-methyl indenes-1-yl)-α-phenyl-benzimide close titanium,
(41) dichloride 2-(2-phenylindan-1-yl)-α-phenyl-benzimide close titanium,
(42) dichloride 2-(fluorenes-9-yl)-α-phenyl-benzimide close titanium,
(43) dichloride 2-(cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(44) dichloride 2-(2-methyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(45) dichloride 2-(3-methyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(46) dichloride 2-(2,3-dimethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(47) dichloride 2-(2,4-dimethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(48) dichloride 2-(2,3,4-trimethylammonium cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(49) dichloride 2-(2,3,5-trimethylammonium cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(50) dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(51) dichloride 2-(2-dimethylaminomethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(52) dichloride 2-(3-dimethylaminomethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(53) dichloride 2-(indenes-1-yl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(54) dichloride 2-(2-methyl indenes-1-yl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(55) dichloride 2-(2-phenylindan-1-yl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(56) dichloride 2-(fluorenes-9-yl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(57) dichloride 2-(cyclopentadienyl)-α-cyclohexyl-benzimide close titanium,
(58) dichloride 2-(2-methyl cyclopentadienyl)-α-cyclohexyl-benzimide close titanium,
(59) dichloride 2-(3-methyl cyclopentadienyl)-α-cyclohexyl-benzimide close titanium,
(60) dichloride 2-(2,3-dimethyl cyclopentadienyl)-α-cyclohexyl-benzimide close titanium,
(61) dichloride 2-(2,4-dimethyl cyclopentadienyl)-α-cyclohexyl-benzimide close titanium,
(62) dichloride 2-(2,3,4-trimethylammonium cyclopentadienyl)-α-cyclohexyl-benzimide close titanium,
(63) dichloride 2-(2,3,5-trimethylammonium cyclopentadienyl)-α-cyclohexyl-benzimide close titanium,
(64) dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-cyclohexyl-benzimide close titanium,
(65) dichloride 2-(2-dimethylaminomethyl cyclopentadienyl)-α-cyclohexyl-benzimide close titanium,
(66) dichloride 2-(3-dimethylaminomethyl cyclopentadienyl)-α-cyclohexyl-benzimide close titanium,
(67) dichloride 2-(indenes-1-yl)-α-cyclohexyl-benzimide close titanium,
(68) dichloride 2-(2-methyl indenes-1-yl)-α-cyclohexyl-benzimide close titanium,
(69) dichloride 2-(2-phenylindan-1-yl)-α-cyclohexyl-benzimide close titanium,
(70) dichloride 2-(fluorenes-9-yl)-α-cyclohexyl-benzimide close titanium,
(71) dichloride 2-(cyclopentadienyl)-α-tertiary butyl-1-naphthalene azomethine close titanium,
(72) dichloride 2-(2-methyl cyclopentadienyl)-α-tertiary butyl-1-naphthalene azomethine close titanium,
(73) dichloride 2-(3-methyl cyclopentadienyl)-α-tertiary butyl-1-naphthalene azomethine close titanium,
(74) dichloride 2-(2,3-dimethyl cyclopentadienyl)-α-tertiary butyl-1-naphthalene azomethine close titanium,
(75) dichloride 2-(2,4-dimethyl cyclopentadienyl)-α-tertiary butyl-1-naphthalene azomethine close titanium,
(76) dichloride 2-(2,3,4-trimethylammonium cyclopentadienyl)-α-tertiary butyl-1-naphthalene azomethine close titanium,
(77) dichloride 2-(2,3,5-trimethylammonium cyclopentadienyl)-α-tertiary butyl-1-naphthalene azomethine close titanium,
(78) dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-1-naphthalene azomethine close titanium,
(79) dichloride 2-(2-dimethylaminomethyl cyclopentadienyl)-α-tertiary butyl-1-naphthalene azomethine close titanium,
(80) dichloride 2-(3-dimethylaminomethyl cyclopentadienyl)-α-tertiary butyl-1-naphthalene azomethine close titanium,
(81) dichloride 2-(indenes-1-yl)-α-tertiary butyl-1-naphthalene azomethine close titanium,
(82) dichloride 2-(2-methyl indenes-1-yl)-α-tertiary butyl-1-naphthalene azomethine close titanium,
(83) dichloride 2-(2-phenylindan-1-yl)-α-tertiary butyl-1-naphthalene azomethine close titanium,
(84) dichloride 2-(fluorenes-9-yl)-α-tertiary butyl-1-naphthalene azomethine close titanium,
(85) dichloride 2-(cyclopentadienyl)-α-normal-butyl-1-naphthalene azomethine close titanium,
(86) dichloride 2-(2-methyl cyclopentadienyl)-α-normal-butyl-1-naphthalene azomethine close titanium,
(87) dichloride 2-(3-methyl cyclopentadienyl)-α-normal-butyl-1-naphthalene azomethine close titanium,
(88) dichloride 2-(2,3-dimethyl cyclopentadienyl)-α-normal-butyl-1-naphthalene azomethine close titanium,
(89) dichloride 2-(2,4-dimethyl cyclopentadienyl)-α-normal-butyl-1-naphthalene azomethine close titanium,
(90) dichloride 2-(2,3,4-trimethylammonium cyclopentadienyl)-α-normal-butyl-1-naphthalene azomethine close titanium,
(91) dichloride 2-(2,3,5-trimethylammonium cyclopentadienyl)-α-normal-butyl-1-naphthalene azomethine close titanium,
(92) dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-normal-butyl-1-naphthalene azomethine close titanium,
(93) dichloride 2-(2-dimethylaminomethyl cyclopentadienyl)-α-normal-butyl-1-naphthalene azomethine close titanium,
(94) dichloride 2-(3-dimethylaminomethyl cyclopentadienyl)-α-normal-butyl-1-naphthalene azomethine close titanium,
(95) dichloride 2-(indenes-1-yl)-α-normal-butyl-1-naphthalene azomethine close titanium,
(96) dichloride 2-(2-methyl indenes-1-yl)-α-normal-butyl-1-naphthalene azomethine close titanium,
(97) dichloride 2-(2-phenylindan-1-yl)-α-normal-butyl-1-naphthalene azomethine close titanium,
(98) dichloride 2-(fluorenes-9-yl)-α-normal-butyl-1-naphthalene azomethine close titanium,
(99) dichloride 2-(cyclopentadienyl)-4-benzopyrone-naphthalene azomethine close titanium,
(100) dichloride 2-(2-methyl cyclopentadienyl)-4-benzopyrone-naphthalene azomethine close titanium,
(101) dichloride 2-(3-methyl cyclopentadienyl)-4-benzopyrone-naphthalene azomethine close titanium,
(102) dichloride 2-(2,3-dimethyl cyclopentadienyl)-4-benzopyrone-naphthalene azomethine close titanium,
(103) dichloride 2-(2,4-dimethyl cyclopentadienyl)-4-benzopyrone-naphthalene azomethine close titanium,
(104) dichloride 2-(2,3,4-trimethylammonium cyclopentadienyl)-4-benzopyrone-naphthalene azomethine close titanium,
(105) dichloride 2-(2,3,5-trimethylammonium cyclopentadienyl)-4-benzopyrone-naphthalene azomethine close titanium,
(106) dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl)-4-benzopyrone-naphthalene azomethine close titanium,
(107) dichloride 2-(2-dimethylaminomethyl cyclopentadienyl)-4-benzopyrone-naphthalene azomethine close titanium,
(108) dichloride 2-(3-dimethylaminomethyl cyclopentadienyl)-4-benzopyrone-naphthalene azomethine close titanium,
(109) dichloride 2-(indenes-1-yl)-4-benzopyrone-naphthalene azomethine close titanium,
(110) dichloride 2-(2-methyl indenes-1-yl)-4-benzopyrone-naphthalene azomethine close titanium,
(111) dichloride 2-(2-phenylindan-1-yl)-4-benzopyrone-naphthalene azomethine close titanium,
(112) dichloride 2-(fluorenes-9-yl)-4-benzopyrone-naphthalene azomethine close titanium,
(113) dichloride 2-(cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine close titanium,
(114) dichloride 2-(2-methyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine close titanium,
(115) dichloride 2-(3-methyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine close titanium,
(116) dichloride 2-(2,3-dimethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine close titanium,
(117) dichloride 2-(2,4-dimethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine close titanium,
(118) dichloride 2-(2,3,4-trimethylammonium cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine close titanium,
(119) dichloride 2-(2,3,5-trimethylammonium cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine close titanium,
(120) dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine close titanium,
(121) dichloride 2-(2-dimethylaminomethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine close titanium,
(122) dichloride 2-(3-dimethylaminomethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine close titanium,
(123) dichloride 2-(indenes-1-yl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine close titanium,
(124) dichloride 2-(2-methyl indenes-1-yl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine close titanium,
(125) dichloride 2-(2-phenylindan-1-yl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine close titanium,
(126) dichloride 2-(fluorenes-9-yl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine close titanium,
(127) dichloride 2-(cyclopentadienyl)-α-cyclohexyl-1-naphthalene azomethine close titanium,
(128) dichloride 2-(2-methyl cyclopentadienyl)-α-cyclohexyl-1-naphthalene azomethine close titanium,
(129) dichloride 2-(3-methyl cyclopentadienyl)-α-cyclohexyl-1-naphthalene azomethine close titanium,
(130) dichloride 2-(2,3-dimethyl cyclopentadienyl)-α-cyclohexyl-1-naphthalene azomethine close titanium,
(131) dichloride 2-(2,4-dimethyl cyclopentadienyl)-α-cyclohexyl-1-naphthalene azomethine close titanium,
(132) dichloride 2-(2,3,4-trimethylammonium cyclopentadienyl)-α-cyclohexyl-1-naphthalene azomethine close titanium,
(133) dichloride 2-(2,3,5-trimethylammonium cyclopentadienyl)-α-cyclohexyl-1-naphthalene azomethine close titanium,
(134) dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-cyclohexyl-1-naphthalene azomethine close titanium,
(135) dichloride 2-(2-dimethylaminomethyl cyclopentadienyl)-α-cyclohexyl-1-naphthalene azomethine close titanium,
(136) dichloride 2-(3-dimethylaminomethyl cyclopentadienyl)-α-cyclohexyl-1-naphthalene azomethine close titanium,
(137) dichloride 2-(indenes-1-yl)-α-cyclohexyl-1-naphthalene azomethine close titanium,
(138) dichloride 2-(2-methyl indenes-1-yl)-α-cyclohexyl-1-naphthalene azomethine close titanium,
(139) dichloride 2-(2-phenylindan-1-yl)-α-cyclohexyl-1-naphthalene azomethine close titanium,
(140) dichloride 2-(fluorenes-9-yl)-α-cyclohexyl-1-naphthalene azomethine close titanium,
(141) dichloride 3-(cyclopentadienyl)-α-tertiary butyl-2-naphthalene azomethine close titanium,
(142) dichloride 3-(2-methyl cyclopentadienyl)-α-tertiary butyl-2-naphthalene azomethine close titanium,
(143) dichloride 3-(3-methyl cyclopentadienyl)-α-tertiary butyl-2-naphthalene azomethine close titanium,
(144) dichloride 3-(2,3-dimethyl cyclopentadienyl)-α-tertiary butyl-2-naphthalene azomethine close titanium,
(145) dichloride 3-(2,4-dimethyl cyclopentadienyl)-α-tertiary butyl-2-naphthalene azomethine close titanium,
(146) dichloride 3-(2,3,4-trimethylammonium cyclopentadienyl)-α-tertiary butyl-2-naphthalene azomethine close titanium,
(147) dichloride 3-(2,3,5-trimethylammonium cyclopentadienyl)-α-tertiary butyl-2-naphthalene azomethine close titanium,
(148) dichloride 3-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-2-naphthalene azomethine close titanium,
(149) dichloride 3-(2-dimethylaminomethyl cyclopentadienyl)-α-tertiary butyl-2-naphthalene azomethine close titanium,
(150) dichloride 3-(3-dimethylaminomethyl cyclopentadienyl)-α-tertiary butyl-2-naphthalene azomethine close titanium,
(151) dichloride 3-(indenes-1-yl)-α-tertiary butyl-2-naphthalene azomethine close titanium,
(152) dichloride 3-(2-methyl indenes-1-yl)-α-tertiary butyl-2-naphthalene azomethine close titanium,
(153) dichloride 3-(2-phenylindan-1-yl)-α-tertiary butyl-2-naphthalene azomethine close titanium,
(154) dichloride 3-(fluorenes-9-yl)-α-tertiary butyl-2-naphthalene azomethine close titanium,
(155) dichloride 3-(cyclopentadienyl)-α-normal-butyl-2-naphthalene azomethine close titanium,
(156) dichloride 3-(2-methyl cyclopentadienyl)-α-normal-butyl-2-naphthalene azomethine close titanium,
(157) dichloride 3-(3-methyl cyclopentadienyl)-α-normal-butyl-2-naphthalene azomethine close titanium,
(158) dichloride 3-(2,3-dimethyl cyclopentadienyl)-α-normal-butyl-2-naphthalene azomethine close titanium,
(159) dichloride 3-(2,4-dimethyl cyclopentadienyl)-α-normal-butyl-2-naphthalene azomethine close titanium,
(160) dichloride 3-(2,3,4-trimethylammonium cyclopentadienyl)-α-normal-butyl-2-naphthalene azomethine close titanium,
(161) dichloride 3-(2,3,5-trimethylammonium cyclopentadienyl)-α-normal-butyl-2-naphthalene azomethine close titanium,
(162) dichloride 3-(2,3,4,5-tetramethyl-ring pentadienyl)-α-normal-butyl-2-naphthalene azomethine close titanium,
(163) dichloride 3-(2-dimethylaminomethyl cyclopentadienyl)-α-normal-butyl-2-naphthalene azomethine close titanium,
(164) dichloride 3-(3-dimethylaminomethyl cyclopentadienyl)-α-normal-butyl-2-naphthalene azomethine close titanium,
(165) dichloride 3-(indenes-1-yl)-α-normal-butyl-2-naphthalene azomethine close titanium,
(166) dichloride 3-(2-methyl indenes-1-yl)-α-normal-butyl-2-naphthalene azomethine close titanium,
(167) dichloride 3-(2-phenylindan-1-yl)-α-normal-butyl-2-naphthalene azomethine close titanium,
(168) dichloride 3-(fluorenes-9-yl)-α-normal-butyl-2-naphthalene azomethine close titanium,
(169) dichloride 3-(cyclopentadienyl)-α-phenyl-2-naphthalene azomethine close titanium,
(170) dichloride 3-(2-methyl cyclopentadienyl)-α-phenyl-2-naphthalene azomethine close titanium,
(171) dichloride 3-(3-methyl cyclopentadienyl)-α-phenyl-2-naphthalene azomethine close titanium,
(172) dichloride 3-(2,3-dimethyl cyclopentadienyl)-α-phenyl-2-naphthalene azomethine close titanium,
(173) dichloride 3-(2,4-dimethyl cyclopentadienyl)-α-phenyl-2-naphthalene azomethine close titanium,
(174) dichloride 3-(2,3,4-trimethylammonium cyclopentadienyl)-α-phenyl-2-naphthalene azomethine close titanium,
(175) dichloride 3-(2,3,5-trimethylammonium cyclopentadienyl)-α-phenyl-2-naphthalene azomethine close titanium,
(176) dichloride 3-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-2-naphthalene azomethine close titanium,
(177) dichloride 3-(2-dimethylaminomethyl cyclopentadienyl)-α-phenyl-2-naphthalene azomethine close titanium,
(178) dichloride 3-(3-dimethylaminomethyl cyclopentadienyl)-α-phenyl-2-naphthalene azomethine close titanium,
(179) dichloride 3-(indenes-1-yl)-α-phenyl-2-naphthalene azomethine close titanium,
(180) dichloride 3-(2-methyl indenes-1-yl)-α-phenyl-2-naphthalene azomethine close titanium,
(181) dichloride 3-(2-phenylindan-1-yl)-α-phenyl-2-naphthalene azomethine close titanium,
(182) dichloride 3-(fluorenes-9-yl)-α-phenyl-2-naphthalene azomethine close titanium,
(183) dichloride 3-(cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine close titanium,
(184) dichloride 3-(2-methyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine close titanium,
(185) dichloride 3-(3-methyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine close titanium,
(186) dichloride 3-(2,3-dimethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine close titanium,
(187) dichloride 3-(2,4-dimethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine close titanium,
(188) dichloride 3-(2,3,4-trimethylammonium cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine close titanium,
(189) dichloride 3-(2,3,5-trimethylammonium cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine close titanium,
(190) dichloride 3-(2,3,4,5-tetramethyl-ring pentadienyl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine close titanium,
(191) dichloride 3-(2-dimethylaminomethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine close titanium,
(192) dichloride 3-(3-dimethylaminomethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine close titanium,
(193) dichloride 3-(indenes-1-yl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine close titanium,
(194) dichloride 3-(2-methyl indenes-1-yl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine close titanium,
(195) dichloride 3-(2-phenylindan-1-yl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine close titanium,
(196) dichloride 3-(fluorenes-9-yl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine close titanium,
(197) dichloride 3-(cyclopentadienyl)-α-cyclohexyl-2-naphthalene azomethine close titanium,
(198) dichloride 3-(2-methyl cyclopentadienyl)-α-cyclohexyl-2-naphthalene azomethine close titanium,
(199) dichloride 3-(3-methyl cyclopentadienyl)-α-cyclohexyl-2-naphthalene azomethine close titanium,
(200) dichloride 3-(2,3-dimethyl cyclopentadienyl)-α-cyclohexyl-2-naphthalene azomethine close titanium,
(201) dichloride 3-(2,4-dimethyl cyclopentadienyl)-α-cyclohexyl-2-naphthalene azomethine close titanium,
(202) dichloride 3-(2,3,4-trimethylammonium cyclopentadienyl)-α-cyclohexyl-2-naphthalene azomethine close titanium,
(203) dichloride 3-(2,3,5-trimethylammonium cyclopentadienyl)-α-cyclohexyl-2-naphthalene azomethine close titanium,
(204) dichloride 3-(2,3,4,5-tetramethyl-ring pentadienyl)-α-cyclohexyl-2-naphthalene azomethine close titanium,
(205) dichloride 3-(2-dimethylaminomethyl cyclopentadienyl)-α-cyclohexyl-2-naphthalene azomethine close titanium,
(206) dichloride 3-(3-dimethylaminomethyl cyclopentadienyl)-α-cyclohexyl-2-naphthalene azomethine close titanium,
(207) dichloride 3-(indenes-1-yl)-α-cyclohexyl-2-naphthalene azomethine close titanium,
(208) dichloride 3-(2-methyl indenes-1-yl)-α-cyclohexyl-2-naphthalene azomethine close titanium,
(209) dichloride 3-(2-phenylindan-1-yl)-α-cyclohexyl-2-naphthalene azomethine close titanium,
(210) dichloride 3-(fluorenes-9-yl)-α-cyclohexyl-2-naphthalene azomethine close titanium,
(211) dichloride 3-dimethylamino-6-(cyclopentadienyl)-α-tertiary butyl-benzimide close titanium,
(212) dichloride 3-dimethylamino-6-(2-methyl cyclopentadienyl)-α-tertiary butyl-benzimide close titanium,
(213) dichloride 3-dimethylamino-6-(3-methyl cyclopentadienyl)-α-tertiary butyl-benzimide close titanium,
(214) dichloride 3-dimethylamino-6-(2,3-dimethyl cyclopentadienyl)-α-tertiary butyl-benzimide close titanium,
(215) dichloride 3-dimethylamino-6-(2,4-dimethyl cyclopentadienyl)-α-tertiary butyl-benzimide close titanium,
(216) dichloride 3-dimethylamino-6-(2,3,4-trimethylammonium cyclopentadienyl)-α-tertiary butyl-benzimide close titanium,
(217) dichloride 3-dimethylamino-6-(2,3,5-trimethylammonium cyclopentadienyl)-α-tertiary butyl-benzimide close titanium,
(218) dichloride 3-dimethylamino-6-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-benzimide close titanium,
(219) dichloride 3-dimethylamino-6-(2-dimethylaminomethyl cyclopentadienyl)-α-tertiary butyl-benzimide close titanium,
(220) dichloride 3-dimethylamino-6-(3-dimethylaminomethyl cyclopentadienyl)-α-tertiary butyl-benzimide close titanium,
(221) dichloride 3-dimethylamino-6-(indenes-1-yl)-α-tertiary butyl-benzimide close titanium,
(222) dichloride 3-dimethylamino-6-(2-methyl indenes-1-yl)-α-tertiary butyl-benzimide close titanium,
(223) dichloride 3-dimethylamino-6-(2-phenylindan-1-yl)-α-tertiary butyl-benzimide close titanium,
(224) dichloride 3-dimethylamino-6-(fluorenes-9-yl)-α-tertiary butyl-benzimide close titanium,
(225) dichloride 3-dimethylamino-6-(cyclopentadienyl)-α-normal-butyl-benzimide close titanium,
(226) dichloride 3-dimethylamino-6-(2-methyl cyclopentadienyl)-α-normal-butyl-benzimide close titanium,
(227) dichloride 3-dimethylamino-6-(3-methyl cyclopentadienyl)-α-normal-butyl-benzimide close titanium,
(228) dichloride 3-dimethylamino-6-(2,3-dimethyl cyclopentadienyl)-α-normal-butyl-benzimide close titanium,
(229) dichloride 3-dimethylamino-6-(2,4-dimethyl cyclopentadienyl)-α-normal-butyl-benzimide close titanium,
(230) dichloride 3-dimethylamino-6-(2,3,4-trimethylammonium cyclopentadienyl)-α-normal-butyl-benzimide close titanium,
(231) dichloride 3-dimethylamino-6-(2,3,5-trimethylammonium cyclopentadienyl)-α-normal-butyl-benzimide close titanium,
(232) dichloride 3-dimethylamino-6-(2,3,4,5-tetramethyl-ring pentadienyl)-α-normal-butyl-benzimide close titanium,
(233) dichloride 3-dimethylamino-6-(2-dimethylaminomethyl cyclopentadienyl)-α-normal-butyl-benzimide close titanium,
(234) dichloride 3-dimethylamino-6-(3-dimethylaminomethyl cyclopentadienyl)-α-normal-butyl-benzimide close titanium,
(235) dichloride 3-dimethylamino-6-(indenes-1-yl)-α-normal-butyl-benzimide close titanium,
(236) dichloride 3-dimethylamino-6-(2-methyl indenes-1-yl)-α-normal-butyl-benzimide close titanium,
(237) dichloride 3-dimethylamino-6-(2-phenylindan-1-yl)-α-normal-butyl-benzimide close titanium,
(238) dichloride 3-dimethylamino-6-(fluorenes-9-yl)-α-normal-butyl-benzimide close titanium,
(239) dichloride 3-dimethylamino-6-(cyclopentadienyl)-α-phenyl-benzimide close titanium,
(240) dichloride 3-dimethylamino-6-(2-methyl cyclopentadienyl)-α-phenyl-benzimide close titanium,
(241) dichloride 3-dimethylamino-6-(3-methyl cyclopentadienyl)-α-phenyl-benzimide close titanium,
(242) dichloride 3-dimethylamino-6-(2,3-dimethyl cyclopentadienyl)-α-phenyl-benzimide close titanium,
(243) dichloride 3-dimethylamino-6-(2,4-dimethyl cyclopentadienyl)-α-phenyl-benzimide close titanium,
(244) dichloride 3-dimethylamino-6-(2,3,4-trimethylammonium cyclopentadienyl)-α-phenyl-benzimide close titanium,
(245) dichloride 3-dimethylamino-6-(2,3,5-trimethylammonium cyclopentadienyl)-α-phenyl-benzimide close titanium,
(246) dichloride 3-dimethylamino-6-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-benzimide close titanium,
(247) dichloride 3-dimethylamino-6-(2-dimethylaminomethyl cyclopentadienyl)-α-phenyl-benzimide close titanium,
(248) dichloride 3-dimethylamino-6-(3-dimethylaminomethyl cyclopentadienyl)-α-phenyl-benzimide close titanium,
(249) dichloride 3-dimethylamino-6-(indenes-1-yl)-α-phenyl-benzimide close titanium,
(250) dichloride 3-dimethylamino-6-(2-methyl indenes-1-yl)-α-phenyl-benzimide close titanium,
(251) dichloride 3-dimethylamino-6-(2-phenylindan-1-yl)-α-phenyl-benzimide close titanium,
(252) dichloride 3-dimethylamino-6-(fluorenes-9-yl)-α-phenyl-benzimide close titanium,
(253) dichloride 3-dimethylamino-6-(cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(254) dichloride 3-dimethylamino-6-(2-methyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(255) dichloride 3-dimethylamino-6-(3-methyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(256) dichloride 3-dimethylamino-6-(2,3-dimethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(257) dichloride 3-dimethylamino-6-(2,4-dimethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(258) dichloride 3-dimethylamino-6-(2,3,4-trimethylammonium cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(259) dichloride 3-dimethylamino-6-(2,3,5-trimethylammonium cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(260) dichloride 3-dimethylamino-6-(2,3,4,5-tetramethyl-ring pentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(261) dichloride 3-dimethylamino-6-(2-dimethylaminomethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(262) dichloride 3-dimethylamino-6-(3-dimethylaminomethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(263) dichloride 6-(indenes-1-yl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(264) dichloride 3-dimethylamino-6-(2-methyl indenes-1-yl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(265) dichloride 3-dimethylamino-6-(2-phenylindan-1-yl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(266) dichloride 3-dimethylamino-6-(fluorenes-9-yl)-α-(2,3, the 4-trimethylphenyl)-benzimide close titanium,
(267) dichloride 3-dimethylamino-6-(cyclopentadienyl)-α-cyclohexyl-benzimide close titanium,
(268) dichloride 3-dimethylamino-6-(2-methyl cyclopentadienyl)-α-cyclohexyl-benzimide close titanium,
(269) dichloride 3-dimethylamino-6-(3-methyl cyclopentadienyl)-α-cyclohexyl-benzimide close titanium,
(270) dichloride 3-dimethylamino-6-(2,3-dimethyl cyclopentadienyl)-α-cyclohexyl-benzimide close titanium,
(271) dichloride 3-dimethylamino-6-(2,4-dimethyl cyclopentadienyl)-α-cyclohexyl-benzimide close titanium,
(272) dichloride 3-dimethylamino-6-(2,3,4-trimethylammonium cyclopentadienyl)-α-cyclohexyl-benzimide close titanium,
(273) dichloride 3-dimethylamino-6-(2,3,5-trimethylammonium cyclopentadienyl)-α-cyclohexyl-benzimide close titanium,
(274) dichloride 3-dimethylamino-6-(2,3,4,5-tetramethyl-ring pentadienyl)-α-cyclohexyl-benzimide close titanium,
(275) dichloride 3-dimethylamino-6-(2-dimethylaminomethyl cyclopentadienyl)-α-cyclohexyl-benzimide close titanium,
(276) dichloride 3-dimethylamino-6-(3-dimethylaminomethyl cyclopentadienyl)-α-cyclohexyl-benzimide close titanium,
(277) dichloride 3-dimethylamino-6-(indenes-1-yl)-α-cyclohexyl-benzimide close titanium,
(278) dichloride 3-dimethylamino-6-(2-methyl indenes-1-yl)-α-cyclohexyl-benzimide close titanium,
(279) dichloride 3-dimethylamino-6-(2-phenylindan-1-yl)-α-cyclohexyl-benzimide close titanium,
(280) dichloride 3-dimethylamino-6-(fluorenes-9-yl)-α-cyclohexyl-benzimide closes titanium etc.
Equally, also can exemplify out the compound that (2-cyclopentadienyl-1-naphthyl) in the above-claimed cpd changes (2-cyclopentadienyl-3-naphthyl) into, (indenes-1-yl) changes the compound of (indenes-2-yl) into, titanium changes the compound of zirconium or hafnium into, and perhaps dichloride changes the compound of dibrominated, two iodate, diformazan alcoholization, diisopropyl alcoholization, two butanolsization, two dimethylaminoization, two diethylinization, dimethyl or two trimethyl silyl methyl etc. into.
Usually transition metal complex of the present invention (I) is used as polymerizing catalyst with being selected from the compound of above-mentioned A1 to A3.
Below A1 is described to A3.
Formula E1 aAl (Z) (3-a)Shown in the object lesson of organo-aluminium compound (A1) comprise for example trialkylaluminiums such as trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three hexyl aluminium; Chlorination aluminum dialkyls such as chlorodimethylalumiu, diethylaluminum chloride, chlorination dipropyl aluminium, di-isobutyl aluminum chloride, chlorination dihexyl aluminium; Dichloride aluminum alkylss such as methylaluminium dichloride, ethylaluminium dichloride, dichloride propyl group aluminium, aluminium isobutyl dichloride, dichloride hexyl aluminium; With hydrogenation aluminum dialkyls such as hydrogenation dimethyl aluminium, diethyl aluminium hydride, hydrogenation dipropyl aluminium, diisobutylaluminium hydride, hydrogenation dihexyl aluminium etc.Preferred trialkylaluminium, more preferably triethyl aluminum and triisobutyl aluminium.
Has formula { Al (E2)-O-} bShown in structure ring-type aikyiaiurnirsoxan beta (A2) and have formula E3{-Al (E3)-O-} cAl (E3) 2Shown in the line style aikyiaiurnirsoxan beta (A3) of structure the object lesson of E2 and E3 comprise alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, n-pentyl, neo-pentyl (preferred C1-C5 alkyl).B is not less than 2 integer, and c is not less than 1 integer.Preferred E2 and E3 are respectively methyl or isobutyl-, and b is 2-40, and c is 1-40.
Above-mentioned aikyiaiurnirsoxan beta can be passed through prepared in various methods, and these preparation methods are not particularly limited, and also can prepare by currently known methods.For example, trialkylaluminium (as trimethyl aluminium etc.) is dissolved in the suitable organic solvent (as benzene, aliphatic hydrocrbon etc.), this solution is contacted with water prepare aikyiaiurnirsoxan beta.Can also exemplify and make trialkylaluminium (as trimethyl aluminium etc.) contact the method for preparing aikyiaiurnirsoxan beta a kind of comprising with the metal-salt that contains crystal water (as copper sulfate hydrate etc.).
Particularly, can exemplified by methyl aikyiaiurnirsoxan beta (MAO) etc.Can exemplify the MMAO (methylaluminoxane of modification) that the methylaluminoxane modification is obtained by adding triisobutyl aluminium in addition.Amount in order to the triisobutyl aluminium that obtains MMAO can be the significant quantity that changes methylaluminoxane, and there is no particular limitation as to it.Perhaps, being used for aikyiaiurnirsoxan beta of the present invention also can be commerical prod.
Transition metal complex of the present invention be selected from A1 and can combine with compound (B) again to the combination of the compound of A3 and be used as polymerizing catalyst.
Used to the present invention below compound (B1), (B2) and (B3) describe.
At formula BQ 1Q 2Q 3Shown in the boron compound (B1), B is the boron atom of three valence states, Q 1To Q 3Can be identical or different, be respectively halogen atom, contain 1-20 carbon atom alkyl, contain 1-20 carbon atom the halo alkyl, contain 1-20 carbon atom substituted silyl, contain the alkoxyl group of 1-20 carbon atom or contain the disubstituted amido of 2-20 carbon atom.Particularly, Q 1To Q 3Comprise and R 1To R 9Described in identical substituting group.Preferred Q 1To Q 3Be respectively halogen atom, contain the alkyl of 1-20 carbon atom or contain the halo alkyl of 1-20 carbon atom.
(B1) object lesson comprises three (pentafluorophenyl group) borine, three (2,3,5,6-tetrafluoro phenyl) borine, three (2,3,4,5-tetrafluoro phenyl) borine, three (3,4, the 5-trifluorophenyl) borine, three (2,3,4-trifluorophenyl) borine, two (pentafluorophenyl group) borines of phenyl etc., more preferably three (pentafluorophenyl group) borine.
At formula Z +(BQ 1Q 2Q 3Q 4) -Shown in the boron compound (B2), Z +Be inorganic or organic cation, B is the boron atom of three valence states, Q 1To Q 4Have and Q described in above-mentioned (B1) 1To Q 3Identical connotation.
For formula Z +(BQ 1Q 2Q 3Q 4) -Shown in the object lesson of compound, as the Z of inorganic cation +Comprise ferrocene (ferrocenium) positively charged ion, the ferrocene cation of alkyl replacement, silver-colored positively charged ion etc., comprise trityl group positively charged ion etc. as organic cations Z+.As (BQ 1Q 2Q 3Q 4) -, its example has four (pentafluorophenyl group) borate, four (2,3,5,6-tetrafluoro phenyl) borate, four (2,3,4,5-tetrafluoro phenyl) borate, four (3,4, the 5-trifluorophenyl) borate, four (2,2, the 4-trifluorophenyl) borate, two (pentafluorophenyl group) borate, four (3, the 5-bis trifluoromethyl phenyl) borates of phenyl etc.
Z +(BQ 1Q 2Q 3Q 4) -The bonded object lesson comprise four (pentafluorophenyl group) boric acid ferrocene, four (pentafluorophenyl group) boric acid 1,1 '-dimethyl ferrocene, four (pentafluorophenyl group) boric acid silver, four (pentafluorophenyl group) boric acid trityl ester, four (3, the 5-bis trifluoromethyl phenyl) boric acid trityl ester etc., more preferably four (pentafluorophenyl group) boric acid trityl ester.
In addition, at formula (L-H) +(BQ 1Q 2Q 3Q 4) -Shown in the boron compound, L is a neutral Lewis base, (L-H) +Be Bronsted acid, B is the boron atom of three valence states, Q 1To Q 4Have and Q described in above-mentioned (B1) 1To Q 3Identical connotation.
For formula (L-H) +(BQ 1Q 2Q 3Q 4) -Shown in the object lesson of compound, Bronsted acid (L-H) +Comprise ammonium, N that trialkyl replaces, N-dialkyl group puratized agricultural spray (anilinium), dialkyl ammonium, three fragrant basic Phosphonium etc., (BQ 1Q 2Q 3Q 4) -Comprise above-mentioned example.
(L-H) +(BQ 1Q 2Q 3Q 4) -The bonded object lesson comprise four (pentafluorophenyl group) boric acid triethyl ammonium, four (pentafluorophenyl group) boric acid tripropyl ammonium, four (pentafluorophenyl group) boric acid, three normal-butyl ammoniums, four (3, the 5-bis trifluoromethyl phenyl) boric acid three normal-butyl ammoniums, four (pentafluorophenyl group) boric acid N, N-dimethyl puratized agricultural spray, four (pentafluorophenyl group) boric acid N, N-diethyl puratized agricultural spray, four (pentafluorophenyl group) boric acid N, N-2,4,6-pentamethyl-puratized agricultural spray, four (3, the 5-bis trifluoromethyl phenyl) boric acid N, N-dimethyl puratized agricultural spray, four (pentafluorophenyl group) boric acid di-isopropyl ammonium, four (pentafluorophenyl group) boric acid dicyclohexyl ammonium, four (pentafluorophenyl group) boric acid triphenyl phosphonium, four (pentafluorophenyl group) boric acid, three (aminomethyl phenyl) Phosphonium, four (pentafluorophenyl group) boric acid, three (3,5-dimethylphenyl) Phosphonium etc., four (pentafluorophenyl group) boric acid, three normal-butyl ammoniums most preferably, four (pentafluorophenyl group) boric acid N, N-dimethyl puratized agricultural spray etc.
Except transition metal complex shown in the formula (I) and compound (A) or its combination, compound (B) also can carry out polyreaction as catalyst component.Can these catalyst components be joined in the polyreaction with any order.Perhaps, can make also that optional catalyst component contacts with each other earlier from aforesaid combination, then thus obtained reaction product is used for polyreaction.
For the consumption of each catalyst component, the mol ratio of compound (A)/transition metal complex is preferably 0.1-10, and 000,5-2000 more preferably; The mol ratio of compound (B)/transition metal complex is preferably 0.01-100, more preferably 0.5-10.If each catalyst component uses with solution state, then the concentration of transition metal complex is preferably 0.0001-5mmol/L shown in the formula (I), more preferably 0.001-1mmol/L; The concentration of compound (A) is preferably 0.01-500mmol/L, more preferably 0.1-100mmol/L (converting the Al atom to); The concentration of compound (B) is preferably 0.0001-5mmol/L, more preferably 0.001-1mmol/L.
In the present invention, as the alkene that is used for the polymeric monomer, can uses containing 2-20 carbon atom, diolefine etc., also can use two or more monomers simultaneously.Exemplify such monomer below, but the present invention is not limited in these compounds.The object lesson of alkene comprises ethene, propylene, butene-1, amylene-1, hexene-1, heptene-1, octene-1, nonylene-1, decylene-1,5-methyl-2-amylene-1, vinyl cyclohexene etc.Diolefin compound comprises the conjugated diolefine and the non-conjugated diene of hydrocarbon compound.The object lesson of such non-conjugated diene compound comprises 1, the 5-hexadiene, 1, the 4-hexadiene, 1, the 4-pentadiene, 1, the 7-octadiene, 1, the 8-nonadiene, 1, the 9-decadiene, the 4-methyl isophthalic acid, the 4-hexadiene, the 5-methyl isophthalic acid, the 4-hexadiene, the 7-methyl isophthalic acid, the 6-octadiene, 5-ethylidene-2-norbornene, Dicyclopentadiene (DCPD), 5-vinyl-2-norbornylene, 5-methyl-2-norbornylene, norbornadiene, 5-methylene-2-norbornene, 1, the 5-cyclooctadiene, 5, the interior methylene radical hexahydro-naphthalene of 8-etc., the object lesson of conjugated diene compound has 1,3-butadiene, isoprene, 1, the 3-hexadiene, 1, the 3-octadiene, 1, the 3-cyclooctadiene, 1 etc.
The monomeric object lesson that constitutes multipolymer includes but not limited to the combination of ethene and propylene, ethene and butene-1, ethene and hexene-1, propylene and butene-1 and above-mentioned any combination and 5-ethylidene-2-norbornene.
In the present invention, also can be with aromatic vinyl compound as monomer.The object lesson of aromatic vinyl compound comprises vinylbenzene, o-methyl styrene, a vinyl toluene, p-methylstyrene, neighbour, right-dimethyl styrene, adjacent ethyl styrene, an ethyl styrene, to ethyl styrene, chloro styrene, to chloro-styrene, alpha-methyl styrene, Vinylstyrene etc.
Polymerization process is not particularly limited, can be solvent polymerization or the slurry polymerization of for example making solvent with halohydrocarbon such as aromatic hydrocarbons such as aliphatic hydrocrbons such as butane, pentane, hexane, heptane or octane, benzene or toluene or methylene dichloride, or the vapour phase polymerization of in gaseous monomer, carrying out, they can be successive polymerizations, also can be batchwise polymerizations.
Polymerization temperature is usually in-50 ℃ to 200 ℃ scopes, specifically preferably in-20 ℃ to 100 ℃ scopes.Polymerization pressure is preferably normal pressure to 60kg/cm 2G (6MPa).Usually suitably determine polymerization cycle according to the kind and the reaction unit of subject polymer, can be in 1 minute to 20 hours scope.In the present invention, can in polyreaction, add chain transfer agents such as hydrogen, to regulate the molecular weight of multipolymer.
Below cyclopentadiene part shown in the formula (II) is described.
As compound shown in the formula (II), can exemplify out the compound of following formula (5), (6) and (7) expression.
Below substituted cyclopentadiene compound shown in the formula (5) is described:
Figure G2006100046087D00571
R wherein 1To R 9And R 20Has connotation same as described above; Condition is R to occur 2And R 3
Perhaps R 4And R 5Interconnect the situation that forms fluorenes ring or indenyl rings with the cyclopentadiene ring.
Tetrahedron Letters, 39 (1998), 1-(2 '-methyl 3 '-indenyl)-2-naphthalene methyl alcohol and 1-(3 '-indenyl)-2-naphthalene methyl alcohol is disclosed among the 6537-6576, but for containing the polymerizing catalyst of these compounds as part, both not open without any prompting yet.In addition, Bull.Chem.Soc.Jpn., 55,3267-3272 (1982) discloses 9-(2-hydroxymethyl-1-naphthyl) fluorenes, 9-[2-(Alpha-hydroxy benzyl)-1-naphthyl] fluorenes and 9-[2-(Alpha-hydroxy ethyl)-1-naphthyl] fluorenes, Bull.Chem.Soc.Jpn., 62,621-623 (1989) discloses 9-[2-(1-hydroxyl-2-trimethyl silyl ethyl)-1-naphthyl] fluorenes.But these documents all do not have open or suggestion contains the polymerizing catalyst of these compounds as part.
Compound shown in the formula (5) can be by making formula (1) carbonyl compound and nucleophilic reagent react and prepare.
The nucleophilic reagent that is used for this class reaction comprises for example hydride and carbanion compound (R 20Li or R 20MgX or metal hydride).Such nucleophilic reagent comprises sodium hydride, lithium aluminum hydride, methylmagnesium-bromide, ethyl-magnesium-bromide, phenyl-magnesium-bromide, bromination normal-butyl magnesium, bromination tertiary butyl magnesium, lithium methide, phenyl lithium, tert-butyl lithium etc.Equally, can also exemplify the compound that magnesium bromide in the above-claimed cpd changes magnesium chloride or magnesium iodide into.
Reaction is implemented in described reaction usually in inert solvent.Such solvent comprises for example aprotic solvent: as aromatic solvents such as benzene and toluene; Aliphatic hydrocarbon solvent such as hexane, heptane; Ether, tetrahydrofuran (THF), 1, ether solvents such as 4-diox; Amide solvent such as hexamethylphosphoramide, dimethyl formamide; Acetonitrile, propionitrile, acetone, diethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone isopolarity solvent; Halogenated solvents such as methylene dichloride, ethylene dichloride, chlorobenzene, dichlorobenzene.Can use the mixture of a kind of solvent or two or more solvents.The consumption of solvent is generally 1-200 times of carbonyl compound weight shown in the formula (1), and preferred 3-50 doubly.
Temperature of reaction is generally-100 ℃ of boiling points to solvent, is preferably-80 ℃ to 120 ℃.
After the reaction, if desired, can in the gained reaction mixture, add entry.Then this mixture separation is become organic layer and water layer, to obtain target compound solution as organic layer.When because in described reaction, use with the solvent of water compatible or use a small amount of solvent and when making organic layer and water layer not easily separated, can after in reaction mixture, adding water-insoluble organic solvents such as toluene, ethyl acetate or chlorobenzene, separate.Cyclopentadiene shown in the formula (5) can be purified by for example following operation: wash the solution of this compound with water, dry described solution, distilling off solvent is also further purified through methods such as recrystallization, distillation, column chromatography processing then.
The object lesson of compound comprises following compounds shown in the formula that obtains thus (5):
(1) 2-(cyclopentadienyl) phenylcarbinol,
(2) 2-(2-methyl cyclopentadienyl) phenylcarbinol,
(3) 2-(3-methyl cyclopentadienyl) phenylcarbinol,
(4) 2-(2,3-dimethyl cyclopentadienyl) phenylcarbinol,
(5) 2-(2,4-dimethyl cyclopentadienyl) phenylcarbinol,
(6) 2-(2,3,4-trimethylammonium cyclopentadienyl) phenylcarbinol,
(7) 2-(2,3,5-trimethylammonium cyclopentadienyl) phenylcarbinol,
(8) 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenylcarbinol,
(9) 2-(2-dimethylaminomethyl cyclopentadienyl) phenylcarbinol,
(10) 2-(3-dimethylaminomethyl cyclopentadienyl) phenylcarbinol,
(11) 2-(cyclopentadienyl)-1-naphthalene methyl alcohol,
(12) 2-(2-methyl cyclopentadienyl)-1-naphthalene methyl alcohol,
(13) 2-(3-methyl cyclopentadienyl)-1-naphthalene methyl alcohol,
(14) 2-(2,3-dimethyl cyclopentadienyl)-1-naphthalene methyl alcohol,
(15) 2-(2,4-dimethyl cyclopentadienyl)-1-naphthalene methyl alcohol,
(16) 2-(2,3,4-trimethylammonium cyclopentadienyl)-1-naphthalene methyl alcohol,
(17) 2-(2,3,5-trimethylammonium cyclopentadienyl)-1-naphthalene methyl alcohol,
(18) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-naphthalene methyl alcohol,
(19) 2-(2-dimethylaminomethyl cyclopentadienyl)-1-naphthalene methyl alcohol,
(20) 2-(3-dimethylaminomethyl cyclopentadienyl)-1-naphthalene methyl alcohol,
(21) 2-(fluorenes-9-yl)-1-naphthalene methyl alcohol,
(22) 1-[2-(cyclopentadienyl) phenyl] ethanol,
(23) 1-[2-(2-methyl cyclopentadienyl) phenyl] ethanol,
(24) 1-[2-(3-methyl cyclopentadienyl) phenyl] ethanol,
(25) 1-[2-(2,3-dimethyl cyclopentadienyl) phenyl] ethanol,
(26) 1-[2-(2,4-dimethyl cyclopentadienyl) phenyl] ethanol,
(27) 1-[2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl] ethanol,
(28) 1-[2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl] ethanol,
(29) 1-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl] ethanol,
(30) 1-[2-(2-dimethylaminomethyl cyclopentadienyl) phenyl] ethanol,
(31) 1-[2-(3-dimethylaminomethyl cyclopentadienyl) phenyl] ethanol,
(32) 1-[2-(cyclopentadienyl)-1-naphthyl] ethanol,
(33) 1-[2-(2-methyl cyclopentadienyl)-1-naphthyl] ethanol,
(34) 1-[2-(3-methyl cyclopentadienyl)-1-naphthyl] ethanol,
(35) 1-[2-(2,3-dimethyl cyclopentadienyl)-1-naphthyl] ethanol,
(36) 1-[2-(2,4-dimethyl cyclopentadienyl)-1-naphthyl] ethanol,
(37) 1-[2-(2,3,4-trimethylammonium cyclopentadienyl)-1-naphthyl] ethanol,
(38) 1-[2-(2,3,5-trimethylammonium cyclopentadienyl)-1-naphthyl] ethanol,
(39) 1-[2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-naphthyl] ethanol,
(40) 1-[2-(2-dimethylaminomethyl cyclopentadienyl)-1-naphthyl] ethanol,
(41) 1-[2-(3-dimethylaminomethyl cyclopentadienyl)-1-naphthyl] ethanol,
(42) 1-[2-(cyclopentadienyl) phenyl]-1-methyl-ethanol,
(43) 1-[2-(2-methyl cyclopentadienyl) phenyl]-1-methyl-ethanol,
(44) 1-[2-(3-methyl cyclopentadienyl) phenyl]-1-methyl-ethanol,
(45) 1-[2-(2,3-dimethyl cyclopentadienyl) phenyl]-1-methyl-ethanol,
(46) 1-[2-(2,4-dimethyl cyclopentadienyl) phenyl]-1-methyl-ethanol,
(47) 1-[2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl]-1-methyl-ethanol,
(48) 1-[2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl]-1-methyl-ethanol,
(49) 1-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl]-1-methyl-ethanol,
(50) 1-[2-(2-dimethylaminomethyl cyclopentadienyl) phenyl]-1-methyl-ethanol,
(51) 1-[2-(3-dimethylaminomethyl cyclopentadienyl) phenyl]-1-methyl-ethanol,
(52) 1-[2-(cyclopentadienyl)-1-naphthyl]-1-methyl-ethanol,
(53) 1-[2-(2-methyl cyclopentadienyl)-1-naphthyl]-1-methyl-ethanol,
(54) 1-[2-(3-methyl cyclopentadienyl)-1-naphthyl]-1-methyl-ethanol,
(55) 1-[2-(2,3-dimethyl cyclopentadienyl)-1-naphthyl]-1-methyl-ethanol,
(56) 1-[2-(2,4-dimethyl cyclopentadienyl)-1-naphthyl]-1-methyl-ethanol,
(57) 1-[2-(2,3,4-trimethylammonium cyclopentadienyl)-1-naphthyl]-1-methyl-ethanol,
(58) 1-[2-(2,3,5-trimethylammonium cyclopentadienyl)-1-naphthyl]-1-methyl-ethanol,
(59) 1-[2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-naphthyl]-1-methyl-ethanol,
(60) 1-[2-(2-dimethylaminomethyl cyclopentadienyl)-1-naphthyl]-1-methyl-ethanol,
(61) 1-[2-(3-dimethylaminomethyl cyclopentadienyl)-1-naphthyl]-1-methyl-ethanol,
(62) [2-(cyclopentadienyl) the phenyl]-tertiary butyl-methyl alcohol,
(63) [2-(2-methyl cyclopentadienyl) the phenyl]-tertiary butyl-methyl alcohol,
(64) [2-(3-methyl cyclopentadienyl) the phenyl]-tertiary butyl-methyl alcohol,
(65) [2-(2,3-dimethyl cyclopentadienyl) the phenyl]-tertiary butyl-methyl alcohol,
(66) [2-(2,4-dimethyl cyclopentadienyl) the phenyl]-tertiary butyl-methyl alcohol,
(67) [2-(2,3,4-trimethylammonium cyclopentadienyl) the phenyl]-tertiary butyl-methyl alcohol,
(68) [2-(2,3,5-trimethylammonium cyclopentadienyl) the phenyl]-tertiary butyl-methyl alcohol,
(69) [2-(2,3,4,5-tetramethyl-ring pentadienyl) the phenyl]-tertiary butyl-methyl alcohol,
(70) [2-(2-dimethylaminomethyl cyclopentadienyl) the phenyl]-tertiary butyl-methoxyl group alcohol,
(71) [2-(3-dimethylaminomethyl cyclopentadienyl) the phenyl]-tertiary butyl-methyl alcohol,
(72) [2-(cyclopentadienyl)-1-the naphthyl]-tertiary butyl-methyl alcohol,
(73) [2-(2-methyl cyclopentadienyl)-1-the naphthyl]-tertiary butyl-methyl alcohol,
(74) [2-(3-methyl cyclopentadienyl)-1-the naphthyl]-tertiary butyl-methyl alcohol,
(75) [2-(2,3-dimethyl cyclopentadienyl)-1-the naphthyl]-tertiary butyl-methyl alcohol,
(76) [2-(2,4-dimethyl cyclopentadienyl)-1-the naphthyl]-tertiary butyl-methyl alcohol,
(77) [2-(2,3,4-trimethylammonium cyclopentadienyl)-1-the naphthyl]-tertiary butyl-methyl alcohol,
(78) [2-(2,3,5-trimethylammonium cyclopentadienyl)-1-the naphthyl]-tertiary butyl-methyl alcohol,
(79) [2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-the naphthyl]-tertiary butyl-methyl alcohol,
(80) [2-(2-dimethylaminomethyl cyclopentadienyl)-1-the naphthyl]-tertiary butyl-methyl alcohol,
(81) [2-(3-dimethylaminomethyl cyclopentadienyl)-1-the naphthyl]-tertiary butyl-methyl alcohol,
(82) [2-(cyclopentadienyl) phenyl] phenyl methanol,
(83) [2-(2-methyl cyclopentadienyl) phenyl] phenyl methanol,
(84) [2-(3-methyl cyclopentadienyl) phenyl] phenyl methanol,
(85) [2-(2,3-dimethyl cyclopentadienyl) phenyl] phenyl methanol,
(86) [2-(2,4-dimethyl cyclopentadienyl) phenyl] phenyl methanol,
(87) [2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl] phenyl methanol,
(88) [2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl] phenyl methanol,
(89) [2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl] phenyl methanol,
(90) [2-(2-dimethylaminomethyl cyclopentadienyl) phenyl] phenyl methoxyl group alcohol,
(91) [2-(3-dimethylaminomethyl cyclopentadienyl) phenyl] phenyl methanol,
(92) [2-(cyclopentadienyl)-1-naphthyl] phenyl methanol,
(93) [2-(2-methyl cyclopentadienyl)-1-naphthyl] phenyl methanol,
(94) [2-(3-methyl cyclopentadienyl)-1-naphthyl] phenyl methanol,
(95) [2-(2,3-dimethyl cyclopentadienyl)-1-naphthyl] phenyl alcohol,
(96) [2-(2,4-dimethyl cyclopentadienyl)-1-naphthyl] phenyl methanol,
(97) [2-(2,3,4-trimethylammonium cyclopentadienyl)-1-naphthyl] phenyl methanol,
(98) [2-(2,3,5-trimethylammonium cyclopentadienyl)-1-naphthyl] phenyl methanol,
(99) [2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-naphthyl] phenyl methanol,
(100) [2-(2-dimethylaminomethyl cyclopentadienyl)-1-naphthyl] phenyl methanol,
(101) [2-(3-dimethylaminomethyl cyclopentadienyl)-1-naphthyl] phenyl methanol,
(102) [2-(cyclopentadienyl) phenyl] diphenyl-carbinol,
(103) [2-(2-methyl cyclopentadienyl) phenyl] diphenyl-carbinol,
(104) [2-(3-methyl cyclopentadienyl) phenyl] diphenyl-carbinol,
(105) [2-(2,3-dimethyl cyclopentadienyl) phenyl] diphenyl-carbinol,
(106) [2-(2,4-dimethyl cyclopentadienyl) phenyl] diphenyl-carbinol,
(107) [2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl] diphenyl-carbinol,
(108) [2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl] diphenyl-carbinol,
(109) [2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl] diphenyl-carbinol,
(110) [2-(2-dimethylaminomethyl cyclopentadienyl) phenyl] diphenylmethyl keto-alcohol,
(111) [2-(3-dimethylaminomethyl cyclopentadienyl) phenyl] diphenyl-carbinol,
(112) [2-(cyclopentadienyl)-1-naphthyl] diphenyl-carbinol,
(113) [2-(2-methyl cyclopentadienyl)-1-naphthyl] diphenyl-carbinol,
(114) [2-(3-methyl cyclopentadienyl)-1-naphthyl] diphenyl-carbinol,
(115) [2-(2,3-dimethyl cyclopentadienyl)-1-naphthyl] phenylbenzene alcohol,
(116) [2-(2,4-dimethyl cyclopentadienyl)-1-naphthyl] diphenyl-carbinol,
(117) [2-(2,3,4-trimethylammonium cyclopentadienyl)-1-naphthyl] diphenyl-carbinol,
(118) [2-(2,3,5-trimethylammonium cyclopentadienyl)-1-naphthyl] diphenyl-carbinol,
(119) [2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-naphthyl] diphenyl-carbinol,
(120) [2-(2-dimethylaminomethyl cyclopentadienyl)-1-naphthyl] diphenyl-carbinol,
(121) [2-(3-dimethylaminomethyl cyclopentadienyl)-1-naphthyl] diphenyl-carbinol etc.
Below amine compound shown in the formula (6) is described;
Figure G2006100046087D00631
R wherein 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 20And R 30Have with above-mentioned formula (I-2) in identical connotation.
The amine compound of formula (6) can or make described compound and nucleophilic reagent reaction obtains by group with imine moiety shown in the reduction-type (9):
Figure G2006100046087D00632
R wherein 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9And R 20Have with above-mentioned formula (I-2) in identical connotation; Condition is R 30It is not hydrogen atom.
Used nucleophilic reagent comprises (R such as metal hydride, organolithium compound, organo-magnesium compound in this reaction 20Li or R 20MgX; Condition is R 20Be not hydrogen atom).
Such nucleophilic reagent comprises metal hydride such as lithium aluminum hydride, sodium borohydride, sodium cyanoborohydride etc.; Methylmagnesium-bromide, ethyl-magnesium-bromide, phenyl-magnesium-bromide, bromination normal-butyl magnesium, bromination tertiary butyl magnesium, lithium methide, phenyl lithium, tert-butyl lithium etc.Equally, can also exemplify the compound that magnesium bromide in the above-claimed cpd changes magnesium chloride or magnesium iodide into.The consumption of nucleophilic reagent is generally about 0.25-5 mole with respect to 1 mole of imines.
Above-mentioned reaction is implemented in solvent usually.Such solvent comprises for example alcoholic solvents such as methyl alcohol, ethanol, Virahol; Aprotic solvent, aromatic solvent such as benzene, toluene for example, aliphatic hydrocarbon solvent such as hexane, heptane, ether, tetrahydrofuran (THF), 1, ether solvents such as 4-diox, amide solvent such as hexamethylphosphoramide, dimethyl formamide, acetonitrile, propionitrile, acetone, diethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone isopolarity solvent, halogenated solvents such as methylene dichloride, ethylene dichloride, chlorobenzene, dichlorobenzene.Can use the mixture of a kind of solvent or two or more solvents.The consumption of solvent is generally 1-200 times of imines weight shown in the formula (9), and preferred 3-50 doubly.
Temperature of reaction is generally-100 ℃ of boiling points to solvent, is generally-80 ℃ to 120 ℃.
After the reaction, if desired, can in the gained reaction mixture, add entry.Then this mixture separation is become organic layer and water layer, to obtain target compound solution as organic layer.When because in described reaction, use with the solvent of water compatible or use a small amount of solvent and when making organic layer and water layer not easily separated, can after in reaction mixture, adding water-insoluble organic solvents such as toluene, ethyl acetate or chlorobenzene, separate.Amine shown in the formula (6) can be purified by for example following operation: wash the described solution of this compound with water, dry described solution, distilling off solvent is also further purified through methods such as recrystallization, distillation, column chromatography processing then.
Group with imine moiety shown in the formula (9) can be by carbonyl compound and the amine compound (R that makes formula (1) 30-NH 2) reaction and make.
The object lesson of group with imine moiety comprises following compounds shown in the formula (9):
(1) N-(2-(cyclopentadienyl) phenyl) methylene radical-N-phenyl amine,
(2) N-(2-(2-methyl cyclopentadienyl) phenyl) methylene radical-N-phenyl amine,
(3) N-(2-(3-methyl cyclopentadienyl) phenyl) methylene radical-N-phenyl amine,
(4) N-(2-(2,3-dimethyl cyclopentadienyl) phenyl) methylene radical-N-phenyl amine,
(5) N-(2-(2,4-dimethyl cyclopentadienyl) phenyl) methylene radical-N-phenyl amine,
(6) N-(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl) methylene radical-N-phenyl amine,
(7) N-(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl) methylene radical-N-phenyl amine,
(8) N-(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl) methylene radical-N-phenyl amine,
(9) N-(2-(2-dimethylamino cyclopentadienyl) phenyl) methylene radical-N-phenyl amine,
(10) N-(2-(3-dimethylamino cyclopentadienyl) phenyl) methylene radical-N-phenyl amine,
(11) N-(2-(indenes-1-yl) phenyl) methylene radical-N-phenyl amine,
(12) N-(2-(2-methyl indenes-1-yl) phenyl) methylene radical-N-phenyl amine,
(13) N-(2-(2-phenylindan-1-yl) phenyl) methylene radical-N-phenyl amine,
(14) N-(2-(cyclopentadienyl) phenyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(15) N-(2-(2-methyl cyclopentadienyl) phenyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(16) N-(2-(3-methyl cyclopentadienyl) phenyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(17) N-(2-(2,3-dimethyl cyclopentadienyl) phenyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(18) N-(2-(2,4-dimethyl cyclopentadienyl) phenyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(19) N-(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(20) N-(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(21) N-(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(22) N-(2-(2-dimethylamino cyclopentadienyl) phenyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(23) N-(2-(3-dimethylamino cyclopentadienyl) phenyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(24) N-(2-(indenes-1-yl) phenyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(25) N-(2-(2-methyl indenes-1-yl) phenyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(26) N-(2-(2-phenylindan-1-yl) phenyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(27) N-(2-(cyclopentadienyl) phenyl) methylene radical-N-tert-butylamine,
(28) N-(2-(2-methyl cyclopentadienyl) phenyl) methylene radical-N-tert-butylamine,
(29) N-(2-(3-methyl cyclopentadienyl) phenyl) methylene radical-N-tert-butylamine,
(30) N-(2-(2,3-dimethyl cyclopentadienyl) phenyl) methylene radical-N-tert-butylamine,
(31) N-(2-(2,4-dimethyl cyclopentadienyl) phenyl) methylene radical-N-tert-butylamine,
(32) N-(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl) methylene radical-N-tert-butylamine,
(33) N-(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl) methylene radical-N-tert-butylamine,
(34) N-(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl) methylene radical-N-tert-butylamine,
(35) N-(2-(2-dimethylamino cyclopentadienyl) phenyl) methylene radical-N-tert-butylamine,
(36) N-(2-(3-dimethylamino cyclopentadienyl) phenyl) methylene radical-N-tert-butylamine,
(37) N-(2-(indenes-1-yl) phenyl) methylene radical-N-tert-butylamine,
(38) N-(2-(2-methyl indenes-1-yl) phenyl) methylene radical-N-tert-butylamine,
(39) N-(2-(2-phenylindan-1-yl) phenyl) methylene radical-N-tert-butylamine,
(40) N-(2-(cyclopentadienyl) phenyl) methylene radical-N-n-butylamine,
(41) N-(2-(2-methyl cyclopentadienyl) phenyl) methylene radical-N-n-butylamine,
(42) N-(2-(3-methyl cyclopentadienyl) phenyl) methylene radical-N-n-butylamine,
(43) N-(2-(2,3-dimethyl cyclopentadienyl) phenyl) methylene radical-N-n-butylamine,
(44) N-(2-(2,4-dimethyl cyclopentadienyl) phenyl) methylene radical-N-n-butylamine,
(45) N-(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl) methylene radical-N-n-butylamine,
(46) N-(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl) methylene radical-N-n-butylamine,
(47) N-(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl) methylene radical-N-n-butylamine,
(48) N-(2-(2-dimethylamino cyclopentadienyl) phenyl) methylene radical-N-n-butylamine,
(49) N-(2-(3-dimethylamino cyclopentadienyl) phenyl) methylene radical-N-n-butylamine,
(50) N-(2-(indenes-1-yl) phenyl) methylene radical-N-n-butylamine,
(51) N-(2-(2-methyl indenes-1-yl) phenyl) methylene radical-N-n-butylamine,
(52) N-(2-(2-phenylindan-1-yl) phenyl) methylene radical-N-n-butylamine,
(53) N-(2-(cyclopentadienyl) phenyl) ethylidene-N-phenyl amine,
(54) N-(2-(2-methyl cyclopentadienyl) phenyl) ethylidene-N-phenyl amine,
(55) N-(2-(3-methyl cyclopentadienyl) phenyl) ethylidene-N-phenyl amine,
(56) N-(2-(2,3-dimethyl cyclopentadienyl) phenyl) ethylidene-N-phenyl amine,
(57) N-(2-(2,4-dimethyl cyclopentadienyl) phenyl) ethylidene-N-phenyl amine,
(58) N-(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl) ethylidene-N-phenyl amine,
(59) N-(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl) ethylidene-N-phenyl amine,
(60) N-(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl) ethylidene-N-phenyl amine,
(61) N-(2-(2-dimethylamino cyclopentadienyl) phenyl) ethylidene-N-phenyl amine,
(62) N-(2-(3-dimethylamino cyclopentadienyl) phenyl) ethylidene-N-phenyl amine,
(63) N-(2-(indenes-1-yl) phenyl) ethylidene-N-phenyl amine,
(64) N-(2-(2-methyl indenes-1-yl) phenyl) ethylidene-N-phenyl amine,
(65) N-(2-(2-phenylindan-1-yl) phenyl) ethylidene-N-phenyl amine,
(66) N-(2-(cyclopentadienyl) phenyl) ethylidene-N-(2,4, the 6-trimethylphenyl) amine,
(67) N-(2-(2-methyl cyclopentadienyl) phenyl) ethylidene-N-(2,4, the 6-trimethylphenyl) amine,
(68) N-(2-(3-methyl cyclopentadienyl) phenyl) ethylidene-N-(2,4, the 6-trimethylphenyl) amine,
(69) N-(2-(2,3-dimethyl cyclopentadienyl) phenyl) ethylidene-N-(2,4, the 6-trimethylphenyl) amine,
(70) N-(2-(2,4-dimethyl cyclopentadienyl) phenyl) ethylidene-N-(2,4, the 6-trimethylphenyl) amine,
(71) N-(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl) ethylidene-N-(2,4, the 6-trimethylphenyl) amine,
(72) N-(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl) ethylidene-N-(2,4, the 6-trimethylphenyl) amine,
(73) N-(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl) ethylidene-N-(2,4, the 6-trimethylphenyl) amine,
(74) N-(2-(2-dimethylamino cyclopentadienyl) phenyl) ethylidene-N-(2,4, the 6-trimethylphenyl) amine,
(75) N-(2-(3-dimethylamino cyclopentadienyl) phenyl) ethylidene-N-(2,4, the 6-trimethylphenyl) amine,
(76) N-(2-(indenes-1-yl) phenyl) ethylidene-N-(2,4, the 6-trimethylphenyl) amine,
(77) N-(2-(2-methyl indenes-1-yl) phenyl) ethylidene-N-(2,4, the 6-trimethylphenyl) amine,
(78) N-(2-(2-phenylindan-1-yl) phenyl) ethylidene-N-(2,4, the 6-trimethylphenyl) amine,
(79) N-(2-(cyclopentadienyl) phenyl) ethylidene-N-tert-butylamine,
(80) N-(2-(2-methyl cyclopentadienyl) phenyl) ethylidene-N-tert-butylamine,
(81) N-(2-(3-methyl cyclopentadienyl) phenyl) ethylidene-N-tert-butylamine,
(82) N-(2-(2,3-dimethyl cyclopentadienyl) phenyl) ethylidene-N-tert-butylamine,
(83) N-(2-(2,4-dimethyl cyclopentadienyl) phenyl) ethylidene-N-tert-butylamine,
(84) N-(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl) ethylidene-N-tert-butylamine,
(85) N-(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl) ethylidene-N-tert-butylamine,
(86) N-(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl) ethylidene-N-tert-butylamine,
(87) N-(2-(2-dimethylamino cyclopentadienyl) phenyl) ethylidene-N-tert-butylamine,
(88) N-(2-(3-dimethylamino cyclopentadienyl) phenyl) ethylidene-N-tert-butylamine,
(89) N-(2-(indenes-1-yl) phenyl) ethylidene-N-tert-butylamine,
(90) N-(2-(2-methyl indenes-1-yl) phenyl) ethylidene-N-tert-butylamine,
(91) N-(2-(2-phenylindan-1-yl) phenyl) ethylidene-N-tert-butylamine,
(92) N-(2-(cyclopentadienyl) phenyl) ethylidene-N-n-butylamine,
(93) N-(2-(2-methyl cyclopentadienyl) phenyl) ethylidene-N-n-butylamine,
(94) N-(2-(3-methyl cyclopentadienyl) phenyl) ethylidene-N-n-butylamine,
(95) N-(2-(2,3-dimethyl cyclopentadienyl) phenyl) ethylidene-N-n-butylamine,
(96) N-(2-(2,4-dimethyl cyclopentadienyl) phenyl) ethylidene-N-n-butylamine,
(97) N-(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl) ethylidene-N-n-butylamine,
(98) N-(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl) ethylidene-N-n-butylamine,
(99) N-(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl) ethylidene-N-n-butylamine,
(100) N-(2-(2-dimethylamino cyclopentadienyl) phenyl) ethylidene-N-n-butylamine,
(101) N-(2-(3-dimethylamino cyclopentadienyl) phenyl) ethylidene-N-n-butylamine,
(102) N-(2-(indenes-1-yl) phenyl) ethylidene-N-n-butylamine,
(103) N-(2-(2-methyl indenes-1-yl) phenyl) ethylidene-N-n-butylamine,
(104) N-(2-(2-phenylindan-1-yl) phenyl) ethylidene-N-n-butylamine,
(105) N-(2-(cyclopentadienyl)-1-naphthyl) methylene radical-N-phenyl amine,
(106) N-(2-(2-methyl cyclopentadienyl)-1-naphthyl) methylene radical-N-phenyl amine,
(107) N-(2-(3-methyl cyclopentadienyl)-1-naphthyl) methylene radical-N-phenyl amine,
(108) N-(2-(2,3-dimethyl cyclopentadienyl)-1-naphthyl) methylene radical-N-phenyl amine,
(109) N-(2-(2,4-dimethyl cyclopentadienyl)-1-naphthyl) methylene radical-N-phenyl amine,
(110) N-(2-(2,3,4-trimethylammonium cyclopentadienyl)-1-naphthyl) methylene radical-N-phenyl amine,
(111) N-(2-(2,3,5-trimethylammonium cyclopentadienyl)-1-naphthyl) methylene radical-N-phenyl amine,
(112) N-(2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-naphthyl) methylene radical-N-phenyl amine,
(113) N-(2-(2-dimethylamino cyclopentadienyl)-1-naphthyl) methylene radical-N-phenyl amine,
(114) N-(2-(3-dimethylamino cyclopentadienyl)-1-naphthyl) methylene radical-N-phenyl amine,
(115) N-(2-(indenes-1-yl)-1-naphthyl) methylene radical-N-phenyl amine,
(116) N-(2-(2-methyl indenes-1-yl)-1-naphthyl) methylene radical-N-phenyl amine,
(117) N-(2-(2-phenylindan-1-yl)-1-naphthyl) methylene radical-N-phenyl amine,
(118) N-(2-(cyclopentadienyl)-1-naphthyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(119) N-(2-(2-methyl cyclopentadienyl)-1-naphthyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(120) N-(2-(3-methyl cyclopentadienyl)-1-naphthyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(121) N-(2-(2,3-dimethyl cyclopentadienyl)-1-naphthyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(122) N-(2-(2,4-dimethyl cyclopentadienyl)-1-naphthyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(123) N-(2-(2,3,4-trimethylammonium cyclopentadienyl)-1-naphthyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(124) N-(2-(2,3,5-trimethylammonium cyclopentadienyl)-1-naphthyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(125) N-(2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-naphthyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(126) N-(2-(2-dimethylamino cyclopentadienyl)-1-naphthyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(127) N-(2-(3-dimethylamino cyclopentadienyl)-1-naphthyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(128) N-(2-(indenes-1-yl)-1-naphthyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(129) N-(2-(2-methyl indenes-1-yl)-1-naphthyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(130) N-(2-(2-phenylindan-1-yl)-1-naphthyl) methylene radical-N-(2,4, the 6-trimethylphenyl) amine,
(131) N-(2-(cyclopentadienyl)-1-naphthyl) methylene radical-N-tert-butylamine,
(132) N-(2-(2-methyl cyclopentadienyl)-1-naphthyl) methylene radical-N-tert-butylamine,
(133) N-(2-(3-methyl cyclopentadienyl)-1-naphthyl) methylene radical-N-tert-butylamine,
(134) N-(2-(2,3-dimethyl cyclopentadienyl)-1-naphthyl) methylene radical-N-tert-butylamine,
(135) N-(2-(2,4-dimethyl cyclopentadienyl)-1-naphthyl) methylene radical-N-tert-butylamine,
(136) N-(2-(2,3,4-trimethylammonium cyclopentadienyl)-1-naphthyl) methylene radical-N-tert-butylamine,
(137) N-(2-(2,3,5-trimethylammonium cyclopentadienyl)-1-naphthyl) methylene radical-N-tert-butylamine,
(138) N-(2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-naphthyl) methylene radical-N-tert-butylamine,
(139) N-(2-(2-dimethylamino cyclopentadienyl)-1-naphthyl) methylene radical-N-tert-butylamine,
(140) N-(2-(3-dimethylamino cyclopentadienyl)-1-naphthyl) methylene radical-N-tert-butylamine,
(141) N-(2-(indenes-1-yl)-1-naphthyl) methylene radical-N-tert-butylamine,
(142) N-(2-(2-methyl indenes-1-yl)-1-naphthyl) methylene radical-N-tert-butylamine,
(143) N-(2-(2-phenylindan-1-yl)-1-naphthyl) methylene radical-N-tert-butylamine,
(144) N-(2-(cyclopentadienyl)-1-naphthyl) methylene radical-N-n-butylamine,
(145) N-(2-(2-methyl cyclopentadienyl)-1-naphthyl) methylene radical-N-n-butylamine,
(146) N-(2-(3-methyl cyclopentadienyl)-1-naphthyl) methylene radical-N-n-butylamine,
(147) N-(2-(2,3-dimethyl cyclopentadienyl)-1-naphthyl) methylene radical-N-n-butylamine,
(148) N-(2-(2,4-dimethyl cyclopentadienyl)-1-naphthyl) methylene radical-N-n-butylamine,
(149) N-(2-(2,3,4-trimethylammonium cyclopentadienyl)-1-naphthyl) methylene radical-N-n-butylamine,
(150) N-(2-(2,3,5-trimethylammonium cyclopentadienyl)-1-naphthyl) methylene radical-N-n-butylamine,
(151) N-(2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-naphthyl) methylene radical-N-n-butylamine,
(152) N-(2-(2-dimethylamino cyclopentadienyl)-1-naphthyl) methylene radical-N-n-butylamine,
(153) N-(2-(3-dimethylamino cyclopentadienyl)-1-naphthyl) methylene radical-N-n-butylamine,
(154) N-(2-(indenes-1-yl)-1-naphthyl) methylene radical-N-n-butylamine,
(155) N-(2-(2-methyl indenes-1-yl)-1-naphthyl) methylene radical-N-n-butylamine,
(156) N-(2-(2-phenylindan-1-yl)-1-naphthyl) methylene radical-N-n-butylamine etc.
The object lesson of amine compound comprises following compounds shown in the formula that obtains thus (6);
(1) methyl N-[(2-(cyclopentadienyl) phenyl)]-the N-phenyl amine,
(2) methyl N-[(2-(2-methyl cyclopentadienyl) phenyl)]-the N-phenyl amine,
(3) methyl N-[(2-(3-methyl cyclopentadienyl) phenyl)]-the N-phenyl amine,
(4) methyl N-[(2-(2,3-dimethyl cyclopentadienyl) phenyl)]-the N-phenyl amine,
(5) methyl N-[(2-(2,4-dimethyl cyclopentadienyl) phenyl)]-the N-phenyl amine,
(6) methyl N-[(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl)]-the N-phenyl amine,
(7) methyl N-[(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl)]-the N-phenyl amine,
(8) methyl N-[(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl)]-the N-phenyl amine,
(9) methyl N-[(2-(2-dimethylaminomethyl cyclopentadienyl) phenyl)]-the N-phenyl amine,
(10) methyl N-[(2-(3-dimethylaminomethyl cyclopentadienyl) phenyl)]-the N-phenyl amine,
(11) methyl N-[(2-(indenes-1-yl) phenyl)]-the N-phenyl amine,
(12) methyl N-[(2-(2-methyl indenes-1-yl) phenyl)]-the N-phenyl amine,
(13) methyl N-[(2-(2-phenylindan-1-yl) phenyl)]-the N-phenyl amine,
(14) methyl N-[(2-(fluorenes-9-yl) phenyl)]-the N-phenyl amine,
(15) methyl N-[(2-(cyclopentadienyl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(16) methyl dichloride N-[(2-(2-methyl cyclopentadienyl) phenyl)]-N-(2,4, the 6-trimethylphenyl) titanium,
(17) methyl N-[(2-(3-methyl cyclopentadienyl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(18) methyl N-[(2-(2,3-dimethyl cyclopentadienyl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(19) methyl N-[(2-(2,4-dimethyl cyclopentadienyl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(20) methyl N-[(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(21) methyl N-[(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(22) methyl N-[(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(23) methyl N-[(2-(2-dimethylaminomethyl cyclopentadienyl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(24) methyl N-[(2-(3-dimethylaminomethyl cyclopentadienyl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(25) methyl N-[(2-(indenes-1-yl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(26) methyl N-[(2-(2-methyl indenes-1-yl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(27) methyl N-[(2-(2-phenylindan-1-yl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(28) methyl N-[(2-(fluorenes-9-yl) phenyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(29) methyl N-[(2-(cyclopentadienyl) phenyl)]-the N-tert-butylamine,
(30) methyl N-[(2-(2-methyl cyclopentadienyl) phenyl)]-the N-tert-butylamine,
(31) methyl N-[(2-(3-methyl cyclopentadienyl) phenyl)]-the N-tert-butylamine,
(32) methyl N-[(2-(2,3-dimethyl cyclopentadienyl) phenyl)]-the N-tert-butylamine,
(33) methyl N-[(2-(2,4-dimethyl cyclopentadienyl) phenyl)]-the N-tert-butylamine,
(34) methyl N-[(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl)]-the N-tert-butylamine,
(35) methyl N-[(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl)]-the N-tert-butylamine,
(36) methyl N-[(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl)]-the N-tert-butylamine,
(37) methyl N-[(2-(2-dimethylaminomethyl cyclopentadienyl) phenyl)]-the N-tert-butylamine,
(38) methyl N-[(2-(3-dimethylaminomethyl cyclopentadienyl) phenyl)]-the N-tert-butylamine,
(39) methyl N-[(2-(indenes-1-yl) phenyl)]-the N-tert-butylamine,
(40) methyl N-[(2-(2-methyl indenes-1-yl) phenyl)]-the N-tert-butylamine,
(41) methyl N-[(2-(2-phenylindan-1-yl) phenyl)]-the N-tert-butylamine,
(42) methyl N-[(2-(fluorenes-9-yl) phenyl)]-the N-tert-butylamine,
(43) methyl N-[(2-(cyclopentadienyl) phenyl)]-the N-n-butylamine,
(44) methyl N-[(2-(2-methyl cyclopentadienyl) phenyl)]-the N-n-butylamine,
(45) methyl N-[(2-(3-methyl cyclopentadienyl) phenyl)]-the N-n-butylamine,
(46) methyl N-[(2-(2,3-dimethyl cyclopentadienyl) phenyl)]-the N-n-butylamine,
(47) methyl N-[(2-(2,4-dimethyl cyclopentadienyl) phenyl)]-the N-n-butylamine,
(48) methyl N-[(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl)]-the N-n-butylamine,
(49) methyl N-[(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl)]-the N-n-butylamine,
(50) methyl N-[(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl)]-the N-n-butylamine,
(51) methyl N-[(2-(2-dimethylaminomethyl cyclopentadienyl) phenyl)]-the N-n-butylamine,
(52) methyl N-[(2-(3-dimethylaminomethyl cyclopentadienyl) phenyl)]-the N-n-butylamine,
(53) methyl N-[(2-(indenes-1-yl) phenyl)]-the N-n-butylamine,
(54) methyl N-[(2-(2-methyl indenes-1-yl) phenyl)]-the N-n-butylamine,
(55) methyl N-[(2-(2-phenylindan-1-yl) phenyl)]-the N-n-butylamine,
(56) methyl N-[(2-(fluorenes-9-yl) phenyl)]-the N-n-butylamine,
(57) N-[1-(2-(cyclopentadienyl) phenyl) ethyl]-the N-phenyl amine,
(58) N-[1-(2-(2-methyl cyclopentadienyl) phenyl) ethyl]-the N-phenyl amine,
(59) N-[1-(2-(3-methyl cyclopentadienyl) phenyl) ethyl]-the N-phenyl amine,
(60) N-[1-(2-(2,3-dimethyl cyclopentadienyl) phenyl) ethyl]-the N-phenyl amine,
(61) N-[1-(2-(2,4-dimethyl cyclopentadienyl) phenyl) ethyl]-the N-phenyl amine,
(62) N-[1-(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl) ethyl]-the N-phenyl amine,
(63) N-[1-(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl) ethyl]-the N-phenyl amine,
(64) N-[1-(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl) ethyl]-the N-phenyl amine,
(65) N-[1-(2-(2-dimethylaminomethyl cyclopentadienyl) phenyl) ethyl]-the N-phenyl amine,
(66) N-[1-(2-(3-dimethylaminomethyl cyclopentadienyl) phenyl) ethyl]-the N-phenyl amine,
(67) N-[1-(2-(indenes-1-yl) phenyl) ethyl]-the N-phenyl amine,
(68) N-[1-(2-(2-methyl indenes-1-yl) phenyl) ethyl]-the N-phenyl amine,
(69) N-[1-(2-(2-phenylindan-1-yl) phenyl) ethyl]-the N-phenyl amine,
(70) N-[1-(2-(fluorenes-9-yl) phenyl) ethyl]-the N-phenyl amine,
(71) N-[1-(2-(cyclopentadienyl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(72) N-[1-(2-(2-methyl cyclopentadienyl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(73) N-[1-(2-(3-methyl cyclopentadienyl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(74) N-[1-(2-(2,3-dimethyl cyclopentadienyl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(75) N-[1-(2-(2,4-dimethyl cyclopentadienyl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(76) N-[1-(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(77) N-[1-(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(78) N-[1-(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(79) N-[1-(2-(2-dimethylaminomethyl cyclopentadienyl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(80) N-[1-(2-(3-dimethylaminomethyl cyclopentadienyl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(81) N-[1-(2-(indenes-1-yl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(82) N-[1-(2-(2-methyl indenes-1-yl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(83) N-[1-(2-(2-phenylindan-1-yl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(84) N-[1-(2-(fluorenes-9-yl) phenyl) ethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(85) N-[1-(2-(cyclopentadienyl) phenyl) ethyl]-the N-tert-butylamine,
(86) N-[1-(2-(2-methyl cyclopentadienyl) phenyl) ethyl]-the N-tert-butylamine,
(87) N-[1-(2-(3-methyl cyclopentadienyl) phenyl) ethyl]-the N-tert-butylamine,
(88) N-[1-(2-(2,3-dimethyl cyclopentadienyl) phenyl) ethyl]-the N-tert-butylamine,
(89) N-[1-(2-(2,4-dimethyl cyclopentadienyl) phenyl) ethyl]-the N-tert-butylamine,
(90) N-[1-(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl) ethyl]-the N-tert-butylamine,
(91) N-[1-(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl) ethyl]-the N-tert-butylamine,
(92) N-[1-(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl) ethyl]-the N-tert-butylamine,
(93) N-[1-(2-(2-dimethylaminomethyl cyclopentadienyl) phenyl) ethyl]-the N-tert-butylamine,
(94) N-[1-(2-(3-dimethylaminomethyl cyclopentadienyl) phenyl) ethyl]-the N-tert-butylamine,
(95) N-[1-(2-(indenes-1-yl) phenyl) ethyl]-the N-tert-butylamine,
(96) N-[1-(2-(2-methyl indenes-1-yl) phenyl) ethyl]-the N-tert-butylamine,
(97) N-[1-(2-(2-phenylindan-1-yl) phenyl) ethyl]-the N-tert-butylamine,
(98) N-[1-(2-(fluorenes-9-yl) phenyl) ethyl]-the N-tert-butylamine,
(99) N-[1-(2-(cyclopentadienyl) phenyl) ethyl]-the N-n-butylamine,
(100) N-[1-(2-(2-methyl cyclopentadienyl) phenyl) ethyl]-the N-n-butylamine,
(101) N-[1-(2-(3-methyl cyclopentadienyl) phenyl) ethyl]-the N-n-butylamine,
(102) N-[1-(2-(2,3-dimethyl cyclopentadienyl) phenyl) ethyl]-the N-n-butylamine,
(103) N-[1-(2-(2,4-dimethyl cyclopentadienyl) phenyl) ethyl]-the N-n-butylamine,
(104) N-[1-(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl) ethyl]-the N-n-butylamine,
(105) N-[1-(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl) ethyl]-the N-n-butylamine,
(106) N-[1-(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl) ethyl]-the N-n-butylamine,
(107) N-[1-(2-(2-dimethylaminomethyl cyclopentadienyl) phenyl) ethyl]-the N-n-butylamine,
(108) N-[1-(2-(3-dimethylaminomethyl cyclopentadienyl) phenyl) ethyl]-the N-n-butylamine,
(109) N-[1-(2-(indenes-1-yl) phenyl) ethyl]-the N-n-butylamine,
(110) N-[1-(2-(2-methyl indenes-1-yl) phenyl) ethyl]-the N-n-butylamine,
(111) N-[1-(2-(2-phenylindan-1-yl) phenyl) ethyl]-the N-n-butylamine,
(112) N-[1-(2-(fluorenes-9-yl) phenyl) ethyl]-the N-n-butylamine,
(113) N-[1-(2-(cyclopentadienyl) phenyl)-1-methylethyl]-the N-phenyl amine,
(114) N-[1-(2-(2-methyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-phenyl amine,
(115) N-[1-(2-(3-methyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-phenyl amine,
(116) N-[1-(2-(2,3-dimethyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-phenyl amine,
(117) N-[1-(2-(2,4-dimethyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-phenyl amine,
(118) N-[1-(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl)-1-methylethyl]-the N-phenyl amine,
(119) N-[1-(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl)-1-methylethyl]-the N-phenyl amine,
(120) N-[1-(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl)-1-methylethyl]-the N-phenyl amine,
(121) N-[1-(2-(2-dimethylaminomethyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-phenyl amine,
(122) N-[1-(2-(3-dimethylaminomethyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-phenyl amine,
(123) N-[1-(2-(indenes-1-yl) phenyl)-1-methylethyl]-the N-phenyl amine,
(124) N-[1-(2-(2-methyl indenes-1-yl) phenyl)-1-methylethyl]-the N-phenyl amine,
(125) N-[1-(2-(2-phenylindan-1-yl) phenyl)-1-methylethyl]-the N-phenyl amine,
(126) N-[1-(2-(fluorenes-9-yl) phenyl)-1-methylethyl]-the N-phenyl amine,
(127) N-[1-(2-(cyclopentadienyl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(128) N-[1-(2-(2-methyl cyclopentadienyl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(129) N-[1-(2-(3-methyl cyclopentadienyl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(130) N-[1-(2-(2,3-dimethyl cyclopentadienyl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(131) N-[1-(2-(2,4-dimethyl cyclopentadienyl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(132) N-[1-(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(133) N-[1-(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(134) N-[1-(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(135) N-[1-(2-(2-dimethylaminomethyl cyclopentadienyl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(136) N-[1-(2-(3-dimethylaminomethyl cyclopentadienyl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(137) N-[1-(2-(indenes-1-yl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(138) N-[1-(2-(2-methyl indenes-1-yl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(139) N-[1-(2-(2-phenylindan-1-yl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(140) N-[1-(2-(fluorenes-9-yl) phenyl)-1-methylethyl]-N-(2,4, the 6-trimethylphenyl) amine,
(141) N-[1-(2-(cyclopentadienyl) phenyl)-1-methylethyl]-the N-tert-butylamine,
(142) N-[1-(2-(2-methyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-tert-butylamine,
(143) N-[1-(2-(3-methyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-tert-butylamine,
(144) N-[1-(2-(2,3-dimethyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-tert-butylamine,
(145) N-[1-(2-(2,4-dimethyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-tert-butylamine,
(146) N-[1-(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl)-1-methylethyl]-the N-tert-butylamine,
(147) N-[1-(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl)-1-methylethyl]-the N-tert-butylamine,
(148) N-[1-(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl)-1-methylethyl]-the N-tert-butylamine,
(149) N-[1-(2-(2-dimethylaminomethyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-tert-butylamine,
(150) N-[1-(2-(3-dimethylaminomethyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-tert-butylamine,
(151) N-[1-(2-(indenes-1-yl) phenyl)-1-methylethyl]-the N-tert-butylamine,
(152) N-[1-(2-(2-methyl indenes-1-yl) phenyl)-1-methylethyl]-the N-tert-butylamine,
(153) N-[1-(2-(2-phenylindan-1-yl) phenyl)-1-methylethyl]-the N-tert-butylamine,
(154) N-[1-(2-(fluorenes-9-yl) phenyl)-1-methylethyl]-the N-tert-butylamine,
(155) N-[1-(2-(cyclopentadienyl) phenyl)-1-methylethyl]-the N-n-butylamine,
(156) N-[1-(2-(2-methyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-n-butylamine,
(157) N-[1-(2-(3-methyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-n-butylamine,
(158) N-[1-(2-(2,3-dimethyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-n-butylamine,
(159) N-[1-(2-(2,4-dimethyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-n-butylamine,
(160) N-[1-(2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl)-1-methylethyl]-the N-n-butylamine,
(161) N-[1-(2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl)-1-methylethyl]-the N-n-butylamine,
(162) N-[1-(2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl)-1-methylethyl]-the N-n-butylamine,
(163) N-[1-(2-(2-dimethylaminomethyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-n-butylamine,
(164) N-[1-(2-(3-dimethylaminomethyl cyclopentadienyl) phenyl)-1-methylethyl]-the N-n-butylamine,
(165) N-[1-(2-(indenes-1-yl) phenyl)-1-methylethyl]-the N-n-butylamine,
(166) N-[1-(2-(2-methyl indenes-1-yl) phenyl)-1-methylethyl]-the N-n-butylamine,
(167) N-[1-(2-(2-phenylindan-1-yl) phenyl)-1-methylethyl]-the N-n-butylamine,
(168) N-[1-(2-(fluorenes-9-yl) phenyl)-1-methylethyl]-the N-n-butylamine,
(169) methyl N-[(2-(cyclopentadienyl)-1-naphthyl)]-the N-phenyl amine,
(170) methyl N-[(2-(2-methyl cyclopentadienyl)-1-naphthyl)]-the N-phenyl amine,
(171) methyl N-[(2-(3-methyl cyclopentadienyl)-1-naphthyl)]-the N-phenyl amine,
(172) methyl N-[(2-(2,3-dimethyl cyclopentadienyl)-1-naphthyl)]-the N-phenyl amine,
(173) methyl N-[(2-(2,4-dimethyl cyclopentadienyl)-1-naphthyl)]-the N-phenyl amine,
(174) methyl N-[(2-(2,3,4-trimethylammonium cyclopentadienyl)-1-naphthyl)]-the N-phenyl amine,
(175) methyl N-[(2-(2,3,5-trimethylammonium cyclopentadienyl)-1-naphthyl)]-the N-phenyl amine,
(176) methyl N-[(2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-naphthyl)]-the N-phenyl amine,
(177) methyl N-[(2-(2-dimethylaminomethyl cyclopentadienyl)-1-naphthyl)]-the N-phenyl amine,
(178) methyl N-[(2-(3-dimethylaminomethyl cyclopentadienyl)-1-naphthyl)]-the N-phenyl amine,
(179) methyl N-[(2-(indenes-1-yl)-1-naphthyl)]-the N-phenyl amine,
(180) methyl N-[(2-(2-methyl indenes-1-yl)-1-naphthyl)]-the N-phenyl amine,
(181) methyl N-[(2-(2-phenylindan-1-yl)-1-naphthyl)]-the N-phenyl amine,
(182) methyl N-[(2-(fluorenes-9-yl)-1-naphthyl)]-the N-phenyl amine,
(183) methyl N-[(2-(cyclopentadienyl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(184) methyl N-[(2-(2-methyl cyclopentadienyl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(185) methyl N-[(2-(3-methyl cyclopentadienyl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(186) methyl N-[(2-(2,3-dimethyl cyclopentadienyl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(187) methyl N-[(2-(2,4-dimethyl cyclopentadienyl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(188) methyl N-[(2-(2,3,4-trimethylammonium cyclopentadienyl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(189) methyl N-[(2-(2,3,5-trimethylammonium cyclopentadienyl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(190) methyl N-[(2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(191) methyl N-[(2-(2-dimethylaminomethyl cyclopentadienyl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(192) methyl N-[(2-(3-dimethylaminomethyl cyclopentadienyl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(193) methyl N-[(2-(indenes-1-yl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(194) methyl N-[(2-(2-methyl indenes-1-yl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(195) methyl N-[(2-(2-phenylindan-1-yl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(196) methyl N-[(2-(fluorenes-9-yl)-1-naphthyl)]-N-(2,4, the 6-trimethylphenyl) amine,
(197) methyl N-[(2-(cyclopentadienyl)-1-naphthyl)]-the N-tert-butylamine,
(198) methyl N-[(2-(2-methyl cyclopentadienyl)-1-naphthyl)]-the N-tert-butylamine,
(199) methyl N-[(2-(3-methyl cyclopentadienyl)-1-naphthyl)]-the N-tert-butylamine,
(200) methyl N-[(2-(2,3-dimethyl cyclopentadienyl)-1-naphthyl)]-the N-tert-butylamine,
(201) methyl N-[(2-(2,4-dimethyl cyclopentadienyl)-1-naphthyl)]-the N-tert-butylamine,
(202) N-[(2-(2,3,4-trimethylammonium cyclopentadiene-first-1-naphthyl) methyl]-the N-tert-butylamine,
(203) N-[(2-(2,3,5-trimethylammonium cyclopentadiene-first-1-naphthyl) methyl]-the N-tert-butylamine,
(204) N-[(2-(2,3,4,5-tetramethyl-ring pentadiene-first-1-naphthyl) methyl]-the N-tert-butylamine,
(205) methyl N-[(2-(2-dimethylaminomethyl cyclopentadienyl)-1-naphthyl)]-the N-tert-butylamine,
(206) methyl N-[(2-(3-dimethylaminomethyl cyclopentadienyl)-1-naphthyl)]-the N-tert-butylamine,
(207) methyl N-[(2-(indenes-1-yl)-1-naphthyl)]-the N-tert-butylamine,
(208) methyl N-[(2-(2-methyl indenes-1-yl)-1-naphthyl)]-the N-tert-butylamine,
(209) methyl N-[(2-(2-phenylindan-1-yl)-1-naphthyl)]-the N-tert-butylamine,
(210) methyl N-[(2-(fluorenes-9-yl)-1-naphthyl)]-the N-tert-butylamine,
(211) methyl N-[(2-(cyclopentadienyl)-1-naphthyl)]-the N-n-butylamine,
(212) methyl N-[(2-(2-methyl cyclopentadienyl)-1-naphthyl)]-the N-n-butylamine,
(213) methyl N-[(2-(3-methyl cyclopentadienyl)-1-naphthyl)]-the N-n-butylamine,
(214) methyl N-[(2-(2,3-dimethyl cyclopentadienyl)-1-naphthyl)]-the N-n-butylamine,
(215) methyl N-[(2-(2,4-dimethyl cyclopentadienyl)-1-naphthyl)]-the N-n-butylamine,
(216) methyl N-[(2-(2,3,4-trimethylammonium cyclopentadienyl)-1-naphthyl)]-the N-n-butylamine,
(217) N-[(2-(2,3,5-trimethylammonium cyclopentadiene-first-1-naphthyl) methyl]-the N-n-butylamine,
(218) methyl N-[(2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-naphthyl)]-the N-n-butylamine,
(219) methyl N-[(2-(2-dimethylaminomethyl cyclopentadienyl)-1-naphthyl)]-the N-n-butylamine,
(220) methyl N-[(2-(3-dimethylaminomethyl cyclopentadienyl)-1-naphthyl)]-the N-n-butylamine,
(221) methyl N-[(2-(indenes-1-yl)-1-naphthyl)]-the N-n-butylamine,
(222) methyl N-[(2-(2-methyl indenes-1-yl)-1-naphthyl)]-the N-n-butylamine,
(223) methyl N-[(2-(2-phenylindan-1-yl)-1-naphthyl)]-the N-n-butylamine,
(224) methyl N-[(2-(fluorenes-9-yl)-1-naphthyl)]-the N-n-butylamine etc.
Below hydrazone compound shown in the formula (7) is described:
R wherein 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9And R 30Have with above-mentioned formula (II) in identical connotation.
The compound of formula (7) can be by making formula (1) carbonyl compound and hydrazine compound (R 30-NHNH 2) reaction and make.
As hydrazine compound, can exemplify out following compounds.
Used hydrazine comprises aromatics hydrazine such as phenylhydrazine in the reaction, the 2-procarbazine, the 3-procarbazine, the 4-procarbazine, 2, the 4-dimethyl hydrazinobenzene, 2, the 6-dimethyl hydrazinobenzene, 3, the 5-dimethyl hydrazinobenzene, 2,4,6-trimethylammonium phenylhydrazine, 2-sec.-propyl phenylhydrazine, 3-sec.-propyl phenylhydrazine, 4-sec.-propyl phenylhydrazine, 2,6-di-isopropyl phenylhydrazine, 2-tertiary butyl phenylhydrazine, 4-tertiary butyl phenylhydrazine, 2,4-di-t-butyl phenylhydrazine, 2,6-di-t-butyl phenylhydrazine, 2-phenyl phenylhydrazine, 4-phenyl phenylhydrazine, 2,4-phenylbenzene phenylhydrazine, 2,6-phenylbenzene phenylhydrazine, the penta fluoro benzene hydrazine, 3,5-two (trifluoromethyl) phenylhydrazine, naphthylhydrazine etc.; Aliphatic series hydrazine such as methylhydrazine, ethyl hydrazine, Iproniazid, uncle's fourth hydrazine, positive fourth hydrazine, isobutyl hydrazine, positive penta hydrazine, just own hydrazine, hexamethylene hydrazine, positive last of the ten Heavenly stems hydrazine, benzyl hydrazine etc.The consumption of hydrazine is generally about 0.5-1.5 mole with respect to 1 mole of carbonyl compound.
Above-mentioned reaction is implemented in solvent usually.Such solvent comprises for example alcoholic solvents such as methyl alcohol, ethanol, Virahol; Aprotic solvent, aromatic solvent such as benzene, toluene for example, aliphatic hydrocarbon solvent such as hexane, heptane, ether, tetrahydrofuran (THF), 1, ether solvents such as 4-diox, amide solvent such as hexamethylphosphoramide, dimethyl formamide, acetonitrile, propionitrile, acetone, diethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone isopolarity solvent, halogenated solvents such as methylene dichloride, ethylene dichloride, chlorobenzene, dichlorobenzene.Can use the mixture of a kind of solvent or two or more solvents.The consumption of solvent is generally the 1-200 weight part with respect to carbonyl compound shown in the 1 weight part formula (1), preferred 3-50 weight part.
Temperature of reaction is generally-100 ℃ of boiling points to solvent, is generally-80 ℃ to 120 ℃.
After the reaction, if desired, can in the gained reaction mixture, add entry.Then this mixture separation is become organic layer and water layer, to obtain target compound solution as organic layer.When because in described reaction, use with the solvent of water compatible or use a small amount of solvent and when making organic layer and water layer not easily separated, can after in reaction mixture, adding water-insoluble organic solvents such as toluene, ethyl acetate or chlorobenzene, separate.Hydrazone compound shown in the formula (7) can be purified by for example following operation: wash the described solution of this compound with water, dry described solution, distilling off solvent is also further purified through methods such as recrystallization, distillation, column chromatography processing then.
The object lesson of hydrazone compound comprises following compounds shown in the formula (7):
(1) 2-(cyclopentadienyl) benzaldehyde-phenylhydrazone,
(2) 2-(2-methyl cyclopentadienyl) benzaldehyde-phenylhydrazone,
(3) 2-(3-methyl cyclopentadienyl) benzaldehyde-phenylhydrazone,
(4) 2-(2,3-dimethyl cyclopentadienyl) benzaldehyde-phenylhydrazone,
(5) 2-(2,4-dimethyl cyclopentadienyl) benzaldehyde-phenylhydrazone,
(6) 2-(3,4-dimethyl cyclopentadienyl) benzaldehyde-phenylhydrazone,
(7) 2-(2,3,4-trimethylammonium cyclopentadienyl) benzaldehyde-phenylhydrazone,
(8) 2-(2,4,5-trimethylammonium cyclopentadienyl) benzaldehyde-phenylhydrazone,
(9) 2-(2,3,4,5-tetramethyl-ring pentadienyl) benzaldehyde-phenylhydrazone,
(10) 2-(2-tertiary butyl cyclopentadienyl) benzaldehyde-phenylhydrazone,
(11) 2-(3-tertiary butyl cyclopentadienyl) benzaldehyde-phenylhydrazone,
(12) 2-(2-dimethylamino cyclopentadienyl) benzaldehyde-phenylhydrazone,
(13) 2-(3-dimethylamino cyclopentadienyl) benzaldehyde-phenylhydrazone,
(14) 2-(indenes-1-yl) benzaldehyde-phenylhydrazone,
(15) 2-(2-methyl indenes-1-yl) benzaldehyde-phenylhydrazone,
(16) 2-(2-phenylindan-1-yl) benzaldehyde-phenylhydrazone,
(17) 2-(fluorenes-9-yl) benzaldehyde-phenylhydrazone,
(18) 2-(cyclopentadienyl) phenyl aldehyde 2-methyl phenylhydrazone,
(19) 2-(2-methyl cyclopentadienyl) phenyl aldehyde 2-methyl phenylhydrazone,
(20) 2-(3-methyl cyclopentadienyl) phenyl aldehyde 2-methyl phenylhydrazone,
(21) 2-(2,3-dimethyl cyclopentadienyl) phenyl aldehyde 2-methyl phenylhydrazone,
(22) 2-(2,4-dimethyl cyclopentadienyl) phenyl aldehyde 2-methyl phenylhydrazone,
(23) 2-(3,4-dimethyl cyclopentadienyl) phenyl aldehyde 2-methyl phenylhydrazone,
(24) 2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl aldehyde 2-methyl phenylhydrazone,
(25) 2-(2,4,5-trimethylammonium cyclopentadienyl) phenyl aldehyde 2-methyl phenylhydrazone,
(26) 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl aldehyde 2-methyl phenylhydrazone,
(27) 2-(2-tertiary butyl cyclopentadienyl) phenyl aldehyde 2-methyl phenylhydrazone,
(28) 2-(3-tertiary butyl cyclopentadienyl) phenyl aldehyde 2-methyl phenylhydrazone,
(29) 2-(2-dimethylamino cyclopentadienyl) phenyl aldehyde 2-methyl phenylhydrazone,
(30) 2-(3-dimethylamino cyclopentadienyl) phenyl aldehyde 2-methyl phenylhydrazone,
(31) 2-(indenes-1-yl) phenyl aldehyde 2-methyl phenylhydrazone,
(32) 2-(2-methyl indenes-1-yl) phenyl aldehyde 2-methyl phenylhydrazone,
(33) 2-(2-phenylindan-1-yl) phenyl aldehyde 2-methyl phenylhydrazone,
(34) 2-(fluorenes-9-yl) phenyl aldehyde 2-methyl phenylhydrazone,
(35) 2-(cyclopentadienyl) phenyl aldehyde 2,4,6-trimethylammonium phenylhydrazone,
(36) 2-(2-methyl cyclopentadienyl) phenyl aldehyde 2,4,6-trimethylammonium phenylhydrazone,
(37) 2-(3-methyl cyclopentadienyl) phenyl aldehyde 2,4,6-trimethylammonium phenylhydrazone,
(38) 2-(2,3-dimethyl cyclopentadienyl) phenyl aldehyde 2,4,6-trimethylammonium phenylhydrazone,
(39) 2-(2,4-dimethyl cyclopentadienyl) phenyl aldehyde 2,4,6-trimethylammonium phenylhydrazone,
(40) 2-(3,4-dimethyl cyclopentadienyl) phenyl aldehyde 2,4,6-trimethylammonium phenylhydrazone,
(41) 2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl aldehyde 2,4,6-trimethylammonium phenylhydrazone,
(42) 2-(2,4,5-trimethylammonium cyclopentadienyl) phenyl aldehyde 2,4,6-trimethylammonium phenylhydrazone,
(43) 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl aldehyde 2,4,6-trimethylammonium phenylhydrazone,
(44) 2-(2-tertiary butyl cyclopentadienyl) phenyl aldehyde 2,4,6-trimethylammonium phenylhydrazone,
(45) 2-(3-tertiary butyl cyclopentadienyl) phenyl aldehyde 2,4,6-trimethylammonium phenylhydrazone,
(46) 2-(2-dimethylamino cyclopentadienyl) phenyl aldehyde 2,4,6-trimethylammonium phenylhydrazone,
(47) 2-(3-dimethylamino cyclopentadienyl) phenyl aldehyde 2,4,6-trimethylammonium phenylhydrazone,
(48) 2-(indenes-1-yl) phenyl aldehyde 2,4,6-trimethylammonium phenylhydrazone,
(49) 2-(2-methyl indenes-1-yl) phenyl aldehyde 2,4,6-trimethylammonium phenylhydrazone,
(50) 2-(2-phenylindan-1-yl) phenyl aldehyde 2,4,6-trimethylammonium phenylhydrazone,
(51) 2-(fluorenes-9-yl) phenyl aldehyde 2,4,6-trimethylammonium phenylhydrazone,
(52) 2-(cyclopentadienyl) phenyl aldehyde 2,6-di-isopropyl phenylhydrazone,
(53) 2-(2-methyl cyclopentadienyl) phenyl aldehyde 2,6-di-isopropyl phenylhydrazone,
(54) 2-(3-methyl cyclopentadienyl) phenyl aldehyde 2,6-di-isopropyl phenylhydrazone,
(55) 2-(2,3-dimethyl cyclopentadienyl) phenyl aldehyde 2,6-di-isopropyl phenylhydrazone,
(56) 2-(2,4-dimethyl cyclopentadienyl) phenyl aldehyde 2,6-di-isopropyl phenylhydrazone,
(57) 2-(3,4-dimethyl cyclopentadienyl) phenyl aldehyde 2,6-di-isopropyl phenylhydrazone,
(58) 2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl aldehyde 2,6-di-isopropyl phenylhydrazone,
(59) 2-(2,4,5-trimethylammonium cyclopentadienyl) phenyl aldehyde 2,6-di-isopropyl phenylhydrazone,
(60) 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl aldehyde 2,6-di-isopropyl phenylhydrazone,
(61) 2-(2-tertiary butyl cyclopentadienyl) phenyl aldehyde 2,6-di-isopropyl phenylhydrazone,
(62) 2-(3-tertiary butyl cyclopentadienyl) phenyl aldehyde 2,6-di-isopropyl phenylhydrazone,
(63) 2-(2-dimethylamino cyclopentadienyl) phenyl aldehyde 2,6-di-isopropyl phenylhydrazone,
(64) 2-(3-dimethylamino cyclopentadienyl) phenyl aldehyde 2,6-di-isopropyl phenylhydrazone,
(65) 2-(indenes-1-yl) phenyl aldehyde 2,6-di-isopropyl phenylhydrazone,
(66) 2-(2-methyl indenes-1-yl) phenyl aldehyde 2,6-di-isopropyl phenylhydrazone,
(67) 2-(2-phenylindan-1-yl) phenyl aldehyde 2,6-di-isopropyl phenylhydrazone,
(68) 2-(fluorenes-9-yl) phenyl aldehyde 2,6-di-isopropyl phenylhydrazone,
(69) 2-(cyclopentadienyl) phenyl aldehyde 2-naphthalene hydrazone,
(70) 2-(2-methyl cyclopentadienyl) phenyl aldehyde 2-naphthalene hydrazone,
(71) 2-(3-methyl cyclopentadienyl) phenyl aldehyde 2-naphthalene hydrazone,
(72) 2-(2,3-dimethyl cyclopentadienyl) phenyl aldehyde 2-naphthalene hydrazone,
(73) 2-(2,4-dimethyl cyclopentadienyl) phenyl aldehyde 2-naphthalene hydrazone,
(74) 2-(3,4-dimethyl cyclopentadienyl) phenyl aldehyde 2-naphthalene hydrazone,
(75) 2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl aldehyde 2-naphthalene hydrazone,
(76) 2-(2,4,5-trimethylammonium cyclopentadienyl) phenyl aldehyde 2-naphthalene hydrazone,
(77) 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl aldehyde 2-naphthalene hydrazone,
(78) 2-(2-tertiary butyl cyclopentadienyl) phenyl aldehyde 2-naphthalene hydrazone,
(79) 2-(3-tertiary butyl cyclopentadienyl) phenyl aldehyde 2-naphthalene hydrazone,
(80) 2-(2-dimethylamino cyclopentadienyl) phenyl aldehyde 2-naphthalene hydrazone,
(81) 2-(3-dimethylamino cyclopentadienyl) phenyl aldehyde 2-naphthalene hydrazone,
(82) 2-(indenes-1-yl) phenyl aldehyde 2-naphthalene hydrazone,
(83) 2-(2-methyl indenes-1-yl) phenyl aldehyde 2-naphthalene hydrazone,
(84) 2-(2-phenylindan-1-yl) phenyl aldehyde 2-naphthalene hydrazone,
(85) 2-(fluorenes-9-yl) phenyl aldehyde 2-naphthalene hydrazone,
(86) 2-(cyclopentadienyl) phenyl aldehyde hexamethylene hydrazone,
(87) 2-(2-methyl cyclopentadienyl) phenyl aldehyde hexamethylene hydrazone,
(88) 2-(3-methyl cyclopentadienyl) phenyl aldehyde hexamethylene hydrazone,
(89) 2-(2,3-dimethyl cyclopentadienyl) phenyl aldehyde hexamethylene hydrazone,
(90) 2-(2,4-dimethyl cyclopentadienyl) phenyl aldehyde hexamethylene hydrazone,
(91) 2-(3,4-dimethyl cyclopentadienyl) phenyl aldehyde hexamethylene hydrazone,
(92) 2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl aldehyde hexamethylene hydrazone,
(93) 2-(2,4,5-trimethylammonium cyclopentadienyl) phenyl aldehyde hexamethylene hydrazone,
(94) 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl aldehyde hexamethylene hydrazone,
(95) 2-(2-tertiary butyl cyclopentadienyl) phenyl aldehyde hexamethylene hydrazone,
(96) 2-(3-tertiary butyl cyclopentadienyl) phenyl aldehyde hexamethylene hydrazone,
(97) 2-(2-dimethylamino cyclopentadienyl) phenyl aldehyde hexamethylene hydrazone,
(98) 2-(3-dimethylamino cyclopentadienyl) phenyl aldehyde hexamethylene hydrazone,
(99) 2-(indenes-1-yl) phenyl aldehyde hexamethylene hydrazone,
(100) 2-(2-methyl indenes-1-yl) phenyl aldehyde hexamethylene hydrazone,
(101) 2-(2-phenylindan-1-yl) phenyl aldehyde hexamethylene hydrazone,
(102) 2-(fluorenes-9-yl) phenyl aldehyde hexamethylene hydrazone,
(103) 2-(cyclopentadienyl) phenyl aldehyde uncle fourth hydrazone,
(104) 2-(2-methyl cyclopentadienyl) phenyl aldehyde uncle fourth hydrazone,
(105) 2-(3-methyl cyclopentadienyl) phenyl aldehyde uncle fourth hydrazone,
(106) 2-(2,3-dimethyl cyclopentadienyl) phenyl aldehyde uncle fourth hydrazone,
(107) 2-(2,4-dimethyl cyclopentadienyl) phenyl aldehyde uncle fourth hydrazone,
(108) 2-(3,4-dimethyl cyclopentadienyl) phenyl aldehyde uncle fourth hydrazone,
(109) 2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl aldehyde uncle fourth hydrazone,
(110) 2-(2,4,5-trimethylammonium cyclopentadienyl) phenyl aldehyde uncle fourth hydrazone,
(111) 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl aldehyde uncle fourth hydrazone,
(112) 2-(2-tertiary butyl cyclopentadienyl) phenyl aldehyde uncle fourth hydrazone,
(113) 2-(3-tertiary butyl cyclopentadienyl) phenyl aldehyde uncle fourth hydrazone,
(114) 2-(2-dimethylamino cyclopentadienyl) phenyl aldehyde uncle fourth hydrazone,
(115) 2-(3-dimethylamino cyclopentadienyl) phenyl aldehyde uncle fourth hydrazone,
(116) 2-(indenes-1-yl) phenyl aldehyde uncle fourth hydrazone,
(117) 2-(2-methyl indenes-1-yl) phenyl aldehyde uncle fourth hydrazone,
(118) 2-(2-phenylindan-1-yl) phenyl aldehyde uncle fourth hydrazone,
(119) 2-(fluorenes-9-yl) phenyl aldehyde uncle fourth hydrazone,
(120) 2-(cyclopentadienyl)-1-naphthaldehyde phenylhydrazone,
(121) 2-(2-methyl cyclopentadienyl)-1-naphthaldehyde phenylhydrazone,
(122) 2-(3-methyl cyclopentadienyl)-1-naphthaldehyde phenylhydrazone,
(123) 2-(2,3-dimethyl cyclopentadienyl)-1-naphthaldehyde phenylhydrazone,
(124) 2-(2,4-dimethyl cyclopentadienyl)-1-naphthaldehyde phenylhydrazone,
(125) 2-(3,4-dimethyl cyclopentadienyl)-1-naphthaldehyde phenylhydrazone,
(126) 2-(2,3,4-trimethylammonium cyclopentadienyl)-1-naphthaldehyde phenylhydrazone,
(127) 2-(2,4,5-trimethylammonium cyclopentadienyl)-1-naphthaldehyde phenylhydrazone,
(128) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-naphthaldehyde phenylhydrazone,
(129) 2-(2-tertiary butyl cyclopentadienyl)-1-naphthaldehyde phenylhydrazone,
(130) 2-(3-tertiary butyl cyclopentadienyl)-1-naphthaldehyde phenylhydrazone,
(131) 2-(2-dimethylamino cyclopentadienyl)-1-naphthaldehyde phenylhydrazone,
(132) 2-(3-dimethylamino cyclopentadienyl)-1-naphthaldehyde phenylhydrazone,
(133) 2-(indenes-1-yl)-1-naphthaldehyde phenylhydrazone,
(134) 2-(2-methyl indenes-1-yl)-1-naphthaldehyde phenylhydrazone,
(135) 2-(2-phenylindan-1-yl)-1-naphthaldehyde phenylhydrazone,
(136) 2-(fluorenes-9-yl)-1-naphthaldehyde phenylhydrazone,
(137) 2-(cyclopentadienyl) methyl phenyl ketone phenylhydrazone,
(138) 2-(2-methyl cyclopentadienyl) methyl phenyl ketone phenylhydrazone,
(139) 2-(3-methyl cyclopentadienyl) methyl phenyl ketone phenylhydrazone,
(140) 2-(2,3-dimethyl cyclopentadienyl) methyl phenyl ketone phenylhydrazone,
(141) 2-(2,4-dimethyl cyclopentadienyl) methyl phenyl ketone phenylhydrazone,
(142) 2-(3,4-dimethyl cyclopentadienyl) methyl phenyl ketone phenylhydrazone,
(143) 2-(2,3,4-trimethylammonium cyclopentadienyl) methyl phenyl ketone phenylhydrazone,
(144) 2-(2,4,5-trimethylammonium cyclopentadienyl) methyl phenyl ketone phenylhydrazone,
(145) 2-(2,3,4,5-tetramethyl-ring pentadienyl) methyl phenyl ketone phenylhydrazone,
(146) 2-(2-tertiary butyl cyclopentadienyl) methyl phenyl ketone phenylhydrazone,
(147) 2-(3-tertiary butyl cyclopentadienyl) methyl phenyl ketone phenylhydrazone,
(148) 2-(2-dimethylamino cyclopentadienyl) methyl phenyl ketone phenylhydrazone,
(149) 2-(3-dimethylamino cyclopentadienyl) methyl phenyl ketone phenylhydrazone,
(150) 2-(indenes-1-yl) methyl phenyl ketone phenylhydrazone,
(151) 2-(2-methyl indenes-1-yl) methyl phenyl ketone phenylhydrazone,
(152) 2-(2-phenylindan-1-yl) methyl phenyl ketone phenylhydrazone,
(153) 2-(fluorenes-9-yl) methyl phenyl ketone phenylhydrazone,
(154) 2-(cyclopentadienyl) methyl phenyl ketone 2-methyl phenylhydrazone,
(155) 2-(2-methyl cyclopentadienyl) methyl phenyl ketone 2-methyl phenylhydrazone,
(156) 2-(3-methyl cyclopentadienyl) methyl phenyl ketone 2-methyl phenylhydrazone,
(157) 2-(2,3-dimethyl cyclopentadienyl) methyl phenyl ketone 2-methyl phenylhydrazone,
(158) 2-(2,4-dimethyl cyclopentadienyl) methyl phenyl ketone 2-methyl phenylhydrazone,
(159) 2-(3,4-dimethyl cyclopentadienyl) methyl phenyl ketone 2-methyl phenylhydrazone,
(160) 2-(2,3,4-trimethylammonium cyclopentadienyl) methyl phenyl ketone 2-methyl phenylhydrazone,
(161) 2-(2,4,5-trimethylammonium cyclopentadienyl) methyl phenyl ketone 2-methyl phenylhydrazone,
(162) 2-(2,3,4,5-tetramethyl-ring pentadienyl) methyl phenyl ketone 2-methyl phenylhydrazone,
(163) 2-(2-tertiary butyl cyclopentadienyl) methyl phenyl ketone 2-methyl phenylhydrazone,
(164) 2-(3-tertiary butyl cyclopentadienyl) methyl phenyl ketone 2-methyl phenylhydrazone,
(165) 2-(2-dimethylamino cyclopentadienyl) methyl phenyl ketone 2-methyl phenylhydrazone,
(166) 2-(3-dimethylamino cyclopentadienyl) methyl phenyl ketone 2-methyl phenylhydrazone,
(167) 2-(indenes-1-yl) methyl phenyl ketone 2-methyl phenylhydrazone,
(168) 2-(2-methyl indenes-1-yl) methyl phenyl ketone 2-methyl phenylhydrazone,
(169) 2-(2-phenylindan-1-yl) methyl phenyl ketone 2-methyl phenylhydrazone,
(170) 2-(fluorenes-9-yl) methyl phenyl ketone 2-methyl phenylhydrazone,
(171) 2-(cyclopentadienyl) methyl phenyl ketone 2,4,6-trimethylammonium phenylhydrazone,
(172) 2-(2-methyl cyclopentadienyl) methyl phenyl ketone 2,4,6-trimethylammonium phenylhydrazone,
(173) 2-(3-methyl cyclopentadienyl) methyl phenyl ketone 2,4,6-trimethylammonium phenylhydrazone,
(174) 2-(2,3-dimethyl cyclopentadienyl) methyl phenyl ketone 2,4,6-trimethylammonium phenylhydrazone,
(175) 2-(2,4-dimethyl cyclopentadienyl) methyl phenyl ketone 2,4,6-trimethylammonium phenylhydrazone,
(176) 2-(3,4-dimethyl cyclopentadienyl) methyl phenyl ketone 2,4,6-trimethylammonium phenylhydrazone,
(177) 2-(2,3,4-trimethylammonium cyclopentadienyl) methyl phenyl ketone 2,4,6-trimethylammonium phenylhydrazone,
(178) 2-(2,4,5-trimethylammonium cyclopentadienyl) methyl phenyl ketone 2,4,6-trimethylammonium phenylhydrazone,
(179) 2-(2,3,4,5-tetramethyl-ring pentadienyl) methyl phenyl ketone 2,4,6-trimethylammonium phenylhydrazone,
(180) 2-(2-tertiary butyl cyclopentadienyl) methyl phenyl ketone 2,4,6-trimethylammonium phenylhydrazone,
(181) 2-(3-tertiary butyl cyclopentadienyl) methyl phenyl ketone 2,4,6-trimethylammonium phenylhydrazone,
(182) 2-(2-dimethylamino cyclopentadienyl) methyl phenyl ketone 2,4,6-trimethylammonium phenylhydrazone,
(183) 2-(3-dimethylamino cyclopentadienyl) methyl phenyl ketone 2,4,6-trimethylammonium phenylhydrazone,
(184) 2-(indenes-1-yl) methyl phenyl ketone 2,4,6-trimethylammonium phenylhydrazone,
(185) 2-(2-methyl indenes-1-yl) methyl phenyl ketone 2,4,6-trimethylammonium phenylhydrazone,
(186) 2-(2-phenylindan-1-yl) methyl phenyl ketone 2,4,6-trimethylammonium phenylhydrazone,
(187) 2-(fluorenes-9-yl) methyl phenyl ketone 2,4,6-trimethylammonium phenylhydrazone,
(188) 2-(cyclopentadienyl) methyl phenyl ketone 2,6-di-isopropyl phenylhydrazone,
(189) 2-(2-methyl cyclopentadienyl) methyl phenyl ketone 2,6-di-isopropyl phenylhydrazone,
(190) 2-(3-methyl cyclopentadienyl) methyl phenyl ketone 2,6-di-isopropyl phenylhydrazone,
(191) 2-(2,3-dimethyl cyclopentadienyl) methyl phenyl ketone 2,6-di-isopropyl phenylhydrazone,
(192) 2-(2,4-dimethyl cyclopentadienyl) methyl phenyl ketone 2,6-di-isopropyl phenylhydrazone,
(193) 2-(3,4-dimethyl cyclopentadienyl) methyl phenyl ketone 2,6-di-isopropyl phenylhydrazone,
(194) 2-(2,3,4-trimethylammonium cyclopentadienyl) methyl phenyl ketone 2,6-di-isopropyl phenylhydrazone,
(195) 2-(2,4,5-trimethylammonium cyclopentadienyl) methyl phenyl ketone 2,6-di-isopropyl phenylhydrazone,
(196) 2-(2,3,4,5-tetramethyl-ring pentadienyl) methyl phenyl ketone 2,6-di-isopropyl phenylhydrazone,
(197) 2-(2-tertiary butyl cyclopentadienyl) methyl phenyl ketone 2,6-di-isopropyl phenylhydrazone,
(198) 2-(3-tertiary butyl cyclopentadienyl) methyl phenyl ketone 2,6-di-isopropyl phenylhydrazone,
(199) 2-(2-dimethylamino cyclopentadienyl) methyl phenyl ketone 2,6-di-isopropyl phenylhydrazone,
(200) 2-(3-dimethylamino cyclopentadienyl) methyl phenyl ketone 2,6-di-isopropyl phenylhydrazone,
(201) 2-(indenes-1-yl) methyl phenyl ketone 2,6-di-isopropyl phenylhydrazone,
(202) 2-(2-methyl indenes-1-yl) methyl phenyl ketone 2,6-di-isopropyl phenylhydrazone,
(203) 2-(2-phenylindan-1-yl) methyl phenyl ketone 2,6-di-isopropyl phenylhydrazone,
(204) 2-(fluorenes-9-yl) methyl phenyl ketone 2,6-di-isopropyl phenylhydrazone,
(205) 2-(cyclopentadienyl) methyl phenyl ketone 2-naphthalene hydrazone,
(206) 2-(2-methyl cyclopentadienyl) methyl phenyl ketone 2-naphthalene hydrazone,
(207) 2-(3-methyl cyclopentadienyl) methyl phenyl ketone 2-naphthalene hydrazone,
(208) 2-(2,3-dimethyl cyclopentadienyl) methyl phenyl ketone 2-naphthalene hydrazone,
(209) 2-(2,4-dimethyl cyclopentadienyl) methyl phenyl ketone 2-naphthalene hydrazone,
(210) 2-(3,4-dimethyl cyclopentadienyl) methyl phenyl ketone 2-naphthalene hydrazone,
(211) 2-(2,3,4-trimethylammonium cyclopentadienyl) methyl phenyl ketone 2-naphthalene hydrazone,
(212) 2-(2,4,5-trimethylammonium cyclopentadienyl) methyl phenyl ketone 2-naphthalene hydrazone,
(213) 2-(2,3,4,5-tetramethyl-ring pentadienyl) methyl phenyl ketone 2-naphthalene hydrazone,
(214) 2-(2-tertiary butyl cyclopentadienyl) methyl phenyl ketone 2-naphthalene hydrazone,
( 215) 2-(3-tertiary butyl cyclopentadienyl) methyl phenyl ketone 2-naphthalene hydrazone,
(216) 2-(2-dimethylamino cyclopentadienyl) methyl phenyl ketone 2-naphthalene hydrazone,
(217) 2-(3-dimethylamino cyclopentadienyl) methyl phenyl ketone 2-naphthalene hydrazone,
(218) 2-(indenes-1-yl) methyl phenyl ketone 2-naphthalene hydrazone,
(219) 2-(2-methyl indenes-1-yl) methyl phenyl ketone 2-naphthalene hydrazone,
(220) 2-(2-phenylindan-1-yl) methyl phenyl ketone 2-naphthalene hydrazone,
(221) 2-(fluorenes-9-yl) methyl phenyl ketone 2-naphthalene hydrazone,
(222) 2-(cyclopentadienyl) methyl phenyl ketone hexamethylene hydrazone,
(223) 2-(2-methyl cyclopentadienyl) methyl phenyl ketone hexamethylene hydrazone,
(224) 2-(3-methyl cyclopentadienyl) methyl phenyl ketone hexamethylene hydrazone,
(225) 2-(2,3-dimethyl cyclopentadienyl) methyl phenyl ketone hexamethylene hydrazone,
(226) 2-(2,4-dimethyl cyclopentadienyl) methyl phenyl ketone hexamethylene hydrazone,
(227) 2-(3,4-dimethyl cyclopentadienyl) methyl phenyl ketone hexamethylene hydrazone,
(228) 2-(2,3,4-trimethylammonium cyclopentadienyl) methyl phenyl ketone hexamethylene hydrazone,
(229) 2-(2,4,5-trimethylammonium cyclopentadienyl) methyl phenyl ketone hexamethylene hydrazone,
(230) 2-(2,3,4,5-tetramethyl-ring pentadienyl) methyl phenyl ketone hexamethylene hydrazone,
(231) 2-(2-tertiary butyl cyclopentadienyl) methyl phenyl ketone hexamethylene hydrazone,
(232) 2-(3-tertiary butyl cyclopentadienyl) methyl phenyl ketone hexamethylene hydrazone,
(233) 2-(2-dimethylamino cyclopentadienyl) methyl phenyl ketone hexamethylene hydrazone,
(234) 2-(3-dimethylamino cyclopentadienyl) methyl phenyl ketone hexamethylene hydrazone,
(235) 2-(indenes-1-yl) methyl phenyl ketone hexamethylene hydrazone,
(236) 2-(2-methyl indenes-1-yl) methyl phenyl ketone hexamethylene hydrazone,
(237) 2-(2-phenylindan-1-yl) methyl phenyl ketone hexamethylene hydrazone,
(238) 2-(fluorenes-9-yl) methyl phenyl ketone hexamethylene hydrazone,
(239) 2-(cyclopentadienyl) methyl phenyl ketone uncle fourth hydrazone,
(240) 2-(2-methyl cyclopentadienyl) methyl phenyl ketone uncle fourth hydrazone,
(241) 2-(3-methyl cyclopentadienyl) methyl phenyl ketone uncle fourth hydrazone,
(242) 2-(2,3-dimethyl cyclopentadienyl) methyl phenyl ketone uncle fourth hydrazone,
(243) 2-(2,4-dimethyl cyclopentadienyl) methyl phenyl ketone uncle fourth hydrazone,
(244) 2-(3,4-dimethyl cyclopentadienyl) methyl phenyl ketone uncle fourth hydrazone,
(245) 2-(2,3,4-trimethylammonium cyclopentadienyl) methyl phenyl ketone uncle fourth hydrazone,
(246) 2-(2,4,5-trimethylammonium cyclopentadienyl) methyl phenyl ketone uncle fourth hydrazone,
(247) 2-(2,3,4,5-tetramethyl-ring pentadienyl) methyl phenyl ketone uncle fourth hydrazone,
(248) 2-(2-tertiary butyl cyclopentadienyl) methyl phenyl ketone uncle fourth hydrazone,
(249) 2-(3-tertiary butyl cyclopentadienyl) methyl phenyl ketone uncle fourth hydrazone,
(250) 2-(2-dimethylamino cyclopentadienyl) methyl phenyl ketone uncle fourth hydrazone,
(251) 2-(3-dimethylamino cyclopentadienyl) methyl phenyl ketone uncle fourth hydrazone,
(252) 2-(indenes-1-yl) methyl phenyl ketone uncle fourth hydrazone,
(253) 2-(2-methyl indenes-1-yl) methyl phenyl ketone uncle fourth hydrazone,
(254) 2-(2-phenylindan-1-yl) methyl phenyl ketone uncle fourth hydrazone,
(255) 2-(fluorenes-9-yl) methyl phenyl ketone uncle fourth hydrazone etc.
Below substituted cyclopentadiene compound shown in the formula (8) is described:
Figure G2006100046087D00921
R wherein 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8And R 9Have with above-mentioned formula (I) in identical connotation.
The compound of formula (8) can make by making the reaction of compound shown in nitrile compound shown in the formula (10) or the formula (11) and nucleophilic reagent (organolithium compound or organo-magnesium compound):
Figure G2006100046087D00922
R wherein 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8And R 9Have with above-mentioned formula (II) in identical connotation,
R wherein 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9And R 30Have with above-mentioned formula (II) in identical connotation.
Used nucleophilic reagent comprises (R such as above-mentioned organolithium compound, organo-magnesium compound in this reaction 1Li or R 1MgX; Wherein X is a halogen atom; Condition is R 1Be not hydrogen atom).
Such nucleophilic reagent comprises methylmagnesium-bromide, ethyl-magnesium-bromide, phenyl-magnesium-bromide, bromination normal-butyl magnesium, bromination tertiary butyl magnesium, lithium methide, phenyl lithium, tert-butyl lithium etc.Equally, can also exemplify the compound that magnesium bromide in the above-claimed cpd changes magnesium chloride or magnesium iodide into.
Though known 2-(4-methoxyl group-indenes-1-yl) benzonitrile can obtain with the reaction of precursor Spironolactone by making the amination methyl aluminum chloride (methylchloroaluminum amide) derived from unmanageable trimethyl aluminium, described method is a universal synthesis method not necessarily, and can not be satisfactory, this is will generate acid amides and carboxylic acid byproduct (Bioorg.Med.Chem.Lett. simultaneously because of it, 1993,3,55).But,, can easily obtain comprising the nitrile compound of the present invention of above-mentioned nitrile compound according to the inventive method.
The object lesson of nitrile compound comprises following compounds shown in the formula (10):
(1) 2-(cyclopentadienyl) benzonitrile,
(2) 2-(2-methyl cyclopentadienyl) benzonitrile,
(3) 2-(3-methyl cyclopentadienyl) benzonitrile,
(4) 2-(2,3-dimethyl cyclopentadienyl) benzonitrile,
(5) 2-(2,4-dimethyl cyclopentadienyl) benzonitrile,
(6) 2-(2,3,4-trimethylammonium cyclopentadienyl) benzonitrile,
(7) 2-(2,3,5-trimethylammonium cyclopentadienyl) benzonitrile,
(8) 2-(2,3,4,5-tetramethyl-ring pentadienyl) benzonitrile,
(9) 2-(2-dimethylamino cyclopentadienyl) benzonitrile,
(10) 2-(3-dimethylamino cyclopentadienyl) benzonitrile,
(11) 2-(indenes-1-yl) benzonitrile,
(12) 2-(2-methyl indenes-1-yl) benzonitrile,
(13) 2-(2-phenylindan-1-yl) benzonitrile,
(14) 2-(cyclopentadienyl)-1-cyano group naphthalene,
(15) 2-(2-methyl cyclopentadienyl)-1-cyano group naphthalene,
(16) 2-(3-methyl cyclopentadienyl)-1-cyano group naphthalene,
(17) 2-(2,3-dimethyl cyclopentadienyl)-1-cyano group naphthalene,
(18) 2-(2,4-dimethyl cyclopentadienyl)-1-cyano group naphthalene,
(19) 2-(2,3,4-trimethylammonium cyclopentadienyl)-1-cyano group naphthalene,
(20) 2-(2,3,5-trimethylammonium cyclopentadienyl)-1-cyano group naphthalene,
(21) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-cyano group naphthalene,
(22) 2-(2-dimethylamino cyclopentadienyl)-1-cyano group naphthalene,
(23) 2-(3-dimethylamino cyclopentadienyl)-1-cyano group naphthalene,
(24) 2-(indenes-1-yl)-1-cyano group naphthalene,
(25) 2-(2-methyl indenes-1-yl)-1-cyano group naphthalene,
(26) 2-(2-phenylindan-1-yl)-1-cyano group naphthalene,
(27) 3-(cyclopentadienyl)-2-cyano group naphthalene,
(28) 3-(2-methyl cyclopentadienyl)-2-cyano group naphthalene,
(29) 3-(3-methyl cyclopentadienyl)-2-cyano group naphthalene,
(30) 3-(2,3-dimethyl cyclopentadienyl)-2-cyano group naphthalene,
(31) 3-(2,4-dimethyl cyclopentadienyl)-2-cyano group naphthalene,
(32) 3-(2,3,4-trimethylammonium cyclopentadienyl)-2-cyano group naphthalene,
(33) 3-(2,3,5-trimethylammonium cyclopentadienyl)-2-cyano group naphthalene,
(34) 3-(2,3,4,5-tetramethyl-ring pentadienyl)-2-cyano group naphthalene,
(35) 3-(2-dimethylamino cyclopentadienyl)-2-cyano group naphthalene,
(36) 3-(3-dimethylamino cyclopentadienyl)-2-cyano group naphthalene,
(37) 3-(indenes-1-yl)-2-cyano group naphthalene,
(38) 3-(2-methyl indenes-1-yl)-2-cyano group naphthalene,
(39) 3-(2-phenylindan-1-yl)-2-cyano group naphthalene,
(40) 3-dimethylamino-6-(cyclopentadienyl) benzonitrile,
(41) 3-dimethylamino-6-(2-methyl cyclopentadienyl) benzonitrile,
(42) 3-dimethylamino-6-(3-methyl cyclopentadienyl) benzonitrile,
(43) 3-dimethylamino-6-(2,3-dimethyl cyclopentadienyl) benzonitrile,
(44) 3-dimethylamino-6-(2,4-dimethyl cyclopentadienyl) benzonitrile,
(45) 3-dimethylamino-6-(2,3,4-trimethylammonium cyclopentadienyl) benzonitrile,
(46) 3-dimethylamino-6-(2,3,5-trimethylammonium cyclopentadienyl) benzonitrile,
(47) 3-dimethylamino-6-(2,3,4,5-tetramethyl-ring pentadienyl) benzonitrile,
(48) 3-dimethylamino-6-(2-dimethylamino cyclopentadienyl) benzonitrile,
(49) 3-dimethylamino-6-(3-dimethylamino cyclopentadienyl) benzonitrile,
(50) 3-dimethylamino-6-(indenes-1-yl) benzonitrile,
(51) 3-dimethylamino-6-(2-methyl indenes-1-yl) benzonitrile,
(52) 3-dimethylamino-6-(2-phenylindan-1-yl) benzonitrile etc.
The object lesson of oxime ether compound comprises following compounds shown in the formula (11):
(1) O-methyl-2-(cyclopentadienyl) benzaldoxime,
(2) O-methyl-2-(2-methyl cyclopentadienyl) benzaldoxime,
(3) O-methyl-2-(3-methyl cyclopentadienyl) benzaldoxime,
(4) O-methyl-2-(2,3-dimethyl cyclopentadienyl) benzaldoxime,
(5) O-methyl-2-(2,4-dimethyl cyclopentadienyl) benzaldoxime,
(6) O-methyl-2-(2,3,4-trimethylammonium cyclopentadienyl) benzaldoxime,
(7) O-methyl-2-(2,3,5-trimethylammonium cyclopentadienyl) benzaldoxime,
(8) O-methyl-2-(2,3,4,5-tetramethyl-ring pentadienyl) benzaldoxime,
(9) O-methyl-2-(2-dimethylamino cyclopentadienyl) benzaldoxime,
(10) O-methyl-2-(3-dimethylamino cyclopentadienyl) benzaldoxime,
(11) O-methyl-2-(indenes-1-yl) benzaldoxime,
(12) O-methyl-2-(2-methyl indenes-1-yl) benzaldoxime,
(13) O-methyl-2-(2-phenylindan-1-yl) benzaldoxime,
(14) O-methyl-2-(cyclopentadienyl)-1-naphthaldehyde oxime,
(15) O-methyl-2-(2-methyl cyclopentadienyl)-1-naphthaldehyde oxime,
(16) O-methyl-(3-methyl cyclopentadienyl)-1-naphthaldehyde oxime,
(17) O-methyl-2-(2,3-dimethyl cyclopentadienyl)-1-naphthaldehyde oxime,
(18) O-methyl-2-(2,4-dimethyl cyclopentadienyl)-1-naphthaldehyde oxime,
(19) O-methyl-2-(2,3,4-trimethylammonium cyclopentadienyl)-1-naphthaldehyde oxime,
(20) O-methyl-2-(2,3,5-trimethylammonium cyclopentadienyl)-1-naphthaldehyde oxime,
(21) O-methyl-2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-naphthaldehyde oxime,
(22) O-methyl-2-(2-dimethylamino cyclopentadienyl)-1-naphthaldehyde oxime,
(23) O-methyl-2-(3-dimethylamino cyclopentadienyl)-1-naphthaldehyde oxime,
(24) O-methyl-2-(indenes-1-yl)-1-naphthaldehyde oxime,
(25) O-methyl-2-(2-methyl indenes-1-yl)-1-naphthaldehyde oxime,
(26) O-methyl-2-(2-phenylindan-1-yl)-1-naphthaldehyde oxime,
(27) O-methyl-3-(cyclopentadienyl)-2-naphthaldehyde oxime,
(28) O-methyl-3-(2-methyl cyclopentadienyl)-2-naphthaldehyde oxime,
(29) O-methyl-3-(3-methyl cyclopentadienyl)-2-naphthaldehyde oxime,
(30) O-methyl-3-(2,3-dimethyl cyclopentadienyl)-2-naphthaldehyde oxime,
(31) O-methyl-3-(2,4-dimethyl cyclopentadienyl)-2-naphthaldehyde oxime,
(32) O-methyl-3-(2,3,4-trimethylammonium cyclopentadienyl)-2-naphthaldehyde oxime,
(33) O-methyl-3-(2,3,5-trimethylammonium cyclopentadienyl)-2-naphthaldehyde oxime,
(34) O-methyl-3-(2,3,4,5-tetramethyl-ring pentadienyl)-2-naphthaldehyde oxime,
(35) O-methyl-3-(2-dimethylamino cyclopentadienyl)-2-naphthaldehyde oxime,
(36) O-methyl-3-(3-dimethylamino cyclopentadienyl)-2-naphthaldehyde oxime,
(37) O-methyl-3-(indenes-1-yl)-2-naphthaldehyde oxime,
(38) O-methyl-3-(2-methyl indenes-1-yl)-2-naphthaldehyde oxime,
(39) O-methyl-3-(2-phenylindan-1-yl)-2-naphthaldehyde oxime,
(40) O-methyl-3-dimethylamino-6-(cyclopentadienyl)-benzaldoxime,
(41) O-methyl-3-dimethylamino-6-(2-methyl cyclopentadienyl)-benzaldoxime,
(42) O-methyl-3-dimethylamino-6-(3-methyl cyclopentadienyl)-benzaldoxime,
(43) O-methyl-3-dimethylamino-6-(2,3-dimethyl cyclopentadienyl)-benzaldoxime,
(44) O-methyl-3-dimethylamino-6-(2,4-dimethyl cyclopentadienyl)-benzaldoxime,
(45) O-methyl-3-dimethylamino-6-(2,3,4-trimethylammonium cyclopentadienyl)-benzaldoxime,
(46) O-methyl-3-dimethylamino-6-(2,3,5-trimethylammonium cyclopentadienyl)-benzaldoxime,
(47) O-methyl-3-dimethylamino-6-(2,3,4,5-tetramethyl-ring pentadienyl)-benzaldoxime,
(48) O-methyl-3-dimethylamino-6-(2-dimethylamino cyclopentadienyl)-benzaldoxime,
(49) O-methyl-3-dimethylamino-6-(3-dimethylamino cyclopentadienyl)-benzaldoxime,
(50) O-methyl-3-dimethylamino-6-(indenes-1-yl)-benzaldoxime,
(51) O-methyl-3-dimethylamino-6-(2-methyl indenes-1-yl)-benzaldoxime,
(52) O-methyl-3-dimethylamino-6-(2-phenylindan-1-yl)-benzaldoxime etc.
Equally, can also exemplify out the compound that O-methyl in the above-claimed cpd changes O-ethyl or O-benzyl into.
Existence is based on the isomer of the nitrogen-oxygen key of oxime ether.The present invention also comprises these isomer and composition thereof.
The reaction of compound shown in nucleophilic reagent and formula (10) or (11) is implemented in inert solvent usually.Such solvent comprises for example aprotic solvent: as aromatic solvents such as benzene and toluene; Aliphatic hydrocarbon solvent such as hexane, heptane; Ether, tetrahydrofuran (THF), 1, ether solvents such as 4-diox; Amide solvent such as hexamethylphosphoramide, dimethyl formamide; Acetonitrile, propionitrile, acetone, diethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone isopolarity solvent; Halogenated solvents such as methylene dichloride, ethylene dichloride, chlorobenzene, dichlorobenzene.Can use the mixture of a kind of solvent or two or more solvents.The consumption of solvent is generally 1-200 times of substituted-cyclopentadienyl weight shown in formula (10) or (11), and preferred 3-50 doubly.
Temperature of reaction is generally-100 ℃ of boiling points to solvent, is preferably-80 ℃ to 120 ℃.
After the reaction, if desired, can in the gained reaction mixture, add entry.Then this mixture separation is become organic layer and water layer, to obtain target compound solution as organic layer.When because in described reaction, use with the solvent of water compatible or use a small amount of solvent and when making organic layer and water layer not easily separated, can after in reaction mixture, adding water-insoluble organic solvents such as toluene, ethyl acetate or chlorobenzene etc., separate.Group with imine moiety shown in the formula (8) can be purified by for example following operation: wash the solution of this compound with water, dry described solution, distilling off solvent is also further purified through methods such as recrystallization, distillation, column chromatography processing then.
The object lesson of group with imine moiety comprises following compounds shown in the formula that obtains thus (8):
(1) 2-(cyclopentadienyl)-α-tertiary butyl-benzimide,
(2) 2-(2-methyl cyclopentadienyl)-α-tertiary butyl-benzimide,
(3) 2-(3-methyl cyclopentadienyl)-α-tertiary butyl-benzimide,
(4) 2-(2,3-dimethyl cyclopentadienyl)-α-tertiary butyl-benzimide,
(5) 2-(2,4-dimethyl cyclopentadienyl)-α-tertiary butyl-benzimide,
(6) 2-(2,3,4-trimethylammonium cyclopentadienyl)-α-tertiary butyl-benzimide,
(7) 2-(2,3,5-trimethylammonium cyclopentadienyl)-α-tertiary butyl-benzimide,
(8) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-benzimide,
(9) 2-(2-dimethylaminomethyl cyclopentadienyl)-α-tertiary butyl-benzimide,
(10) 2-(3-dimethylaminomethyl cyclopentadienyl)-α-tertiary butyl-benzimide,
(11) 2-(indenes-1-yl)-α-tertiary butyl-benzimide,
(12) 2-(2-methyl indenes-1-yl)-α-tertiary butyl-benzimide,
(13) 2-(2-phenylindan-1-yl)-α-tertiary butyl-benzimide,
(14) 2-(fluorenes-9-yl)-α-tertiary butyl-benzimide,
(15) 2-(cyclopentadienyl)-α-normal-butyl-benzimide,
(16) 2-(2-methyl cyclopentadienyl)-α-normal-butyl-benzimide,
(17) 2-(3-methyl cyclopentadienyl)-α-normal-butyl-benzimide,
(18) 2-(2,3-dimethyl cyclopentadienyl)-α-normal-butyl-benzimide,
(19) 2-(2,4-dimethyl cyclopentadienyl)-α-normal-butyl-benzimide,
(20) 2-(2,3,4-trimethylammonium cyclopentadienyl)-α-normal-butyl-benzimide,
(21) 2-(2,3,5-trimethylammonium cyclopentadienyl)-α-normal-butyl-benzimide,
(22) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-normal-butyl-benzimide,
(23) 2-(2-dimethylaminomethyl cyclopentadienyl)-α-normal-butyl-benzimide,
(24) 2-(3-dimethylaminomethyl cyclopentadienyl)-α-normal-butyl-benzimide,
(25) 2-(indenes-1-yl)-α-normal-butyl-benzimide,
(26) 2-(2-methyl indenes-1-yl)-α-normal-butyl-benzimide,
(27) 2-(2-phenylindan-1-yl)-α-normal-butyl-benzimide,
(28) 2-(fluorenes-9-yl)-α-normal-butyl-benzimide,
(29) 2-(cyclopentadienyl)-α-phenyl-benzimide,
(30) 2-(2-methyl cyclopentadienyl)-α-phenyl-benzimide,
(31) 2-(3-methyl cyclopentadienyl)-α-phenyl-benzimide,
(32) 2-(2,3-dimethyl cyclopentadienyl)-α-phenyl-benzimide,
(33) 2-(2,4-dimethyl cyclopentadienyl)-α-phenyl-benzimide,
(34) 2-(2,3,4-trimethylammonium cyclopentadienyl)-α-phenyl-benzimide,
(35) 2-(2,3,5-trimethylammonium cyclopentadienyl)-α-phenyl-benzimide,
(36) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-benzimide,
(37) 2-(2-dimethylaminomethyl cyclopentadienyl)-α-phenyl-benzimide,
(38) 2-(3-dimethylaminomethyl cyclopentadienyl)-α-phenyl-benzimide,
(39) 2-(indenes-1-yl)-α-phenyl-benzimide,
(40) 2-(2-methyl indenes-1-yl)-α-phenyl-benzimide,
(41) 2-(2-phenylindan-1-yl)-α-phenyl-benzimide,
(42) 2-(fluorenes-9-yl)-α-phenyl-benzimide,
(43) 2-(cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(44) 2-(2-methyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(45) 2-(3-methyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(46) 2-(2,3-dimethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(47) 2-(2,4-dimethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(48) 2-(2,3,4-trimethylammonium cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(49) 2-(2,3,5-trimethylammonium cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(50) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(51) 2-(2-dimethylaminomethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(52) 2-(3-dimethylaminomethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(53) 2-(indenes-1-yl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(54) 2-(2-methyl indenes-1-yl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(55) 2-(2-phenylindan-1-yl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(56) 2-(fluorenes-9-yl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(57) 2-(cyclopentadienyl)-α-cyclohexyl-benzimide,
(58) 2-(2-methyl cyclopentadienyl)-α-cyclohexyl-benzimide,
(59) 2-(3-methyl cyclopentadienyl)-α-cyclohexyl-benzimide,
(60) 2-(2,3-dimethyl cyclopentadienyl)-α-cyclohexyl-benzimide,
(61) 2-(2,4-dimethyl cyclopentadienyl)-α-cyclohexyl-benzimide,
(62) 2-(2,3,4-trimethylammonium cyclopentadienyl)-α-cyclohexyl-benzimide,
(63) 2-(2,3,5-trimethylammonium cyclopentadienyl)-α-cyclohexyl-benzimide,
(64) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-cyclohexyl-benzimide,
(65) 2-(2-dimethylaminomethyl cyclopentadienyl)-α-cyclohexyl-benzimide,
(66) 2-(3-dimethylaminomethyl cyclopentadienyl)-α-cyclohexyl-benzimide,
(67) 2-(indenes-1-yl)-α-cyclohexyl-benzimide,
(68) 2-(2-methyl indenes-1-yl)-α-cyclohexyl-benzimide,
(69) 2-(2-phenylindan-1-yl)-α-cyclohexyl-benzimide,
(70) 2-(fluorenes-9-yl)-α-cyclohexyl-benzimide,
(71) 2-(cyclopentadienyl)-α-tertiary butyl-1-naphthalene azomethine,
(72) 2-(2-methyl cyclopentadienyl)-α-tertiary butyl-1-naphthalene azomethine,
(73) 2-(3-methyl cyclopentadienyl)-α-tertiary butyl-1-naphthalene azomethine,
(74) 2-(2,3-dimethyl cyclopentadienyl)-α-tertiary butyl-1-naphthalene azomethine,
(75) 2-(2,4-dimethyl cyclopentadienyl)-α-tertiary butyl-1-naphthalene azomethine,
(76) 2-(2,3,4-trimethylammonium cyclopentadienyl)-α-tertiary butyl-1-naphthalene azomethine,
(77) 2-(2,3,5-trimethylammonium cyclopentadienyl)-α-tertiary butyl-1-naphthalene azomethine,
(78) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-1-naphthalene azomethine,
(79) 2-(2-dimethylaminomethyl cyclopentadienyl)-α-tertiary butyl-1-naphthalene azomethine,
(80) 2-(3-dimethylaminomethyl cyclopentadienyl)-α-tertiary butyl-1-naphthalene azomethine,
(81) 2-(indenes-1-yl)-α-tertiary butyl-1-naphthalene azomethine,
(82) 2-(2-methyl indenes-1-yl)-α-tertiary butyl-1-naphthalene azomethine,
(83) 2-(2-phenylindan-1-yl)-α-tertiary butyl-1-naphthalene azomethine,
(84) 2-(fluorenes-9-yl)-α-tertiary butyl-1-naphthalene azomethine,
(85) 2-(cyclopentadienyl)-α-normal-butyl-1-naphthalene azomethine,
(86) 2-(2-methyl cyclopentadienyl)-α-normal-butyl-1-naphthalene azomethine,
(87) 2-(3-methyl cyclopentadienyl)-α-normal-butyl-1-naphthalene azomethine,
(88) 2-(2,3-dimethyl cyclopentadienyl)-α-normal-butyl-1-naphthalene azomethine,
(89) 2-(2,4-dimethyl cyclopentadienyl)-α-normal-butyl-1-naphthalene azomethine,
(90) 2-(2,3,4-trimethylammonium cyclopentadienyl)-α-normal-butyl-1-naphthalene azomethine,
(91) 2-(2,3,5-trimethylammonium cyclopentadienyl)-α-normal-butyl-1-naphthalene azomethine,
(92) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-normal-butyl-1-naphthalene azomethine,
(93) 2-(2-dimethylaminomethyl cyclopentadienyl)-α-normal-butyl-1-naphthalene azomethine,
(94) 2-(3-dimethylaminomethyl cyclopentadienyl)-α-normal-butyl-1-naphthalene azomethine,
(95) 2-(indenes-1-yl)-α-normal-butyl-1-naphthalene azomethine,
(96) 2-(2-methyl indenes-1-yl)-α-normal-butyl-1-naphthalene azomethine,
(97) 2-(2-phenylindan-1-yl)-α-normal-butyl-1-naphthalene azomethine,
(98) 2-(fluorenes-9-yl)-α-normal-butyl-1-naphthalene azomethine,
(99) 2-(cyclopentadienyl)-4-benzopyrone-naphthalene azomethine,
(100) 2-(2-methyl cyclopentadienyl)-4-benzopyrone-naphthalene azomethine,
(101) 2-(3-methyl cyclopentadienyl)-4-benzopyrone-naphthalene azomethine,
(102) 2-(2,3-dimethyl cyclopentadienyl)-4-benzopyrone-naphthalene azomethine,
(103) 2-(2,4-dimethyl cyclopentadienyl)-4-benzopyrone-naphthalene azomethine,
(104) 2-(2,3,4-trimethylammonium cyclopentadienyl)-4-benzopyrone-naphthalene azomethine,
(105) 2-(2,3,5-trimethylammonium cyclopentadienyl)-4-benzopyrone-naphthalene azomethine,
(106) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-4-benzopyrone-naphthalene azomethine,
(107) 2-(2-dimethylaminomethyl cyclopentadienyl)-4-benzopyrone-naphthalene azomethine,
(108) 2-(3-dimethylaminomethyl cyclopentadienyl)-4-benzopyrone-naphthalene azomethine,
(109) 2-(indenes-1-yl)-4-benzopyrone-naphthalene azomethine,
(110) 2-(2-methyl indenes-1-yl)-4-benzopyrone-naphthalene azomethine,
(111) 2-(2-phenylindan-1-yl)-4-benzopyrone-naphthalene azomethine,
(112) 2-(fluorenes-9-yl)-4-benzopyrone-naphthalene azomethine,
(113) 2-(cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine,
(114) 2-(2-methyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine,
(115) 2-(3-methyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine,
(116) 2-(2,3-dimethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine,
(117) 2-(2,4-dimethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine,
(118) 2-(2,3,4-trimethylammonium cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine,
(119) 2-(2,3,5-trimethylammonium cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine,
(120) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine,
(121) 2-(2-dimethylaminomethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine,
(122) 2-(3-dimethylaminomethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine,
(123) 2-(indenes-1-yl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine,
(124) 2-(2-methyl indenes-1-yl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine,
(125) 2-(2-phenylindan-1-yl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine,
(126) 2-(fluorenes-9-yl)-α-(2,3, the 4-trimethylphenyl)-1-naphthalene azomethine,
(127) 2-(cyclopentadienyl)-α-cyclohexyl-1-naphthalene azomethine,
(128) 2-(2-methyl cyclopentadienyl)-α-cyclohexyl-1-naphthalene azomethine,
(129) 2-(3-methyl cyclopentadienyl)-α-cyclohexyl-1-naphthalene azomethine,
(130) 2-(2,3-dimethyl cyclopentadienyl)-α-cyclohexyl-1-naphthalene azomethine,
(131) 2-(2,4-dimethyl cyclopentadienyl)-α-cyclohexyl-1-naphthalene azomethine,
(132) 2-(2,3,4-trimethylammonium cyclopentadienyl)-α-cyclohexyl-1-naphthalene azomethine,
(133) 2-(2,3,5-trimethylammonium cyclopentadienyl)-α-cyclohexyl-1-naphthalene azomethine,
(134) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-cyclohexyl-1-naphthalene azomethine,
(135) 2-(2-dimethylaminomethyl cyclopentadienyl)-α-cyclohexyl-1-naphthalene azomethine,
(136) 2-(3-dimethylaminomethyl cyclopentadienyl)-α-cyclohexyl-1-naphthalene azomethine,
(137) 2-(indenes-1-yl)-α-cyclohexyl-1-naphthalene azomethine,
(138) 2-(2-methyl indenes-1-yl)-α-cyclohexyl-1-naphthalene azomethine,
(139) 2-(2-phenylindan-1-yl)-α-cyclohexyl-1-naphthalene azomethine,
(140) 2-(fluorenes-9-yl)-α-cyclohexyl-1-naphthalene azomethine,
(141) 3-(cyclopentadienyl)-α-tertiary butyl-2-naphthalene azomethine,
(142) 3-(2-methyl cyclopentadienyl)-α-tertiary butyl-2-naphthalene azomethine,
(143) 3-(3-methyl cyclopentadienyl)-α-tertiary butyl-2-naphthalene azomethine,
(144) 3-(2,3-dimethyl cyclopentadienyl)-α-tertiary butyl-2-naphthalene azomethine,
(145) 3-(2,4-dimethyl cyclopentadienyl)-α-tertiary butyl-2-naphthalene azomethine,
(146) 3-(2,3,4-trimethylammonium cyclopentadienyl)-α-tertiary butyl-2-naphthalene azomethine,
(147) 3-(2,3,5-trimethylammonium cyclopentadienyl)-α-tertiary butyl-2-naphthalene azomethine,
(148) 3-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-2-naphthalene azomethine,
(149) 3-(2-dimethylaminomethyl cyclopentadienyl)-α-tertiary butyl-2-naphthalene azomethine,
(150) 3-(3-dimethylaminomethyl cyclopentadienyl)-α-tertiary butyl-2-naphthalene azomethine,
(151) 3-(indenes-1-yl)-α-tertiary butyl-2-naphthalene azomethine,
(152) 3-(2-methyl indenes-1-yl)-α-tertiary butyl-2-naphthalene azomethine,
(153) 3-(2-phenylindan-1-yl)-α-tertiary butyl-2-naphthalene azomethine,
(154) 3-(fluorenes-9-yl)-α-tertiary butyl-2-naphthalene azomethine,
(155) 3-(cyclopentadienyl)-α-normal-butyl-2-naphthalene azomethine,
(156) 3-(2-methyl cyclopentadienyl)-α-normal-butyl-2-naphthalene azomethine,
(157) 3-(3-methyl cyclopentadienyl)-α-normal-butyl-2-naphthalene azomethine,
(158) 3-(2,3-dimethyl cyclopentadienyl)-α-normal-butyl-2-naphthalene azomethine,
(159) 3-(2,4-dimethyl cyclopentadienyl)-α-normal-butyl-2-naphthalene azomethine,
(160) 3-(2,3,4-trimethylammonium cyclopentadienyl)-α-normal-butyl-2-naphthalene azomethine,
(161) 3-(2,3,5-trimethylammonium cyclopentadienyl)-α-normal-butyl-2-naphthalene azomethine,
(162) 3-(2,3,4,5-tetramethyl-ring pentadienyl)-α-normal-butyl-2-naphthalene azomethine,
(163) 3-(2-dimethylaminomethyl cyclopentadienyl)-α-normal-butyl-2-naphthalene azomethine,
(164) 3-(3-dimethylaminomethyl cyclopentadienyl)-α-normal-butyl-2-naphthalene azomethine,
(165) 3-(indenes-1-yl)-α-normal-butyl-2-naphthalene azomethine,
(166) 3-(2-methyl indenes-1-yl)-α-normal-butyl-2-naphthalene azomethine,
(167) 3-(2-phenylindan-1-yl)-α-normal-butyl-2-naphthalene azomethine,
(168) 3-(fluorenes-9-yl)-α-normal-butyl-2-naphthalene azomethine,
(169) 3-(cyclopentadienyl)-α-phenyl-2-naphthalene azomethine,
(170) 3-(2-methyl cyclopentadienyl)-α-phenyl-2-naphthalene azomethine,
(171) 3-(3-methyl cyclopentadienyl)-α-phenyl-2-naphthalene azomethine,
(172) 3-(2,3-dimethyl cyclopentadienyl)-α-phenyl-2-naphthalene azomethine,
(173) 3-(2,4-dimethyl cyclopentadienyl)-α-phenyl-2-naphthalene azomethine,
(174) 3-(2,3,4-trimethylammonium cyclopentadienyl)-α-phenyl-2-naphthalene azomethine,
(175) 3-(2,3,5-trimethylammonium cyclopentadienyl)-α-phenyl-2-naphthalene azomethine,
(176) 3-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-2-naphthalene azomethine,
(177) 3-(2-dimethylaminomethyl cyclopentadienyl)-α-phenyl-2-naphthalene azomethine,
(178) 3-(3-dimethylaminomethyl cyclopentadienyl)-α-phenyl-2-naphthalene azomethine,
(179) 3-(indenes-1-yl)-α-phenyl-2-naphthalene azomethine,
(180) 3-(2-methyl indenes-1-yl)-α-phenyl-2-naphthalene azomethine,
(181) 3-(2-phenylindan-1-yl)-α-phenyl-2-naphthalene azomethine,
(182) 3-(fluorenes-9-yl)-α-phenyl-2-naphthalene azomethine,
(183) 3-(cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine,
(184) 3-(2-methyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine,
(185) 3-(3-methyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine,
(186) 3-(2,3-dimethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine,
(187) 3-(2,4-dimethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine,
(188) 3-(2,3,4-trimethylammonium cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine,
(189) 3-(2,3,5-trimethylammonium cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine,
(190) 3-(2,3,4,5-tetramethyl-ring pentadienyl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine,
(191) 3-(2-dimethylaminomethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine,
(192) 3-(3-dimethylaminomethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine,
(193) 3-(indenes-1-yl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine,
(194) 3-(2-methyl indenes-1-yl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine,
(195) 3-(2-phenylindan-1-yl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine,
(196) 3-(fluorenes-9-yl)-α-(2,3, the 4-trimethylphenyl)-2-naphthalene azomethine,
(197) 3-(cyclopentadienyl)-α-cyclohexyl-2-naphthalene azomethine,
(198) 3-(2-methyl cyclopentadienyl)-α-cyclohexyl-2-naphthalene azomethine,
(199) 3-(3-methyl cyclopentadienyl)-α-cyclohexyl-2-naphthalene azomethine,
(200) 3-(2,3-dimethyl cyclopentadienyl)-α-cyclohexyl-2-naphthalene azomethine,
(201) 3-(2,4-dimethyl cyclopentadienyl)-α-cyclohexyl-2-naphthalene azomethine,
(202) 3-(2,3,4-trimethylammonium cyclopentadienyl)-α-cyclohexyl-2-naphthalene azomethine,
(203) 3-(2,3,5-trimethylammonium cyclopentadienyl)-α-cyclohexyl-2-naphthalene azomethine,
(204) 3-(2,3,4,5-tetramethyl-ring pentadienyl)-α-cyclohexyl-2-naphthalene azomethine,
(205) 3-(2-dimethylaminomethyl cyclopentadienyl)-α-cyclohexyl-2-naphthalene azomethine,
(206) 3-(3-dimethylaminomethyl cyclopentadienyl)-α-cyclohexyl-2-naphthalene azomethine,
(207) 3-(indenes-1-yl)-α-cyclohexyl-2-naphthalene azomethine,
(208) 3-(2-methyl indenes-1-yl)-α-cyclohexyl-2-naphthalene azomethine,
(209) 3-(2-phenylindan-1-yl)-α-cyclohexyl-2-naphthalene azomethine,
(210) 3-(fluorenes-9-yl)-α-cyclohexyl-2-naphthalene azomethine,
(211) 3-dimethylamino-6-(cyclopentadienyl)-α-tertiary butyl-benzimide,
(212) 3-dimethylamino-6-(2-methyl cyclopentadienyl)-α-tertiary butyl-benzimide,
(213) 3-dimethylamino-6-(3-methyl cyclopentadienyl)-α-tertiary butyl-benzimide,
(214) 3-dimethylamino-6-(2,3-dimethyl cyclopentadienyl)-α-tertiary butyl-benzimide,
(215) 3-dimethylamino-6-(2,4-dimethyl cyclopentadienyl)-α-tertiary butyl-benzimide,
(216) 3-dimethylamino-6-(2,3,4-trimethylammonium cyclopentadienyl)-α-tertiary butyl-benzimide,
(217) 3-dimethylamino-6-(2,3,5-trimethylammonium cyclopentadienyl)-α-tertiary butyl-benzimide,
(218) 3-dimethylamino-6-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-benzimide,
(219) 3-dimethylamino-6-(2-dimethylaminomethyl cyclopentadienyl)-α-tertiary butyl-benzimide,
(220) 3-dimethylamino-6-(3-dimethylaminomethyl cyclopentadienyl)-α-tertiary butyl-benzimide,
(221) 3-dimethylamino-6-(indenes-1-yl)-α-tertiary butyl-benzimide,
(222) 3-dimethylamino-6-(2-methyl indenes-1-yl)-α-tertiary butyl-benzimide,
(223) 3-dimethylamino-6-(2-phenylindan-1-yl)-α-tertiary butyl-benzimide,
(224) 3-dimethylamino-6-(fluorenes-9-yl)-α-tertiary butyl-benzimide,
(225) 3-dimethylamino-6-(cyclopentadienyl)-α-normal-butyl-benzimide,
(226) 3-dimethylamino-6-(2-methyl cyclopentadienyl)-α-normal-butyl-benzimide,
(227) 3-dimethylamino-6-(3-methyl cyclopentadienyl)-α-normal-butyl-benzimide,
(228) 3-dimethylamino-6-(2,3-dimethyl cyclopentadienyl)-α-normal-butyl-benzimide,
(229) 3-dimethylamino-6-(2,4-dimethyl cyclopentadienyl)-α-normal-butyl-benzimide,
(230) 3-dimethylamino-6-(2,3,4-trimethylammonium cyclopentadienyl)-α-normal-butyl-benzimide,
(231) 3-dimethylamino-6-(2,3,5-trimethylammonium cyclopentadienyl)-α-normal-butyl-benzimide,
(232) 3-dimethylamino-6-(2,3,4,5-tetramethyl-ring pentadienyl)-α-normal-butyl-benzimide,
(233) 3-dimethylamino-6-(2-dimethylaminomethyl cyclopentadienyl)-α-normal-butyl-benzimide,
(234) 3-dimethylamino-6-(3-dimethylaminomethyl cyclopentadienyl)-α-normal-butyl-benzimide,
(235) 3-dimethylamino-6-(indenes-1-yl)-α-normal-butyl-benzimide,
(236) 3-dimethylamino-6-(2-methyl indenes-1-yl)-α-normal-butyl-benzimide,
(237) 3-dimethylamino-6-(2-phenylindan-1-yl)-α-normal-butyl-benzimide,
(238) 3-dimethylamino-6-(fluorenes-9-yl)-α-normal-butyl-benzimide,
(239) 3-dimethylamino-6-(cyclopentadienyl)-α-phenyl-benzimide,
(240) 3-dimethylamino-6-(2-methyl cyclopentadienyl)-α-phenyl-benzimide,
(241) 3-dimethylamino-6-(3-methyl cyclopentadienyl)-α-phenyl-benzimide,
(242) 3-dimethylamino-6-(2,3-dimethyl cyclopentadienyl)-α-phenyl-benzimide,
(243) 3-dimethylamino-6-(2,4-dimethyl cyclopentadienyl)-α-phenyl-benzimide,
(244) 3-dimethylamino-6-(2,3,4-trimethylammonium cyclopentadienyl)-α-phenyl-benzimide,
(245) 3-dimethylamino-6-(2,3,5-trimethylammonium cyclopentadienyl)-α-phenyl-benzimide,
(246) 3-dimethylamino-6-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-benzimide,
(247) 3-dimethylamino-6-(2-dimethylaminomethyl cyclopentadienyl)-α-phenyl-benzimide,
(248) 3-dimethylamino-6-(3-dimethylaminomethyl cyclopentadienyl)-α-phenyl-benzimide,
(249) 3-dimethylamino-6-(indenes-1-yl)-α-phenyl-benzimide,
(250) 3-dimethylamino-6-(2-methyl indenes-1-yl)-α-phenyl-benzimide,
(251) 3-dimethylamino-6-(2-phenylindan-1-yl)-α-phenyl-benzimide,
(252) 3-dimethylamino-6-(fluorenes-9-yl)-α-phenyl-benzimide,
(253) 3-dimethylamino-6-(cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(254) 3-dimethylamino-6-(2-methyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(255) 3-dimethylamino-6-(3-methyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(256) 3-dimethylamino-6-(2,3-dimethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(257) 3-dimethylamino-6-(2,4-dimethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(258) 3-dimethylamino-6-(2,3,4-trimethylammonium cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(259) 3-dimethylamino-6-(2,3,5-trimethylammonium cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(260) 3-dimethylamino-6-(2,3,4,5-tetramethyl-ring pentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(261) 3-dimethylamino-6-(2-dimethylaminomethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(262) 3-dimethylamino-6-(3-dimethylaminomethyl cyclopentadienyl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(263) 3-dimethylamino-6-(indenes-1-yl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(264) 3-dimethylamino-6-(2-methyl indenes-1-yl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(265) 3-dimethylamino-6-(2-phenylindan-1-yl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(266) 3-dimethylamino-6-(fluorenes-9-yl)-α-(2,3, the 4-trimethylphenyl)-benzimide,
(267) 3-dimethylamino-6-(cyclopentadienyl)-α-cyclohexyl-benzimide,
(268) 3-dimethylamino-6-(2-methyl cyclopentadienyl)-α-cyclohexyl-benzimide,
(269) 3-dimethylamino-6-(3-methyl cyclopentadienyl)-α-cyclohexyl-benzimide,
(270) 3-dimethylamino-6-(2,3-dimethyl cyclopentadienyl)-α-cyclohexyl-benzimide,
(271) 3-dimethylamino-6-(2,4-dimethyl cyclopentadienyl)-α-cyclohexyl-benzimide,
(272) 3-dimethylamino-6-(2,3,4-trimethylammonium cyclopentadienyl)-α-cyclohexyl-benzimide,
(273) 3-dimethylamino-6-(2,3,5-trimethylammonium cyclopentadienyl)-α-cyclohexyl-benzimide,
(274) 3-dimethylamino-6-(2,3,4,5-tetramethyl-ring pentadienyl)-α-cyclohexyl-benzimide,
(275) 3-dimethylamino-6-(2-dimethylaminomethyl cyclopentadienyl)-α-cyclohexyl-benzimide,
(276) 3-dimethylamino-6-(3-dimethylaminomethyl cyclopentadienyl)-α-cyclohexyl-benzimide,
(277) 3-dimethylamino-6-(indenes-1-yl)-α-cyclohexyl-benzimide,
(278) 3-dimethylamino-6-(2-methyl indenes-1-yl)-α-cyclohexyl-benzimide,
(279) 3-dimethylamino-6-(2-phenylindan-1-yl)-α-cyclohexyl-benzimide,
(280) 3-dimethylamino-6-(fluorenes-9-yl)-α-cyclohexyl-benzimide etc.
Nitrile compound shown in the formula (10) can be by making the preparation of oxime ether compound shown in the formula (11) and alkali reaction.
Be used for comprising lithium methide with the alkali of the reaction of compound shown in the formula (11), lithium ethide, n-Butyl Lithium, s-butyl lithium, trimethylsilyl ethinylation lithium, the trimethylsilyl lithium methide, vinyl lithium, phenyl lithium, lithium methoxide, lithium ethoxide, trimethyl carbinol lithium, sodium methylate, sodium ethylate, sodium tert-butoxide, potassium methylate, potassium ethylate, potassium tert.-butoxide, lithium amide, the dimethylamino lithium, the diisopropylaminoethyl lithium, two (trimethylsilyl) lithium amide, sodium amide, diisopropylaminoethyl sodium, two (trimethylsilyl) sodium amide etc., preferred amination basic metal such as lithium amide, the dimethylamino lithium, the diisopropylaminoethyl lithium, two (trimethylsilyl) lithium amide, sodium amide, diisopropylaminoethyl sodium, two (trimethylsilyl) sodium amide etc.
The consumption of alkali is generally about 0.5-3 mole with respect to oxime ether compound shown in 1 mole of formula (11), is preferably about 1.9-2.5 mole.
Method to reaction is not particularly limited, but this method can be included in solvent and exists shown in the downdraft mode (11) and drip alkali in the oxime ether compound usually, perhaps oxime ether compound shown in the adding formula (11) in alkali.Temperature of reaction is generally-80 ℃ to solvent boiling point, preferred-80 ℃ to 40 ℃.
Used solvent is that reaction is the inert solvent in the reaction.Such solvent comprises aromatic solvents such as benzene,toluene,xylene, aliphatic hydrocarbon solvents such as hexane, heptane, ether, tetrahydrofuran (THF), 1, ether solvents such as 4-diox, amide solvents such as hexamethyl phosphoric triamide, dimethyl formamide.Can use the mixture of a kind of solvent or two or more solvents.The consumption of solvent is generally the 1-200 weight part with respect to oxime ether compound shown in the 1 weight part formula (11), preferred 3-50 weight part.
After the reaction, if desired, can in the gained reaction mixture, add entry.Then this mixture separation is become organic layer and water layer, to obtain target compound solution as organic layer.When because in described reaction, use with the solvent of water compatible or use a small amount of solvent and when making organic layer and water layer not easily separated, can after in reaction mixture, adding water-insoluble organic solvents such as toluene, ethyl acetate or chlorobenzene, separate.
Can be by for example nitrile compound shown in the following operation separate type (10): wash the described solution of this compound with water, dry described solution, distilling off solvent and further separating then through methods such as recrystallization, distillation, column chromatography processing.
Oxime ether compound shown in the formula (11) can make carbonyl compound shown in the formula (1) and the reaction of oxime ether by ordinary method.
By making the transistion metal compound reaction of substituted-cyclopentadienyl ligand compound shown in the formula (II) that obtains thus and formula (III), can make the transition metal complex of formula (I).
To the X in the transistion metal compound shown in the formula (III) 1To X 4Be described.Preferably incite somebody to action wherein each X 1To X 4Be C 1-5The described transistion metal compound of hydrocarbon-substituted-amino is used to prepare described transition metal complex.
Transistion metal compound shown in the formula (III) comprise four (dimethylamino) titanium,
Four (diethylamino) titanium,
Four (dimethylamino) zirconium,
Four (diethylamino) zirconium,
Four (dimethylamino) hafnium,
Four (diethylamino) hafnium,
Chlorination three (dimethylamino) titanium,
Chlorination three (diethylamino) titanium,
Chlorination three (dimethylamino) zirconium,
Chlorination three (diethylamino) zirconium,
Chlorination three (dimethylamino) hafnium,
Chlorination three (diethylamino) hafnium,
Molybdenyl dichloride (dimethylamino) titanium,
Molybdenyl dichloride (diethylamino) titanium,
Molybdenyl dichloride (dimethylamino) zirconium,
Molybdenyl dichloride (diethylamino) zirconium,
Molybdenyl dichloride (dimethylamino) hafnium,
Molybdenyl dichloride (diethylamino) hafnium etc.
Above-mentioned reaction is carried out in the inert solvent of reaction usually.Such solvent comprises for example aprotic solvent: as aromatic solvents such as benzene, toluene; Aliphatic hydrocarbon solvent such as hexane, heptane; Ether, tetrahydrofuran (THF), 1, ether solvents such as 4-diox; Amide solvent such as hexamethylphosphoramide, dimethyl formamide; Acetonitrile, propionitrile, acetone, diethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone isopolarity solvent; Halogenated solvents such as methylene dichloride, ethylene dichloride, chlorobenzene, dichlorobenzene.Aromatic solvents such as preferred benzene, toluene; Aliphatic hydrocarbon solvent such as hexane, heptane.Can use the mixture of a kind of solvent or two or more solvents.The consumption of solvent is generally the 1-200 weight part with respect to substituted-cyclopentadienyl ligand compound shown in the 1 weight part formula (II), preferred 3-50 weight part.
This reaction can be undertaken by following operation: substituted-cyclopentadienyl shown in the adding formula (II) in solvent, and then to wherein adding transistion metal compound shown in the formula (III).Can obtain transition metal complex shown in the formula (I) thus.
Temperature of reaction is generally-100 ℃ of boiling points to solvent, preferred-80 ℃ to 120 ℃.
By with the reaction of halogen compounds such as chlorosilane or hydrogenchloride, can be with X wherein 1And X 2The transition metal complex that is respectively substituted-amino changes into its halogenide.The transition metal complex that obtains thus is included in the compound described in formula (I-1), (I-2), (I-3) and the explanation (I-4).
Below carbonyl compound of formula (1) and preparation method thereof is described, this compound is the starting raw material of substituted-cyclopentadienyl ligand compound (5), (6), (7) and (8).
In the presence of magnesium compound or organolithium compound, make the cyclopentenone reaction of the halogen compounds of formula (2) and formula (3), cyclopentenol shown in the formula that obtains with acid treatment (4) then can make the carbonyl compound of formula (1) thus.
In halogen compounds shown in the formula (2), substituent X is represented chlorine, bromine or iodine atom, preferred bromine atoms or iodine atom.
Substituent R 10And R 11The C of optional replacement 1-10Alkyl comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, neo-pentyl, amyl group, n-hexyl, n-octyl, positive decyl, methyl fluoride, difluoromethyl, trifluoromethyl, fluoro ethyl, two fluoro ethyls, trifluoroethyl, tetrafluoro ethyl, pentafluoroethyl group, perfluoro propyl, perfluoro butyl, perfluor amyl group, perfluoro hexyl, perfluoro capryl, perfluor decyl etc., preferable methyl, ethyl, sec.-propyl, the tertiary butyl, amyl group etc.Perhaps, R 10And R 11Can be connected one to the other to and form 5 or 6 yuan of rings together, preferred ethylidene and propylidene.
The object lesson of described halogen compounds comprises:
(1) 1-chloro-2-(1,3-dioxolane-2-yl)-benzene,
(2) 1-chloro-2-(2-methyl isophthalic acid, 3-dioxolane-butyl oxide link-2-yl)-benzene,
(3) 1-chloro-2-(2-ethyl-1,3-butyl oxide link-2-yl)-benzene,
(4) 1-chloro-2-(2-phenyl-1,3-butyl oxide link-2-yl)-benzene,
(5) 1-chloro-2-(dimethoxy-methyl)-benzene,
(6) 1-chloro-2-(1, the 1-dimethoxy-ethyl)-benzene,
(7) 1-chloro-2-(1,1-dimethoxy-1-phenyl methyl)-benzene,
(8) 1-bromo-2-(1,3-dioxolane-2-yl)-benzene,
(9) 1-bromo-2-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-benzene,
(10) 1-bromo-2-(2-ethyl-1,3-dioxolane-2-yl)-benzene,
(11) 1-bromo-2-(2-phenyl-1,3-dioxolane-2-yl)-benzene,
(12) 1-bromo-2-(dimethoxy-methyl)-benzene,
(13) 1-bromo-2-(1, the 1-dimethoxy-ethyl)-benzene,
(14) 1-bromo-2-(1,1-dimethoxy-1-phenyl methyl)-benzene,
(15) 1-iodo-2-(1,3-dioxolane-2-yl)-benzene,
(16) 1-iodo-2-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-benzene,
(17) 1-iodo-2-(2-ethyl-1,3-dioxolane-2-yl)-benzene,
(18) 1-iodo-2-(2-phenyl-1,3-dioxolane-2-yl)-benzene,
(19) 1-iodo-2-(dimethoxy-methyl)-benzene,
(20) 1-iodo-2-(1, the 1-dimethoxy-ethyl)-benzene,
(21) 1-iodo-2-(1,1-dimethoxy-1-phenyl methyl)-benzene,
(22) 1-chloro-2-(1,3-dioxolane-2-yl)-naphthalene,
(23) 1-chloro-2-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-naphthalene,
(24) 1-chloro-2-(2-ethyl-1,3-dioxolane-2-yl)-naphthalene,
(25) 1-chloro-2-(2-phenyl-1,3-dioxolane-2-yl)-naphthalene,
(26) 1-chloro-2-(dimethoxy-methyl)-naphthalene,
(27) 1-chloro-2-(1, the 1-dimethoxy-ethyl)-naphthalene,
(28) 1-chloro-2-(1,1-dimethoxy-1-phenyl methyl)-naphthalene,
(29) 1-bromo-2-(1,3-dioxolane-2-yl)-naphthalene,
(30) 1-bromo-2-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-naphthalene,
(31) 1-bromo-2-(2-ethyl-1,3-dioxolane-2-yl)-naphthalene,
(32) 1-bromo-2-(2-phenyl-1,3-dioxolane-2-yl)-naphthalene,
(33) 1-bromo-2-(dimethoxy-methyl)-naphthalene,
(34) 1-bromo-2-(1, the 1-dimethoxy-ethyl)-naphthalene,
(35) 1-bromo-2-(1,1-dimethoxy-1-phenyl methyl)-naphthalene,
(36) 1-iodo-2-(1,3-dioxolane-2-yl)-naphthalene,
(37) 1-iodo-2-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-naphthalene,
(38) 1-iodo-2-(2-ethyl-1,3-dioxolane-2-yl)-naphthalene,
(39) 1-iodo-2-(2-phenyl-1,3-dioxolane-2-yl)-naphthalene,
(40) 1-iodo-2-(dimethoxy-methyl)-naphthalene,
(41) 1-iodo-2-(1, the 1-dimethoxy-ethyl)-naphthalene,
(42) 1-iodo-2-(1,1-dimethoxy-1-phenyl methyl)-naphthalene,
(43) 1-chloro-2-(1,3-dioxolane-2-yl)-4-tert.-butylbenzene,
(44) 1-chloro-2-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-4-tert.-butylbenzene,
(45) 1-chloro-2-(2-ethyl-1,3-dioxolane-2-yl)-4-tert.-butylbenzene,
(46) 1-chloro-2-(2-phenyl-1,3-dioxolane-2-yl)-4-tert.-butylbenzene,
(47) 1-chloro-2-(dimethoxy-methyl)-4-tert.-butylbenzene,
(48) 1-chloro-2-(1, the 1-dimethoxy-ethyl)-4-tert.-butylbenzene,
(49) 1-chloro-2-(1,1-dimethoxy-1-phenyl methyl)-4-tert.-butylbenzene,
(50) 1-bromo-2-(1,3-dioxolane-2-yl)-4-tert.-butylbenzene,
(51) 1-bromo-2-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-4-tert.-butylbenzene,
(52) 1-bromo-2-(2-ethyl-1,3-dioxolane-2-yl)-4-tert.-butylbenzene,
(53) 1-bromo-2-(2-phenyl-1,3-dioxolane-2-yl)-4-tert.-butylbenzene,
(54) 1-bromo-2-(dimethoxy-methyl)-4-tert.-butylbenzene,
(55) 1-bromo-2-(1, the 1-dimethoxy-ethyl)-4-tert.-butylbenzene,
(56) 1-bromo-2-(1,1-dimethoxy-1-phenyl methyl)-4-tert.-butylbenzene,
(57) 1-iodo-2-(1,3-dioxolane-2-yl)-4-tert.-butylbenzene,
(58) 1-iodo-2-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-4-tert.-butylbenzene,
(59) 1-iodo-2-(2-ethyl-1,3-dioxolane-2-yl)-4-tert.-butylbenzene,
(60) 1-iodo-2-(2-phenyl-1,3-dioxolane-2-yl)-4-tert.-butylbenzene,
(61) 1-iodo-2-(dimethoxy-methyl)-4-tert.-butylbenzene,
(62) 1-iodo-2-(1, the 1-dimethoxy-ethyl)-4-tert.-butylbenzene,
(63) 1-iodo-2-(1,1-dimethoxy-1-phenyl methyl)-4-tert.-butylbenzene etc.
The preparation method's of formula (1) carbonyl compound the first step is to make that cyclopentenone reacts in the presence of magnesium compound or organolithium compound shown in halogen compounds shown in the formula (2) and the formula (3), obtains the step of cyclopentenol shown in the formula (4).
The organolithium compound that is used for above-mentioned reaction comprises lithium methide, lithium ethide, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, phenyl lithium etc.The consumption of organolithium compound is generally the 0.5-3 mole with respect to halogen compounds shown in 1 mole of formula (2), preferred 0.9-2.5 mole.
Cyclopentenone comprises shown in the formula (3):
(1) the 2-cyclopentenone,
(2) 2-methyl cyclopentene ketone,
(3) 3-methyl cyclopentene ketone,
(4) 2,3-dimethylcyclopentene ketone,
(5) 2,4-dimethylcyclopentene ketone,
(6) 3,4-dimethylcyclopentene ketone,
(7) 2,3,4-trimethyl-cyclopentene ketone,
(8) 2,3,5-trimethyl-cyclopentene ketone,
(9) 2,3,4,5-tetramethyl-ring pentenone,
(10) 2-tertiary butyl cyclopentenone,
(11) 3-tertiary butyl cyclopentenone,
(12) 4-tertiary butyl cyclopentenone,
(13) 5-tertiary butyl cyclopentenone,
(14) 2-dimethylamino cyclopentenone,
(15) 3-dimethylamino cyclopentenone,
(16) 4-dimethylamino cyclopentenone,
(17) 5-dimethylamino cyclopentenone,
(18) 2-methyl indone
(19) 2-phenyl indone,
(20) 2-trimethylsilyl cyclopentenone,
(21) 3-trimethylsilyl cyclopentenone,
(22) 4-trimethylsilyl cyclopentenone and
(23) 5-trimethylsilyl cyclopentenone.
Above-mentioned reaction is undertaken by following operation usually: make the reaction of halogen compounds shown in the formula (2) and magnesium compound or organolithium compound in the presence of solvent, then to wherein adding cyclopentenone shown in the formula (3).Make the temperature of halogen compounds shown in the formula (2) and magnesium compound or organolithium compound reaction be generally-80 ℃ to solvent boiling point.When making the reaction of halogen compounds shown in the formula (2) and organolithium compound, preferred-80 ℃ to 40 ℃ of temperature of reaction, when using magnesium, preferred 10 ℃ to 100 ℃.
React the temperature of reaction of cyclopentenone shown in the back adding formula (3) usually-80 ℃ of scopes, preferred-50 ℃ to 60 ℃ with magnesium compound or organolithium compound to solvent boiling point.
The reaction solvent for use is the inert solvent of reaction.Such solvent comprises for example aromatic solvent such as benzene,toluene,xylene; Aliphatic hydrocarbon solvent such as hexane, heptane; Ether, tetrahydrofuran (THF), 1, ether solvents such as 4-diox; Amide solvent such as hexamethyl phosphoric triamide, dimethyl formamide.Can use the mixture of a kind of solvent or two or more solvents.The consumption of solvent is generally 1-200 times of halogen compounds weight shown in the formula (2), and preferred 3-50 doubly.
After the reaction, in the gained reaction mixture, add entry, then this mixture separation is become organic layer and water layer, to obtain target compound solution as organic layer.When because in described reaction, use with the solvent of water compatible or use a small amount of solvent and when making organic layer and water layer not easily separated, can after in reaction mixture, adding water-insoluble organic solvents such as toluene, ethyl acetate, chlorobenzene, separate.The solution of formula (4) cyclopentenol that obtains thus can be directly used in step subsequently, perhaps from described solvent, be used further to next step behind the purification cyclopentenol.Cyclopentenol shown in the formula (4) can be purified by for example following operation: wash described solution with water, dry described solution, distilling off solvent is also further purified through methods such as recrystallization, distillation, column chromatography processing then.
Cyclopentenol comprises shown in the formula that obtains thus (4):
(1) 1-(1,3-dioxolane-2-yl)-2-(1-hydroxyl-2-cyclopentenyl) benzene,
(2) 1-(1,3-dioxolane-2-yl)-2-(1-hydroxy-2-methyl-2-cyclopentenyl) benzene,
(3) 1-(1,3-dioxolane-2-yl)-2-(1-hydroxy-3-methyl-2-cyclopentenyl) benzene,
(4) 1-(1,3-dioxolane-2-yl)-2-(1-hydroxyl-2,3-dimethyl-2-cyclopentenyl) benzene,
(5) 1-(1,3-dioxolane-2-yl)-2-(1-hydroxyl-2,4-dimethyl-2-cyclopentenyl) benzene,
(6) 1-(1,3-dioxolane-2-yl)-2-(1-hydroxyl-3,4-dimethyl-2-cyclopentenyl) benzene,
(7) 1-(1,3-dioxolane-2-yl)-2-(1-hydroxyl-2,3,4-trimethylammonium -The 2-cyclopentenyl) benzene,
(8) 1-(1,3-dioxolane-2-yl)-2-(2-hydroxyl-2,4,5-trimethylammonium-2-cyclopentenyl) benzene,
(9) 1-(1,3-dioxolane-2-yl)-2-(1-hydroxyl-2,3,4,5-tetramethyl--2-cyclopentenyl) benzene,
(10) 1-(1,3-dioxolane-2-yl)-2-(the 1-hydroxyl-2-tertiary butyl-2-cyclopentenyl) benzene,
(11) 1-(1,3-dioxolane-2-yl)-2-(the 1-hydroxyl-3-tertiary butyl-2-cyclopentenyl) benzene,
(12) 1-(1,3-dioxolane-2-yl)-2-(1-hydroxyl-2-dimethylamino-2-cyclopentenyl) benzene,
(13) 1-(1,3-dioxolane-2-yl)-2-(1-hydroxyl-3-dimethylamino-2-cyclopentenyl) benzene,
(14) 1-(1,3-dioxolane-2-yl)-2-(1-hydroxy-2-methyl indane-1-yl) benzene,
(15) 1-(1,3-dioxolane-2-yl)-2-(1-hydroxyl-2-phenyl indan-1-yl) benzene,
(16) 1-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-2-(1-hydroxyl-2-cyclopentenyl) benzene,
(17) 1-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-2-(1-hydroxy-2-methyl-2-cyclopentenyl) benzene,
(18) 1-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-2-(1-hydroxy-3-methyl-2-cyclopentenyl) benzene,
(19) 1-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-2-(1-hydroxyl-2,3-dimethyl-2-cyclopentenyl) benzene,
(20) 1-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-2-(1-hydroxyl-2,4-dimethyl-2-cyclopentenyl) benzene,
(21) 1-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-2-(1-hydroxyl-3,4-dimethyl-2-cyclopentenyl) benzene,
(22) 1-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-2-(1-hydroxyl-2,3,4-trimethylammonium-2-cyclopentenyl) benzene,
(23) 1-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-2-(2-hydroxyl-2,4,5-trimethylammonium-2-cyclopentenyl) benzene,
(24) 1-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-2-(1-hydroxyl-2,3,4,5-tetramethyl--2-cyclopentenyl) benzene,
(25) 1-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-2-(the 1-hydroxyl-2-tertiary butyl-2-cyclopentenyl) benzene,
(26) 1-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-2-(the 1-hydroxyl-3-tertiary butyl-2-cyclopentenyl) benzene,
(27) 1-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-2-(1-hydroxyl-2-dimethylamino-2-cyclopentenyl) benzene,
(28) 1-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-2-(1-hydroxyl-3-dimethylamino-2-cyclopentenyl) benzene,
(29) 1-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-2-(1-hydroxy-2-methyl indane-1-yl) benzene,
(30) 1-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-2-(1-hydroxyl-2-phenyl indan-1-yl) benzene,
(31) 1-(2-ethyl-1,3-dioxolane-2-yl)-2-(1-hydroxyl-2-cyclopentenyl) benzene,
(32) 1-(2-ethyl-1,3-dioxolane-2-yl)-2-(1-hydroxy-2-methyl-2-cyclopentenyl) benzene,
(33) 1-(2-ethyl-1,3-dioxolane-2-yl)-2-(1-hydroxy-3-methyl-2-cyclopentenyl) benzene,
(34) 1-(2-ethyl-1,3-dioxolane-2-yl)-2-(1-hydroxyl-2,3-dimethyl-2-cyclopentenyl) benzene,
(35) 1-(2-ethyl-1,3-dioxolane-2-yl)-2-(1-hydroxyl-2,4-dimethyl-2-cyclopentenyl) benzene,
(36) 1-(2-ethyl-1,3-dioxolane-2-yl)-2-(1-hydroxyl-3,4-dimethyl-2-cyclopentenyl) benzene,
(37) 1-(2-ethyl-1,3-dioxolane-2-yl)-2-(1-hydroxyl-2,3,4-trimethylammonium-2-cyclopentenyl) benzene,
(38) 1-(2-ethyl-1,3-dioxolane-2-yl)-2-(2-hydroxyl-2,4,5-trimethylammonium-2-cyclopentenyl) benzene,
(39) 1-(2-ethyl-1,3-dioxolane-2-yl)-2-(1-hydroxyl-2,3,4,5-tetramethyl--2-cyclopentenyl) benzene,
(40) 1-(2-ethyl-1,3-dioxolane-2-yl)-2-(the 1-hydroxyl-2-tertiary butyl-2-cyclopentenyl) benzene,
(41) 1-(2-ethyl-1,3-dioxolane-2-yl)-2-(the 1-hydroxyl-3-tertiary butyl-2-cyclopentenyl) benzene,
(42) 1-(2-ethyl-1,3-dioxolane-2-yl)-2-(1-hydroxyl-2-dimethylamino-2-cyclopentenyl) benzene,
(43) 1-(2-ethyl-1,3-dioxolane-2-yl)-2-(1-hydroxyl-3-dimethylamino-2-cyclopentenyl) benzene,
(44) 1-(2-ethyl-1,3-dioxolane-2-yl)-2-(1-hydroxy-2-methyl indane-1-yl) benzene,
(45) 1-(2-ethyl-1,3-dioxolane-2-yl)-2-(1-hydroxyl-2-phenyl indan-1-yl) benzene,
(46) 1-(2-phenyl-1,3-dioxolane-2-yl)-2-(1-hydroxyl-2-cyclopentenyl) benzene,
(47) 1-(2-phenyl-1,3-dioxolane-2-yl)-2-(1-hydroxy-2-methyl-2-cyclopentenyl) benzene,
(48) 1-(2-phenyl-1,3-dioxolane-2-yl)-2-(1-hydroxy-3-methyl-2-cyclopentenyl) benzene,
(49) 1-(2-phenyl-1,3-dioxolane-2-yl)-2-(1-hydroxyl-2,3-dimethyl-2-cyclopentenyl) benzene,
(50) 1-(2-phenyl-1,3-dioxolane-2-yl)-2-(1-hydroxyl-2,4-dimethyl-2-cyclopentenyl) benzene,
(51) 1-(2-phenyl-1,3-dioxolane-2-yl)-2-(1-hydroxyl-3,4-dimethyl-2-cyclopentenyl) benzene,
(52) 1-(2-phenyl-1,3-dioxolane-2-yl)-2-(1-hydroxyl-2,3,4-trimethylammonium-2-cyclopentenyl) benzene,
(53) 1-(2-phenyl-1,3-dioxolane-2-yl)-2-(2-hydroxyl-2,4,5-trimethylammonium-2-cyclopentenyl) benzene,
(54) 1-(2-phenyl-1,3-dioxolane-2-yl)-2-(1-hydroxyl-2,3,4,5-tetramethyl--2-cyclopentenyl) benzene,
(55) 1-(2-phenyl-1,3-dioxolane-2-yl)-2-(the 1-hydroxyl-2-tertiary butyl-2-cyclopentenyl) benzene,
(56) 1-(2-phenyl-1,3-dioxolane-2-yl)-2-(the 1-hydroxyl-3-tertiary butyl-2-cyclopentenyl) benzene,
(57) 1-(2-phenyl-1,3-dioxolane-2-yl)-2-(1-hydroxyl-2-dimethylamino-2-cyclopentenyl) benzene,
(58) 1-(2-phenyl-1,3-dioxolane-2-yl)-2-(1-hydroxyl-3-dimethylamino-2-cyclopentenyl) benzene,
(59) 1-(2-phenyl-1,3-dioxolane-2-yl)-2-(1-hydroxy-2-methyl indane-1-yl) benzene,
(60) 1-(2-phenyl-1,3-dioxolane-2-yl)-2-(1-hydroxyl-2-phenyl indan-1-yl) benzene,
(61) 1-(dimethoxy-methyl)-2-(1-hydroxyl-2-cyclopentenyl) benzene,
(62) 1-(dimethoxy-methyl)-2-(1-hydroxy-2-methyl-2-cyclopentenyl) benzene,
(63) 1-(dimethoxy-methyl)-2-(1-hydroxy-3-methyl-2-cyclopentenyl) benzene,
(64) 1-(dimethoxy-methyl)-2-(1-hydroxyl-2,3-dimethyl-2-cyclopentenyl) benzene,
(65) 1-(dimethoxy-methyl)-2-(1-hydroxyl-2,4-dimethyl-2-cyclopentenyl) benzene,
(66) 1-(dimethoxy-methyl)-2-(1-hydroxyl-3,4-dimethyl-2-cyclopentenyl) benzene,
(67) 1-(dimethoxy-methyl)-2-(1-hydroxyl-2,3,4-trimethylammonium-2-cyclopentenyl) benzene,
(68) 1-(dimethoxy-methyl)-2-(2-hydroxyl-2,4,5-trimethylammonium-2-cyclopentenyl) benzene,
(69) 1-(dimethoxy-methyl)-2-(1-hydroxyl-2,3,4,5-tetramethyl--2-cyclopentenyl) benzene,
(70) 1-(dimethoxy-methyl)-2-(the 1-hydroxyl-2-tertiary butyl-2-cyclopentenyl) benzene,
(71) 1-(dimethoxy-methyl)-2-(the 1-hydroxyl-3-tertiary butyl-2-cyclopentenyl) benzene,
(72) 1-(dimethoxy-methyl)-2-(1-hydroxyl-2-dimethylamino-2-cyclopentenyl) benzene,
(73) 1-(dimethoxy-methyl)-2-(1-hydroxyl-3-dimethylamino-2-cyclopentenyl) benzene,
(74) 1-(dimethoxy-methyl)-2-(1-hydroxy-2-methyl indane-1-yl) benzene,
(75) 1-(dimethoxy-methyl)-2-(1-hydroxyl-2-phenyl indan-1-yl) benzene,
(76) 1-(1, the 1-dimethoxy-ethyl)-2-(1-hydroxyl-2-cyclopentenyl) benzene,
(77) 1-(1, the 1-dimethoxy-ethyl)-2-(1-hydroxy-2-methyl-2-cyclopentenyl) benzene,
(78) 1-(1, the 1-dimethoxy-ethyl)-2-(1-hydroxy-3-methyl-2-cyclopentenyl) benzene,
(79) 1-(1, the 1-dimethoxy-ethyl)-2-(1-hydroxyl-2,3-dimethyl-2-cyclopentenyl) benzene,
(80) 1-(1, the 1-dimethoxy-ethyl)-2-(1-hydroxyl-2,4-dimethyl-2-cyclopentenyl) benzene,
(81) 1-(1, the 1-dimethoxy-ethyl)-2-(1-hydroxyl-3,4-dimethyl-2-cyclopentenyl) benzene,
(82) 1-(1, the 1-dimethoxy-ethyl)-2-(1-hydroxyl-2,3,4-trimethylammonium-2-cyclopentenyl) benzene,
(83) 1-(1, the 1-dimethoxy-ethyl)-2-(2-hydroxyl-2,4,5-trimethylammonium-2-cyclopentenyl) benzene,
(84) 1-(1, the 1-dimethoxy-ethyl)-2-(1-hydroxyl-2,3,4,5-tetramethyl--2-cyclopentenyl) benzene,
(85) 1-(1, the 1-dimethoxy-ethyl)-2-(the 1-hydroxyl-2-tertiary butyl-2-cyclopentenyl) benzene,
(86) 1-(1, the 1-dimethoxy-ethyl)-2-(the 1-hydroxyl-3-tertiary butyl-2-cyclopentenyl) benzene,
(87) 1-(1, the 1-dimethoxy-ethyl)-2-(1-hydroxyl-2-dimethylamino-2-cyclopentenyl) benzene,
(88) 1-(1, the 1-dimethoxy-ethyl)-2-(1-hydroxyl-3-dimethylamino-2-cyclopentenyl) benzene,
(89) 1-(1, the 1-dimethoxy-ethyl)-2-(1-hydroxy-2-methyl indane-1-yl) benzene,
(90) 1-(1, the 1-dimethoxy-ethyl)-2-(1-hydroxyl-2-phenyl indan-1-yl) benzene,
(91) 1-(1,1-dimethoxy propyl group)-2-(1-hydroxyl-2-cyclopentenyl) benzene,
(92) 1-(1,1-dimethoxy propyl group)-2-(1-hydroxy-2-methyl-2-cyclopentenyl) benzene,
(93) 1-(1,1-dimethoxy propyl group)-2-(1-hydroxy-3-methyl-2-cyclopentenyl) benzene,
(94) 1-(1,1-dimethoxy propyl group)-2-(1-hydroxyl-2,3-dimethyl-2-cyclopentenyl) benzene,
(95) 1-(1,1-dimethoxy propyl group)-2-(1-hydroxyl-2,4-dimethyl-2-cyclopentenyl) benzene,
(96) 1-(1,1-dimethoxy propyl group)-2-(1-hydroxyl-3,4-dimethyl-2-cyclopentenyl) benzene,
(97) 1-(1,1-dimethoxy propyl group)-2-(1-hydroxyl-2,3,4-trimethylammonium-2-cyclopentenyl) benzene,
(98) 1-(1,1-dimethoxy propyl group)-2-(2-hydroxyl-2,4,5-trimethylammonium-2-cyclopentenyl) benzene,
(99) 1-(1,1-dimethoxy propyl group)-2-(1-hydroxyl-2,3,4,5-tetramethyl--2-cyclopentenyl) benzene,
(100) 1-(1,1-dimethoxy propyl group)-2-(the 1-hydroxyl-2-tertiary butyl-2-cyclopentenyl) benzene,
(101) 1-(1,1-dimethoxy propyl group)-2-(the 1-hydroxyl-3-tertiary butyl-2-cyclopentenyl) benzene,
(102) 1-(1,1-dimethoxy propyl group)-2-(1-hydroxyl-2-dimethylamino-2-cyclopentenyl) benzene,
(103) 1-(1,1-dimethoxy propyl group)-2-(1-hydroxyl-3-dimethylamino-2-cyclopentenyl) benzene,
(104) 1-(1,1-dimethoxy propyl group)-2-(1-hydroxy-2-methyl indane-1-yl) benzene,
(105) 1-(1,1-dimethoxy propyl group)-2-(1-hydroxyl-2-phenyl indan-1-yl) benzene,
(106) 1-(1,1-dimethoxy-1-phenyl methyl)-2-(1-hydroxyl-2-cyclopentenyl) benzene,
(107) 1-(1,1-dimethoxy-1-phenyl methyl)-2-(1-hydroxy-2-methyl-2-cyclopentenyl) benzene,
(108) 1-(1,1-dimethoxy-1-phenyl methyl)-2-(1-hydroxy-3-methyl-2-cyclopentenyl) benzene,
(109) 1-(1,1-dimethoxy-1-phenyl methyl)-2-(1-hydroxyl-2,3-dimethyl-2-cyclopentenyl) benzene,
(110) 1-(1,1-dimethoxy-1-phenyl methyl)-2-(1-hydroxyl-2,4-dimethyl-2-cyclopentenyl) benzene,
(111) 1-(1,1-dimethoxy-1-phenyl methyl)-2-(1-hydroxyl-3,4-dimethyl-2-cyclopentenyl) benzene,
(112) 1-(1,1-dimethoxy-1-phenyl methyl)-2-(1-hydroxyl-2,3,4-trimethylammonium-2-cyclopentenyl) benzene,
(113) 1-(1,1-dimethoxy-1-phenyl methyl)-2-(2-hydroxyl-2,4,5-trimethylammonium-2-cyclopentenyl) benzene,
(114) 1-(1,1-dimethoxy-1-phenyl methyl)-2-(1-hydroxyl-2,3,4,5-tetramethyl--2-cyclopentenyl) benzene,
(115) 1-(1,1-dimethoxy-1-phenyl methyl)-2-(the 1-hydroxyl-2-tertiary butyl-2-cyclopentenyl) benzene,
(116) 1-(1,1-dimethoxy-1-phenyl methyl)-2-(the 1-hydroxyl-3-tertiary butyl-2-cyclopentenyl) benzene,
(117) 1-(1,1-dimethoxy-1-phenyl methyl)-2-(1-hydroxyl-2-dimethylamino-2-cyclopentenyl) benzene,
(118) 1-(1,1-dimethoxy-1-phenyl methyl)-2-(1-hydroxyl-3-dimethylamino-2-cyclopentenyl) benzene,
(119) 1-(1,1-dimethoxy-1-phenyl methyl)-2-(1-hydroxy-2-methyl indane-1-yl) benzene,
(120) 1-(1,1-dimethoxy-1-phenyl methyl)-2-(1-hydroxyl-2-phenyl indan-1-yl) benzene etc.
Equally, can also exemplify out the compound etc. that benzene in the above-claimed cpd changes substituted benzene into or replaces naphthalene.
Second step was the step that makes carbonyl compound (substituted cyclopentadiene part) shown in the cyclopentenol of formula (4) and the acid-respons production (1).
The acid that is used for above-mentioned reaction comprises mineral acid example hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid etc.; Carboxylic acid such as formic acid, acetate, Mono Chloro Acetic Acid, trifluoroacetic acid, propionic acid, valeric acid, phenylformic acid etc.; Sulfonic acid such as methylsulfonic acid, trifluoromethanesulfonic acid, Phenylsulfonic acid, toluenesulphonic acids etc.These acid can be used separately, also can be used as mixture or diluting soln such as the aqueous solution and use.Consumption to acid is not particularly limited.
Above-mentioned reaction is carried out in the presence of solvent usually, generates carbonyl compound shown in the formula (1) with cyclopentadiene structure by cyclopentenol shown in the adding formula (4) in acid.Reaction is carried out at-20 ℃ of boiling points to solvent usually, preferred 0-80 ℃.
The solvent that is used to react comprises aromatic solvents such as benzene,toluene,xylene; Aliphatic hydrocarbon solvent such as hexane, heptane; Ether, tetrahydrofuran (THF), 1, ether solvents such as 4-diox; Amide solvent such as hexamethyl phosphoric triamide, dimethyl formamide; Alcoholic solvents such as methyl alcohol, ethanol, propyl alcohol, butanols; Ketone solvents such as acetone, cyclopentanone, methyl iso-butyl ketone (MIBK); And water.Can use the mixture of a kind of solvent or two or more solvents.Described solvent can be a homogeneous system, also can be two-phase system.The consumption of solvent is generally the 1-200 weight part with respect to halogen compounds shown in the 1 weight part formula (2), preferred 5-30 weight part.
After the reaction, if desired, can in the gained reaction mixture, add entry, then this mixture separation be become organic layer and water layer, to obtain target compound solution as organic layer.When because in described reaction, use with the solvent of water compatible or use a small amount of solvent and when making organic layer and water layer not easily separated, can after in reaction mixture, adding water-insoluble organic solvents such as toluene, ethyl acetate, chlorobenzene, separate.Carbonyl compound shown in the formula (1) can be purified by for example following operation: wash described solution with water, dry described solution, distilling off solvent is also further purified through methods such as recrystallization, distillation, column chromatography processing then.
At J.Org.Chem., 2-(indenes-1-yl) phenyl aldehyde is disclosed in 1974,39,829 and Aust.J.Chem., 1993,46,1515.But described compound is by with chromic acid oxidation 3, and 6-dibenzo three ring [3,3,0,0] octadienes synthesize, and the result has occurred obtaining raw material 3,6-dibenzo three ring [3,3,0,0] octadiene aspects such problem that has difficulties.At Chem.Ber., 1992,125,2-(2-benzyl-3-phenyl-1H-indenes-1-yl) phenyl aldehyde as by product has been described among the 1461-1469 in full (polyindane) compound of polyindene synthetic.
The object lesson of carbonyl compound comprises following compounds shown in the formula (1):
(1) 2-(cyclopentadienyl) phenyl aldehyde,
(2) 2-(2-methyl cyclopentadienyl) phenyl aldehyde,
(3) 2-(3-methyl cyclopentadienyl) phenyl aldehyde,
(4) 2-(2,3-dimethyl cyclopentadienyl) phenyl aldehyde,
(5) 2-(2,4-dimethyl cyclopentadienyl) phenyl aldehyde,
(6) 2-(3,4-dimethyl cyclopentadienyl) phenyl aldehyde,
(7) 2-(2,3,4-trimethylammonium cyclopentadienyl) phenyl aldehyde,
(8) 2-(2,4,5-trimethylammonium cyclopentadienyl) phenyl aldehyde,
(9) 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl aldehyde,
(10) 2-(2-tertiary butyl cyclopentadienyl) phenyl aldehyde,
(11) 2-(3-tertiary butyl cyclopentadienyl) phenyl aldehyde,
(12) 2-(2-dimethylamino cyclopentadienyl) phenyl aldehyde,
(13) 2-(3-dimethylamino cyclopentadienyl) phenyl aldehyde,
(14) 2-(cyclopentadienyl) methyl phenyl ketone,
(15) 2-(2-methyl cyclopentadienyl) methyl phenyl ketone,
(16) 2-(3-methyl cyclopentadienyl) methyl phenyl ketone,
(17) 2-(2,3-dimethyl cyclopentadienyl) methyl phenyl ketone,
(18) 2-(2,4-dimethyl cyclopentadienyl) methyl phenyl ketone,
(19) 2-(3,4-dimethyl cyclopentadienyl) methyl phenyl ketone,
(20) 2-(2,3,4-trimethylammonium cyclopentadienyl) methyl phenyl ketone,
(21) 2-(2,4,5-trimethylammonium cyclopentadienyl) methyl phenyl ketone,
(22) 2-(2,3,4,5-tetramethyl-ring pentadienyl) methyl phenyl ketone,
(23) 2-(2-tertiary butyl cyclopentadienyl) methyl phenyl ketone,
(24) 2-(3-tertiary butyl cyclopentadienyl) methyl phenyl ketone,
(25) 2-(2-dimethylamino cyclopentadienyl) methyl phenyl ketone,
(26) 2-(3-dimethylamino cyclopentadienyl) methyl phenyl ketone,
(27) 2-(cyclopentadienyl) Propiophenone,
(28) 2-(2-methyl cyclopentadienyl) Propiophenone,
(29) 2-(3-methyl cyclopentadienyl) Propiophenone,
(30) 2-(2,3-dimethyl cyclopentadienyl) Propiophenone,
(31) 2-(2,4-dimethyl cyclopentadienyl) Propiophenone,
(32) 2-(3,4-dimethyl cyclopentadienyl) Propiophenone,
(33) 2-(2,3,4-trimethylammonium cyclopentadienyl) Propiophenone,
(34) 2-(2,4,5-trimethylammonium cyclopentadienyl) Propiophenone,
(35) 2-(2,3,4,5-tetramethyl-ring pentadienyl) Propiophenone,
(36) 2-(2-tertiary butyl cyclopentadienyl) Propiophenone,
(37) 2-(3-tertiary butyl cyclopentadienyl) Propiophenone,
(38) 2-(2-dimethylamino cyclopentadienyl) Propiophenone,
(39) 2-(3-dimethylamino cyclopentadienyl) Propiophenone,
(40) 2-(cyclopentadienyl) benzophenone,
(41) 2-(2-methyl cyclopentadienyl) benzophenone,
(42) 2-(3-methyl cyclopentadienyl) benzophenone,
(43) 2-(2,3-dimethyl cyclopentadienyl) benzophenone,
(44) 2-(2,4-dimethyl cyclopentadienyl) benzophenone,
(45) 2-(3,4-dimethyl cyclopentadienyl) benzophenone,
(46) 2-(2,3,4-trimethylammonium cyclopentadienyl) benzophenone,
(47) 2-(2,4,5-trimethylammonium cyclopentadienyl) benzophenone,
(48) 2-(2,3,4,5-tetramethyl-ring pentadienyl) benzophenone,
(49) 2-(2-tertiary butyl cyclopentadienyl) benzophenone,
(50) 2-(3-tertiary butyl cyclopentadienyl) benzophenone,
(51) 2-(2-dimethylamino cyclopentadienyl) benzophenone,
(52) 2-(3-dimethylamino cyclopentadienyl) benzophenone,
(53) 3-(cyclopentadienyl)-2-naphthaldehyde,
(54) 3-(2-methyl cyclopentadienyl)-2-naphthaldehyde,
(55) 3-(3-methyl cyclopentadienyl)-2-naphthaldehyde,
(56) 3-(2,3-dimethyl cyclopentadienyl)-2-naphthaldehyde,
(57) 3-(2,4-dimethyl cyclopentadienyl)-2-naphthaldehyde,
(58) 3-(3,4-dimethyl cyclopentadienyl)-2-naphthaldehyde,
(59) 3-(2,3,4-trimethylammonium cyclopentadienyl)-2-naphthaldehyde,
(60) 3-(2,4,5-trimethylammonium cyclopentadienyl)-2-naphthaldehyde,
(61) 3-(2,3,4,5-tetramethyl-ring pentadienyl)-2-naphthaldehyde,
(62) 3-(2-tertiary butyl cyclopentadienyl)-2-naphthaldehyde,
(63) 3-(3-tertiary butyl cyclopentadienyl)-2-naphthaldehyde,
(64) 3-(2-dimethylamino cyclopentadienyl)-2-naphthaldehyde,
(65) 3-(3-dimethylamino cyclopentadienyl)-2-naphthaldehyde,
(66) 3-(cyclopentadienyl)-2-acetylnaphthalene,
(67) 3-(2-methyl cyclopentadienyl)-2-acetylnaphthalene,
(68) 3-(3-methyl cyclopentadienyl)-2-acetylnaphthalene,
(69) 3-(2,3-dimethyl cyclopentadienyl)-2-acetylnaphthalene,
(70) 3-(2,4-dimethyl cyclopentadienyl)-2-acetylnaphthalene,
(71) 3-(3,4-dimethyl cyclopentadienyl)-2-acetylnaphthalene,
(72) 3-(2,3,4-trimethylammonium cyclopentadienyl)-2-acetylnaphthalene,
(73) 3-(2,4,5-trimethylammonium cyclopentadienyl)-2-acetylnaphthalene,
(74) 3-(2,3,4,5-tetramethyl-ring pentadienyl)-2-acetylnaphthalene,
(75) 3-(2-tertiary butyl cyclopentadienyl)-2-acetylnaphthalene,
(76) 3-(3-tertiary butyl cyclopentadienyl)-2-acetylnaphthalene,
(77) 3-(2-dimethylamino cyclopentadienyl)-2-acetylnaphthalene,
(78) 3-(3-dimethylamino cyclopentadienyl)-2-acetylnaphthalene,
(79) 3-(cyclopentadienyl)-2-propionyl naphthalene,
(80) 3-(2-methyl cyclopentadienyl)-2-propionyl naphthalene,
(81) 3-(3-methyl cyclopentadienyl)-2-propionyl naphthalene,
(82) 3-(2,3-dimethyl cyclopentadienyl)-2-propionyl naphthalene,
(83) 3-(2,4-dimethyl cyclopentadienyl)-2-propionyl naphthalene,
(84) 3-(3,4-dimethyl cyclopentadienyl)-2-propionyl naphthalene,
(85) 3-(2,3,4-trimethylammonium cyclopentadienyl)-2-propionyl naphthalene,
(86) 3-(2,4,5-trimethylammonium cyclopentadienyl)-2-propionyl naphthalene,
(87) 3-(2,3,4,5-tetramethyl-ring pentadienyl)-2-propionyl naphthalene,
(88) 3-(2-tertiary butyl cyclopentadienyl)-2-propionyl naphthalene,
(89) 3-(3-tertiary butyl cyclopentadienyl)-2-propionyl naphthalene,
(90) 3-(2-dimethylamino cyclopentadienyl)-2-propionyl naphthalene,
(91) 3-(3-dimethylamino cyclopentadienyl)-2-propionyl naphthalene,
(92) 3-(cyclopentadienyl)-2-benzoyl naphthalene,
(93) 3-(2-methyl cyclopentadienyl)-2-benzoyl naphthalene,
(94) 3-(3-methyl cyclopentadienyl)-2-benzoyl naphthalene,
(95) 3-(2,3-dimethyl cyclopentadienyl)-2-benzoyl naphthalene,
(96) 3-(2,4-dimethyl cyclopentadienyl)-2-benzoyl naphthalene,
(97) 3-(3,4-dimethyl cyclopentadienyl)-2-benzoyl naphthalene,
(98) 3-(2,3,4-trimethylammonium cyclopentadienyl)-2-benzoyl naphthalene,
(99) 3-(2,4,5-trimethylammonium cyclopentadienyl)-2-benzoyl naphthalene,
(100) 3-(2,3,4,5-tetramethyl-ring pentadienyl)-2-benzoyl naphthalene,
(101) 3-(2-tertiary butyl cyclopentadienyl)-2-benzoyl naphthalene,
(102) 3-(3-tertiary butyl cyclopentadienyl)-2-benzoyl naphthalene,
(103) 3-(2-dimethylamino cyclopentadienyl)-2-benzoyl naphthalene,
(104) 3-(3-dimethylamino cyclopentadienyl)-2-benzoyl naphthalene,
(105) 2-(cyclopentadienyl)-1-naphthaldehyde,
(106) 2-(2-methyl cyclopentadienyl)-1-naphthaldehyde,
(107) 2-(3-methyl cyclopentadienyl)-1-naphthaldehyde,
(108) 2-(2,3-dimethyl cyclopentadienyl)-1-naphthaldehyde,
(109) 2-(2,4-dimethyl cyclopentadienyl)-1-naphthaldehyde,
(110) 2-(3,4-dimethyl cyclopentadienyl)-1-naphthaldehyde,
(111) 2-(2,3,4-trimethylammonium cyclopentadienyl)-1-naphthaldehyde,
(112) 2-(2,4,5-trimethylammonium cyclopentadienyl)-1-naphthaldehyde,
(113) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-naphthaldehyde,
(114) 2-(2-tertiary butyl cyclopentadienyl)-1-naphthaldehyde,
(115) 2-(3-tertiary butyl cyclopentadienyl)-1-naphthaldehyde,
(116) 2-(2-dimethylamino cyclopentadienyl)-1-naphthaldehyde,
(117) 2-(3-dimethylamino cyclopentadienyl)-1-naphthaldehyde,
(118) 2-(cyclopentadienyl)-1-acetonaphthone,
(119) 2-(2-methyl cyclopentadienyl)-1-acetonaphthone,
(120) 2-(3-methyl cyclopentadienyl)-1-acetonaphthone,
(121) 2-(2,3-dimethyl cyclopentadienyl)-1-acetonaphthone,
(122) 2-(2,4-dimethyl cyclopentadienyl)-1-acetonaphthone,
(123) 2-(3,4-dimethyl cyclopentadienyl)-1-acetonaphthone,
(124) 2-(2,3,4-trimethylammonium cyclopentadienyl)-1-acetonaphthone,
(125) 2-(2,4,5-trimethylammonium cyclopentadienyl)-1-acetonaphthone,
(126) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-acetonaphthone,
(127) 2-(2-tertiary butyl cyclopentadienyl)-1-acetonaphthone,
(128) 2-(3-tertiary butyl cyclopentadienyl)-1-acetonaphthone,
(129) 2-(2-dimethylamino cyclopentadienyl)-1-acetonaphthone,
(130) 2-(3-dimethylamino cyclopentadienyl)-1-acetonaphthone,
(131) 2-(cyclopentadienyl)-1-propionyl naphthalene,
(132) 2-(2-methyl cyclopentadienyl)-1-propionyl naphthalene,
(133) 2-(3-methyl cyclopentadienyl)-1-propionyl naphthalene,
(134) 2-(2,3-dimethyl cyclopentadienyl)-1-propionyl naphthalene,
(135) 2-(2,4-dimethyl cyclopentadienyl)-1-propionyl naphthalene,
(136) 2-(3,4-dimethyl cyclopentadienyl)-1-propionyl naphthalene,
(137) 2-(2,3,4-trimethylammonium cyclopentadienyl)-1-propionyl naphthalene,
(138) 2-(2,4,5-trimethylammonium cyclopentadienyl)-1-propionyl naphthalene,
(139) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-propionyl naphthalene,
(140) 2-(2-tertiary butyl cyclopentadienyl)-1-propionyl naphthalene,
(141) 2-(3-tertiary butyl cyclopentadienyl)-1-propionyl naphthalene,
(142) 2-(2-dimethylamino cyclopentadienyl)-1-propionyl naphthalene,
(143) 2-(3-dimethylamino cyclopentadienyl)-1-propionyl naphthalene,
(144) 2-(cyclopentadienyl)-1-benzoyl naphthalene,
(145) 2-(2-methyl cyclopentadienyl)-1-benzoyl naphthalene,
(146) 2-(3-methyl cyclopentadienyl)-1-benzoyl naphthalene,
(147) 2-(2,3-dimethyl cyclopentadienyl)-1-benzoyl naphthalene,
(148) 2-(2,4-dimethyl cyclopentadienyl)-1-benzoyl naphthalene,
(149) 2-(3,4-dimethyl cyclopentadienyl)-1-benzoyl naphthalene,
(150) 2-(2,3,4-trimethylammonium cyclopentadienyl)-1-benzoyl naphthalene,
(151) 2-(2,4,5-trimethylammonium cyclopentadienyl)-1-benzoyl naphthalene,
(152) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-1-benzoyl naphthalene,
(153) 2-(2-tertiary butyl cyclopentadienyl)-1-benzoyl naphthalene,
(154) 2-(3-tertiary butyl cyclopentadienyl)-1-benzoyl naphthalene,
(155) 2-(2-dimethylamino cyclopentadienyl)-1-benzoyl naphthalene,
(156) 2-(3-dimethylamino cyclopentadienyl)-1-benzoyl naphthalene,
(157) 2-(cyclopentadienyl)-5-tert.-butylbenzene formaldehyde,
(158) 2-(2-methyl cyclopentadienyl)-5-tert.-butylbenzene formaldehyde,
(159) 2-(3-methyl cyclopentadienyl)-5-tert.-butylbenzene formaldehyde,
(160) 2-(2,3-dimethyl cyclopentadienyl)-5-tert.-butylbenzene formaldehyde,
(161) 2-(2,4-dimethyl cyclopentadienyl)-5-tert.-butylbenzene formaldehyde,
(162) 2-(3,4-dimethyl cyclopentadienyl)-5-tert.-butylbenzene formaldehyde,
(163) 2-(2,3,4-trimethylammonium cyclopentadienyl)-5-tert.-butylbenzene formaldehyde,
(164) 2-(2,4,5-trimethylammonium cyclopentadienyl)-5-tert.-butylbenzene formaldehyde,
(165) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-5-tert.-butylbenzene formaldehyde,
(166) 2-(2-tertiary butyl cyclopentadienyl)-5-tert.-butylbenzene formaldehyde,
(167) 2-(3-tertiary butyl cyclopentadienyl)-5-tert.-butylbenzene formaldehyde,
(168) 2-(2-dimethylamino cyclopentadienyl)-5-tert.-butylbenzene formaldehyde,
(169) 2-(3-dimethylamino cyclopentadienyl)-5-tert.-butylbenzene formaldehyde,
(170) 2-(cyclopentadienyl)-5-tert.-butylbenzene ethyl ketone,
(171) 2-(2-methyl cyclopentadienyl)-5-tert.-butylbenzene ethyl ketone,
(172) 2-(3-methyl cyclopentadienyl)-5-tert.-butylbenzene ethyl ketone,
(173) 2-(2,3-dimethyl cyclopentadienyl)-5-tert.-butylbenzene ethyl ketone,
(174) 2-(2,4-dimethyl cyclopentadienyl)-5-tert.-butylbenzene ethyl ketone,
(175) 2-(3,4-dimethyl cyclopentadienyl)-5-tert.-butylbenzene ethyl ketone,
(176) 2-(2,3,4-trimethylammonium cyclopentadienyl)-5-tert.-butylbenzene ethyl ketone,
(177) 2-(2,4,5-trimethylammonium cyclopentadienyl)-5-tert.-butylbenzene ethyl ketone,
(178) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-5-tert.-butylbenzene ethyl ketone,
(179) 2-(2-tertiary butyl cyclopentadienyl)-5-tert.-butylbenzene ethyl ketone,
(180) 2-(3-tertiary butyl cyclopentadienyl)-5-tert.-butylbenzene ethyl ketone,
(181) 2-(2-dimethylamino cyclopentadienyl)-5-tert.-butylbenzene ethyl ketone,
(182) 2-(3-dimethylamino cyclopentadienyl)-5-tert.-butylbenzene ethyl ketone,
(183) 2-(cyclopentadienyl)-5-tert-butyl-phenyl ethyl ketone,
(184) 2-(2-methyl cyclopentadienyl)-5-tert-butyl-phenyl ethyl ketone,
(185) 2-(3-methyl cyclopentadienyl)-5-tert-butyl-phenyl ethyl ketone,
(186) 2-(2,3-dimethyl cyclopentadienyl)-5-tert-butyl-phenyl ethyl ketone,
(187) 2-(2,4-dimethyl cyclopentadienyl)-5-tert-butyl-phenyl ethyl ketone,
(188) 2-(3,4-dimethyl cyclopentadienyl)-5-tert-butyl-phenyl ethyl ketone,
(189) 2-(2,3,4-trimethylammonium cyclopentadienyl)-5-tert-butyl-phenyl ethyl ketone,
(190) 2-(2,4,5-trimethylammonium cyclopentadienyl)-5-tert-butyl-phenyl ethyl ketone,
(191) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-5-tert-butyl-phenyl ethyl ketone,
(192) 2-(2-tertiary butyl cyclopentadienyl)-5-tert-butyl-phenyl ethyl ketone,
(193) 2-(3-tertiary butyl cyclopentadienyl)-5-tert-butyl-phenyl ethyl ketone,
(194) 2-(2-dimethylamino cyclopentadienyl)-5-tert-butyl-phenyl ethyl ketone,
(195) 2-(3-dimethylamino cyclopentadienyl)-5-tert-butyl-phenyl ethyl ketone,
(196) 2-(cyclopentadienyl)-5-tertiary butyl benzophenone,
(197) 2-(2-methyl cyclopentadienyl)-5-tertiary butyl benzophenone,
(198) 2-(3-methyl cyclopentadienyl)-5-tertiary butyl benzophenone,
(199) 2-(2,3-dimethyl cyclopentadienyl)-5-tertiary butyl benzophenone,
(200) 2-(2,4-dimethyl cyclopentadienyl)-5-tertiary butyl benzophenone,
(201) 2-(3,4-dimethyl cyclopentadienyl)-5-tertiary butyl benzophenone,
(202) 2-(2,3,4-trimethylammonium cyclopentadienyl)-5-tertiary butyl benzophenone,
(203) 2-(2,4,5-trimethylammonium cyclopentadienyl)-5-tertiary butyl benzophenone,
(204) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-5-tertiary butyl benzophenone,
(205) 2-(2-tertiary butyl cyclopentadienyl)-5-tertiary butyl benzophenone,
(206) 2-(3-tertiary butyl cyclopentadienyl)-5-tertiary butyl benzophenone,
(207) 2-(2-dimethylamino cyclopentadienyl)-5-tertiary butyl benzophenone,
(208) 2-(3-dimethylamino cyclopentadienyl)-5-tertiary butyl benzophenone,
(209) 2-(cyclopentadienyl)-5-chlorobenzaldehyde,
(210) 2-(2-methyl cyclopentadienyl)-5-chlorobenzaldehyde,
(211) 2-(3-methyl cyclopentadienyl)-5-chlorobenzaldehyde,
(212) 2-(2,3-dimethyl cyclopentadienyl)-5-chlorobenzaldehyde,
(213) 2-(2,4-dimethyl cyclopentadienyl)-5-chlorobenzaldehyde,
(214) 2-(3,4-dimethyl cyclopentadienyl)-5-chlorobenzaldehyde,
(215) 2-(2,3,4-trimethylammonium cyclopentadienyl)-5-chlorobenzaldehyde,
(216) 2-(2,4,5-trimethylammonium cyclopentadienyl)-5-chlorobenzaldehyde,
(217) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-5-chlorobenzaldehyde,
(218) 2-(2-tertiary butyl cyclopentadienyl)-5-chlorobenzaldehyde,
(219) 2-(3-tertiary butyl cyclopentadienyl)-5-chlorobenzaldehyde,
(220) 2-(2-dimethylamino cyclopentadienyl)-5-chlorobenzaldehyde,
(221) 2-(3-dimethylamino cyclopentadienyl)-5-chlorobenzaldehyde,
(222) 2-(cyclopentadienyl)-5-chloro-acetophenone,
(223) 2-(2-methyl cyclopentadienyl)-5-chloro-acetophenone,
(224) 2-(3-methyl cyclopentadienyl)-5-chloro-acetophenone,
(225) 2-(2,3-dimethyl cyclopentadienyl)-5-chloro-acetophenone,
(226) 2-(2,4-dimethyl cyclopentadienyl)-5-chloro-acetophenone,
(227) 2-(3,4-dimethyl cyclopentadienyl)-5-chloro-acetophenone,
(228) 2-(2,3,4-trimethylammonium cyclopentadienyl-5-chloro-acetophenone,
(229) 2-(2,4,5-trimethylammonium cyclopentadienyl)-5-chloro-acetophenone,
(230) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-5-chloro-acetophenone,
(231) 2-(2-tertiary butyl cyclopentadienyl)-5-chloro-acetophenone,
(232) 2-(3-tertiary butyl cyclopentadienyl)-5-chloro-acetophenone,
(233) 2-(2-dimethylamino cyclopentadienyl)-5-chloro-acetophenone,
(234) 2-(3-dimethylamino cyclopentadienyl)-5-chloro-acetophenone,
(235) 2-(cyclopentadienyl)-5-chloro-phenyl-ethyl ketone,
(236) 2-(2-methyl cyclopentadienyl)-5-chloro-phenyl-ethyl ketone,
(237) 2-(3-methyl cyclopentadienyl)-5-chloro-phenyl-ethyl ketone,
(238) 2-(2,3-dimethyl cyclopentadienyl)-5-chloro-phenyl-ethyl ketone,
(239) 2-(2,4-dimethyl cyclopentadienyl)-5-chloro-phenyl-ethyl ketone,
(240) 2-(3,4-dimethyl cyclopentadienyl)-5-chloro-phenyl-ethyl ketone,
(241) 2-(2,3,4-trimethylammonium cyclopentadienyl)-5-chloro-phenyl-ethyl ketone,
(242) 2-(2,4,5-trimethylammonium cyclopentadienyl)-5-chloro-phenyl-ethyl ketone,
(243) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-5-chloro-phenyl-ethyl ketone,
(244) 2-(2-tertiary butyl cyclopentadienyl)-5-chloro-phenyl-ethyl ketone,
(245) 2-(3-tertiary butyl cyclopentadienyl)-5-chloro-phenyl-ethyl ketone,
(246) 2-(2-dimethylamino cyclopentadienyl)-5-chloro-phenyl-ethyl ketone,
(247) 2-(3-dimethylamino cyclopentadienyl)-5-chloro-phenyl-ethyl ketone,
(248) 2-(cyclopentadienyl)-5-chloro benzophenone,
(249) 2-(2-methyl cyclopentadienyl)-5-chloro benzophenone,
(250) 2-(3-methyl cyclopentadienyl)-5-chloro benzophenone,
(251) 2-(2,3-dimethyl cyclopentadienyl)-5-chloro benzophenone,
(252) 2-(2,4-dimethyl cyclopentadienyl)-5-chloro benzophenone,
(253) 2-(3,4-dimethyl cyclopentadienyl)-5-chloro benzophenone,
(254) 2-(2,3,4-trimethylammonium cyclopentadienyl)-5-chloro benzophenone,
(255) 2-(2,4,5-trimethylammonium cyclopentadienyl)-5-chloro benzophenone,
(256) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-5-chloro benzophenone,
(257) 2-(2-tertiary butyl cyclopentadienyl)-5-chloro benzophenone,
(258) 2-(3-tertiary butyl cyclopentadienyl)-5-chloro benzophenone,
(259) 2-(2-dimethylamino cyclopentadienyl)-5-chloro benzophenone,
(260) 2-(3-dimethylamino cyclopentadienyl)-5-chloro benzophenone,
(261) 2-(cyclopentadienyl)-5-methoxybenzaldehyde,
(262) 2-(2-methyl cyclopentadienyl)-5-methoxybenzaldehyde,
(263) 2-(3-methyl cyclopentadienyl)-5-methoxybenzaldehyde,
(264) 2-(2,3-dimethyl cyclopentadienyl)-5-methoxybenzaldehyde,
(265) 2-(2,4-dimethyl cyclopentadienyl)-5-methoxybenzaldehyde,
(266) 2-(3,4-dimethyl cyclopentadienyl)-5-methoxybenzaldehyde,
(267) 2-(2,3,4-trimethylammonium cyclopentadienyl)-5-methoxybenzaldehyde,
(268) 2-(2,4,5-trimethylammonium cyclopentadienyl)-5-methoxybenzaldehyde,
(269) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-5-methoxybenzaldehyde,
(270) 2-(2-tertiary butyl cyclopentadienyl)-5-methoxybenzaldehyde,
(271) 2-(3-tertiary butyl cyclopentadienyl)-5-methoxybenzaldehyde,
(272) 2-(2-dimethylamino cyclopentadienyl)-5-methoxybenzaldehyde,
(273) 2-(3-dimethylamino cyclopentadienyl)-5-methoxybenzaldehyde,
(274) 2-(cyclopentadienyl)-5-methoxyacetophenone,
(275) 2-(2-methyl cyclopentadienyl)-5-methoxyacetophenone,
(276) 2-(3-methyl cyclopentadienyl)-5-methoxyacetophenone,
(277) 2-(2,3-dimethyl cyclopentadienyl)-5-methoxyacetophenone,
(278) 2-(2,4-dimethyl cyclopentadienyl)-5-methoxyacetophenone,
(279) 2-(3,4-dimethyl cyclopentadienyl)-5-methoxyacetophenone,
(280) 2-(2,3,4-trimethylammonium cyclopentadienyl)-5-methoxyacetophenone,
(281) 2-(2,4,5-trimethylammonium cyclopentadienyl)-5-methoxyacetophenone,
(282) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-5-methoxyacetophenone,
(283) 2-(2-tertiary butyl cyclopentadienyl)-5-methoxyacetophenone,
(284) 2-(3-tertiary butyl cyclopentadienyl)-5-methoxyacetophenone,
(285) 2-(2-dimethylamino cyclopentadienyl)-5-methoxyacetophenone,
(286) 2-(3-dimethylamino cyclopentadienyl)-5-methoxyacetophenone,
(287) 2-(cyclopentadienyl)-5-p-methoxy-phenyl ethyl ketone,
(288) 2-(2-methyl cyclopentadienyl)-5-p-methoxy-phenyl ethyl ketone,
(289) 2-(3-methyl cyclopentadienyl)-5-p-methoxy-phenyl ethyl ketone,
(290) 2-(2,3-dimethyl cyclopentadienyl)-5-p-methoxy-phenyl ethyl ketone,
(291) 2-(2,4-dimethyl cyclopentadienyl)-5-p-methoxy-phenyl ethyl ketone,
(292) 2-(3,4-dimethyl cyclopentadienyl)-5-p-methoxy-phenyl ethyl ketone,
(293) 2-(2,3,4-trimethylammonium cyclopentadienyl)-5-p-methoxy-phenyl ethyl ketone,
(294) 2-(2,4,5-trimethylammonium cyclopentadienyl)-5-p-methoxy-phenyl ethyl ketone,
(295) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-5-p-methoxy-phenyl ethyl ketone,
(296) 2-(2-tertiary butyl cyclopentadienyl)-5-p-methoxy-phenyl ethyl ketone,
(297) 2-(3-tertiary butyl cyclopentadienyl)-5-p-methoxy-phenyl ethyl ketone,
(298) 2-(2-dimethylamino cyclopentadienyl)-5-p-methoxy-phenyl ethyl ketone,
(299) 2-(3-dimethylamino cyclopentadienyl)-5-p-methoxy-phenyl ethyl ketone,
(300) 2-(cyclopentadienyl)-5-methoxyl group benzophenone,
(301) 2-(2-methyl cyclopentadienyl)-5-methoxyl group benzophenone,
(302) 2-(3-methyl cyclopentadienyl)-5-methoxyl group benzophenone,
(303) 2-(2,3-dimethyl cyclopentadienyl)-5-methoxyl group benzophenone,
(304) 2-(2,4-dimethyl cyclopentadienyl)-5-methoxyl group benzophenone,
(305) 2-(3,4-dimethyl cyclopentadienyl)-5-methoxyl group benzophenone,
(306) 2-(2,3,4-trimethylammonium cyclopentadienyl)-5-methoxyl group benzophenone,
(307) 2-(2,4,5-trimethylammonium cyclopentadienyl)-5-methoxyl group benzophenone,
(308) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-5-methoxyl group benzophenone,
(309) 2-(2-tertiary butyl cyclopentadienyl)-5-methoxyl group benzophenone,
(310) 2-(3-tertiary butyl cyclopentadienyl)-5-methoxyl group benzophenone,
(311) 2-(2-dimethylamino cyclopentadienyl)-5-methoxyl group benzophenone,
(312) 2-(3-dimethylamino cyclopentadienyl)-5-methoxyl group benzophenone,
(313) 2-(cyclopentadienyl)-5-methoxyl group benzophenone,
(314) 2-(methyl cyclopentadienyl)-5-methoxyl group benzophenone,
(315) 2-(dimethyl cyclopentadienyl)-5-methoxyl group benzophenone,
(316) 2-(trimethylammonium cyclopentadienyl)-5-methoxyl group benzophenone,
(317) 2-(tetramethyl-ring pentadienyl)-5-methoxyl group benzophenone,
(318) 2-(tertiary butyl cyclopentadienyl)-5-methoxyl group benzophenone,
(319) 2-(dimethylamino cyclopentadienyl)-5-methoxyl group benzophenone etc.
Embodiment
The following examples are done concrete illustrating to the present invention, but the present invention is not limited.
In table 1-5, used following abbreviation.
TIBA: triisobutyl aluminium
MMAO: modified methylaluminoxane (methylaluminoxane of modification) by adding triisobutyl aluminium
AB: four (pentafluorophenyl group) boric acid dimethyl puratized agricultural spray
CB: four (pentafluorophenyl group) boric acid triphenyl methyl esters
PE: polyethylene
Tm: the fusing point of polymkeric substance
Embodiment 1
Synthesizing of 1-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-2-(1-hydroxyl-2,3,4,5-tetramethyl--2-cyclopentenyl) benzene
Under nitrogen atmosphere, with 2-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-bromobenzene (1.22g, tetrahydrofuran (THF) 5.0mmol) (7.3g) solution is cooled to-10 ℃, to the hexane solution that wherein drips n-Butyl Lithium (1.56M, 3.4mL).Under this temperature, kept 1 hour, in this mixture, drip 2,3,4 then, 5-tetramethyl-ring pentenone (0.73g, tetrahydrofuran (THF) 5.3mmol) (4.9g) solution.After temperature is increased to 25 ℃, this mixture was stirred 3 hours.After adding toluene and water quencher reaction, remove water layer.With saturated brine washing gained organic layer,, remove and desolvate then through dried over sodium sulfate.After concentrating,, obtain 1-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-2-(1-hydroxyl-2,3,4,5-tetramethyl--2-cyclopentenyl) benzene (0.53g, yield 35.0%) with cold hexane wash resistates.
1H-NMR(CDCl 3)：δ7.65(1H)，7.15(3H)，5.83(1H)，4.08(1H)，3.89(2H)，2.34(1H)，1.95(3H)，1.82(1H)，1.68(3H)，1.36(3H)，1.09(3H)，1.03(3H)；
MS(EI)m/z 284(M-H 2O)，269，239，222，207，192，178，165.
Embodiment 2
Synthesizing of 2-(2,3,4,5-tetramethyl-ring pentadienyl) methyl phenyl ketone
Under nitrogen atmosphere, with 2-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-bromobenzene (24.31g, ether 100.0mmol) (146g) solution is cooled to-70 ℃, to the hexane solution that wherein drips n-Butyl Lithium (1.56M, 67.3mL).Under this temperature, kept 1 hour, in this mixture, drip 2,3,4 then, 5-tetramethyl-ring pentenone (14.51g, ether 5.3mmol) (97g) solution.After temperature is increased to 25 ℃, this mixture was stirred 3 hours.After adding toluene and water quencher reaction, remove water layer.With saturated brine washing gained organic layer, then through dried over sodium sulfate.Remove and desolvate, obtain the crude product of 1-(2-methyl isophthalic acid, 3-dioxolane-2-yl)-2-(1-hydroxyl-2,3,4,5-tetramethyl--2-cyclopentenyl) benzene.In the gained crude product, add tetrahydrofuran (THF) (320g), 3% aqueous hydrochloric acid (80g) and acetone (32g), this mixture was stirred 24 hours at 25 ℃.After the reaction, in reaction mixture, add toluene.Water and saturated brine washing organic layer through dried over sodium sulfate, remove and desolvate.By the purification by silica gel column chromatography resistates, obtain 2-(2,3,4,5-tetramethyl-ring pentadienyl) methyl phenyl ketones (10.00g, yield 41.6%).
1H-NMR(CDCl 3)：δ7.51(1H)，7.43(1H)，7.28(1H)，7.15(1H)，3.08-2.57(1H)，2.26(3H)，1.92(3H)，1.85(3H)，1.81-1.63(3H)，1.11(3H)；
MS(EI)m/z 284(M +)，269，239，222，207，192，178，165.
Embodiment 3
Synthesizing of 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl aldehyde
Under nitrogen atmosphere, with 2-(1,3-dioxolane-2-yl)-bromobenzene (34.36g, ether 150.0mmol) (206g) solution is cooled to-70 ℃, to the hexane solution that wherein drips n-Butyl Lithium (1.56M, 100.96mL).Under this temperature, kept 1 hour, in this mixture, drip 2,3,4 then, 5-tetramethyl-ring pentenone (21.77g, ether 157.5mmol) (137g) solution.After temperature is increased to 25 ℃, this mixture was stirred 3 hours.After adding toluene and water quencher reaction, remove water layer.With saturated brine washing gained organic layer, then through dried over sodium sulfate.Remove and desolvate, obtain the crude product of 1-(1,3-dioxolane-2-yl)-2-(1-hydroxyl-2,3,4,5-tetramethyl--2-cyclopentenyl) benzene.In the gained crude product, add tetrahydrofuran (THF) (770g), 3% aqueous hydrochloric acid (385.2g) and acetone (77g), this mixture was stirred 24 hours at 25 ℃.After the reaction, in reaction mixture, add toluene.Water and saturated brine washing organic layer through dried over sodium sulfate, remove and desolvate.By the purification by silica gel column chromatography resistates, obtain 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl aldehydes (15.78g, yield 46.5%).
1H-NMR(CDCl 3)：δ9.91(1H)，7.97(1H)，7.56(1H)，7.37(1H)，7.22(1H)，3.22-2.75(1H)，1.94(3H)，1.87(3H)，1.74(3H)，0.95(3H)；
MS(EI)m/z 226(M +)，221，193，178，165.
Embodiment 4
Synthesizing of 2-(2,3,4,5-tetramethyl-ring pentadienyl) benzylalcohol
At room temperature, ((0.42g 11.0mmol), stirs this mixture 3 hours to add sodium borohydride among the 2.26g, ethanolic soln 10.0mmol) (29.0mL) to 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl aldehyde.In this reaction mixture, add toluene (20.0mL) and deionized water (20.0mL), organic layer is separated with water layer.Use the dried over sodium sulfate organic layer, distillation removes and desolvates then, obtains 2-(2,3,4,5-tetramethyl-ring pentadienyl) benzylalcohols (2.23g, yield 96.0%), is light color oily matter.
1H-NMR(CDCl 3)：δ7.47-6.82(4H)，4.48(2H)，3.05-2.70(1H)，2.35(1H)，1.97(3H)，1.85(3H)，1.68(3H)，1.22-0.91(3H)；
MS(EI)m/z 228(M +)，213，195，180，165，128，115.
Embodiment 5
Synthesizing of { 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl } phenylcarbinol
At-78 ℃, (drip the hexanaphthene and the ethereal solution (17.7mL) of 1.05M phenyl lithium among the 2.0g, tetrahydrofuran solution 8.80mmol) (34.0mL) to 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl aldehyde.Mixture temperature is increased to room temperature, this mixture was stirred 4 hours.In this reaction mixture solution, add deionized water (20.0mL) and toluene (20.0mL), organic layer is separated with water layer.Use the dried over sodium sulfate organic layer, distillation removes and desolvates then,, obtains { 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl } phenylcarbinol (2.83g, yield 87.0%) by silicagel column (hexane/ethyl acetate=9/1) purifying, is faint yellow oily thing.
1H-NMR(CDCl 3)：δ7.77-6.91(4H)，6.45-5.55(2H)，3.21-2.25(1H)，1.88-1.45(9H)，1.16-0.82(3H)；
MS(EI)m/z 304(M +)，286，271，256，193，165，77.
Embodiment 6
Two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl) benzyloxy root closes the synthetic of titanium [complex compound 1]
At-30 ℃, (drip four (dimethylamino) titanium (0.29g, toluene solution 1.3mmol) (1.7mL) among the 0.3g, toluene solution 1.3mmol) (5.2mL) to 2-(2,3,4,5-tetramethyl-ring pentadienyl) benzylalcohol.Mixture was at room temperature stirred 30 minutes, stirred 5 hours at 110 ℃ then.Distillation removes and desolvates, and obtains two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl) benzyloxy roots and closes titanium (0.30g, yield 83.3%).
1H-NMR(C 6D 6)：δ7.25-6.88(4H)，5.46(2H)，3.16(12H)，1.97(6H)，1.86(6H).
Embodiment 7
Dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl) benzyloxy root closes the synthetic of titanium [complex compound 2]
At 0 ℃, close titanium to two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl) benzyloxy root and (drip trimethylchlorosilane (3.67g, pentane solution 33.8mmol) (5.0mL) among the 0.84g, pentane solution 3.1mmol) (15.2mL).Mixture was at room temperature stirred 15 hours.Obtain dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl) benzyloxy root and close titanium (1.00g, yield 94.3%), be yellow solid.
1H-NMR(C 6D 6)：δ7.06-6.64(4H)，5.12(2H)，2.16(6H)，1.63(6H).
Embodiment 8
Under nitrogen atmosphere, the toluene (5.0mL) of packing in autoclave makes temperature-stable at 70 ℃.The ethene of packing into then makes pressure-stabilisation until being pressurized to 0.60MPa.To wherein adding MMAO (100 μ l, 1.0M, Northeast chemistry) and two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl) benzyloxy root closes titanium (0.25 μ mol), make its polyase 13 0 minute.As the polymeric result, every mole of titanium per hour generates 7.36 * 10 4The polymkeric substance of g, the molecular weight of this polymkeric substance (Mw) is 2,360,000, molecular weight distribution (Mw/Mn) is 3.7.
Embodiment 9
Except replacing MMAO, and use outside four (pentafluorophenyl group) boric acid triphenylcarbenium (0.75 μ mol), equally with embodiment 8 carry out polymerization with the hexane solution (100 μ L, 1.0M, Northeast chemistry) of triisobutyl aluminium.As the polymeric result, every mole of titanium per hour generates 6.56 * 10 4
The polymkeric substance of g, the molecular weight of this polymkeric substance (Mw) is 737,000, molecular weight distribution (Mw/Mn) is 2.6.
Embodiment 10
Except closing titanium as outside the catalyst component, equally with embodiment 8 carry out polymerization with dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl) benzyloxy root.As the polymeric result, every mole of titanium per hour generates 1.65 * 10 5The polymkeric substance of g, the molecular weight of this polymkeric substance (Mw) is 143,000, molecular weight distribution (Mw/Mn) is 1.6.
Embodiment 11
Except using dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl) the benzyloxy root closes titanium as catalyst component, hexane solution (100 μ L, 1.0M, Northeast chemistry) with triisobutyl aluminium replaces MMAO, and use outside four (pentafluorophenyl group) boric acid triphenylcarbenium (0.75 μ mol), equally with embodiment 8 carry out polymerization.As the polymeric result, every mole of titanium per hour generates 2.69 * 10 5The polymkeric substance of g, the molecular weight of this polymkeric substance (Mw) is 786,000, molecular weight distribution (Mw/Mn) is 2.7.
Embodiment 12
Except using dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl) the benzyloxy root closes titanium as catalyst component, hexane solution (100 μ L, 1.0M, Northeast chemistry) with triisobutyl aluminium replaces MMAO, and use outside four (pentafluorophenyl group) boric acid dimethyl puratized agricultural spray (0.75 μ mol), equally with embodiment 8 carry out polymerization.As the polymeric result, every mole of titanium per hour generates 2.38 * 10 5The polymkeric substance of g, the molecular weight of this polymkeric substance (Mw) is 674,000, molecular weight distribution (Mw/Mn) is 2.4.
Embodiment 13
N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenylmethylene]-N-phenyl amine synthetic
Under nitrogen atmosphere, aniline (31.5mmol) is added drop-wise in the ethanolic soln (90.0mL) of 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl aldehyde (30.0mmol), at room temperature stir this mixture.After vapor-phase chromatography determined that aldehyde disappears, decompression was heated up in a steamer and is desolvated, and obtains N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenylmethylene]-N-phenyl amine (9.00g, yield 100%).
1H-NMR(C 6D 6)：δ8.75-8.65(1H)，7.42-6.96(9H)，3.01-2.50(1H)，1.73-0.76(12H).
MS(EI)m/z 301，286，270，254，195，145.
Embodiment 14
N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-phenyl amine synthetic
To N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenylmethylene]-add sodium borohydride (4.5mmol) in the ethanolic soln (9.0ml) of N-phenyl amine (3.0mmol), this mixture was at room temperature reacted 3 hours.In this mixture, add entry and toluene then.The dry organic layer that concentrates.By purification by silica gel column chromatography gained oily matter, obtain N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-phenyl amine (0.60g, yield 66.0%), be yellow oil.
1H-NMR(CDCl 3)：δ7.42-7.36(1H)，7.22-7.08(5H)，6.73-6.68(1H)，6.50-6.44(2H)，4.06-4.01(2H)，3.52-3.45(1H)，3.01-2.53(1H)，1.79-1.58(9H)，0.96-0.86(3H)；
MS(EI)m/z 303，286，210，195.
Embodiment 15
Two (dimethylamino) N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-the N-phenyl amine closes the synthetic of titanium [complex compound 3]
At-78 ℃, to N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-drip the toluene solution (1.9mL) of four (dimethylamino) titanium (1.0mmol) in the toluene solution (5.3ml) of N-phenyl amine (1.0mmol).Afterwards, this mixture was at room temperature stirred 1 hour, stirred 5 hours at 100 ℃ then, obtain red solution.Decompression is heated up in a steamer and is desolvated, and obtains two (dimethylamino) N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyls]-the N-phenyl amine closes titanium (0.30g, yield 100%), is red solid.
1H-NMR(C 6D 6)：δ7.24-6.83(9H)，4.44(2H)，3.00(12H)，1.94(6H)，1.71(6H).
Embodiment 16
Dichloride N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-the N-phenyl amine closes the synthetic of titanium [complex compound 4]
At 0 ℃, to two (dimethylamino) N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-the N-phenyl amine closes the toluene solution (24.0mL) that adds trimethylsilyl chloride (55.0mmol) in the toluene solution (32.0mL) of titanium (5.0mmol), then this mixture at room temperature stirred 16 hours.Decompression is heated up in a steamer and is desolvated, and adds hexane (25.0mL) in resistates.The solid of filtering-depositing obtains dichloride N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-the N-phenyl amine closes titanium (2.18g, yield 100%), is orange solids.
1H-NMR(C 6D 6)：δ7.46-7.43(2H)，7.20-6.85(7H)，4.64(2H)，2.07(6H)，1.83(6H).
Embodiment 17
Two (dimethylamino) N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-the N-phenyl amine closes the synthetic of zirconium [complex compound 5]
At-78 ℃, to N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-drip the toluene solution (10.0mL) of four (dimethylamino) zirconium (3.0mmol) in the toluene solution (15.0ml) of N-phenyl amine (3.0mmol).Afterwards, this mixture was at room temperature stirred 1 hour, stirred 5 hours at 100 ℃ then, obtain yellow solution.Decompression is heated up in a steamer and is desolvated, and obtains two (dimethylamino) N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyls]-the N-phenyl amine closes zirconium (1.43g, yield 100%), is brown solid.
1H-NMR(C 6D 6)：δ7.43-6.77(9H)，4.26(2H)，2.89(12H)，1.95(6H)，1.71(6H).
Embodiment 18
Dichloride N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-the N-phenyl amine closes the synthetic of zirconium [complex compound 6]
At 0 ℃, to two (dimethylamino) N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-the N-phenyl amine closes the hexane solution (6.0mL) that adds trimethylsilyl chloride (33.0mmol) in the hexane solution (24.0mL) of zirconium (3.0mmol), then this mixture at room temperature stirred 16 hours.The solid of filtering-depositing obtains dichloride N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-the N-phenyl amine closes zirconium (0.59g, yield 47.0%), is the yellow-green colour powder.
1H-NMR(C 6D 6)：δ7.48-7.44(2H)，7.22-6.94(7H)，4.64(2H)，2.02(6H)，1.79(6H).
" homopolymerization of ethene "
Embodiment 19
Under nitrogen atmosphere, the toluene (5.0mL) of packing in autoclave makes temperature-stable at 70 ℃.The ethene of packing into then makes pressure-stabilisation until being pressurized to 0.60MPa.To wherein adding MMAO (250 μ mol, 5.8wt%Al, Tosoh-Akzo company) and dichloride N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-the N-phenyl amine closes titanium (0.25 μ mol), makes its polyase 13 0 minute.As the polymeric result, every mole of titanium per hour generates 5.85 * 10 5The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 1,030,000, molecular weight distribution (Mw/Mn) is 2.1.
Embodiment 20
Under nitrogen atmosphere, the toluene (5.0mL) of packing in autoclave makes temperature-stable at 70 ℃.The ethene of packing into then makes pressure-stabilisation until being pressurized to 0.60MPa.To the hexane solution that wherein adds triisobutyl aluminium (100 μ L, 1.0M, Northeast chemistry), dichloride N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-the N-phenyl amine closes titanium (0.25 μ mol) and four (pentafluorophenyl group) boric acid triphenylcarbenium (0.75 μ mol), makes its polymerization 24 minutes.As the polymeric result, every mole of titanium per hour generates 1.70 * 10 6The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 1,070,000, molecular weight distribution (Mw/Mn) is 1.9.
Embodiment 21
Except replacing four (pentafluorophenyl group) boric acid triphenylcarbenium with four (pentafluorophenyl group) boric acid dimethyl puratized agricultural spray, polymerization time became outside 21 minutes by 24 minutes, carried out polymerization with method similar to Example 20.As the polymeric result, every mole of titanium per hour generates 1.91 * 10 6The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 1,040,000, molecular weight distribution (Mw/Mn) is 2.3.
Embodiment 22
Except replacing four (pentafluorophenyl group) boric acid triphenylcarbenium with three (pentafluorophenyl group) borine, polymerization time became outside 30 minutes by 24 minutes, to carry out polymerization with embodiment 21 similar methods.As the polymeric result, every mole of titanium per hour generates 5.60 * 10 4The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 172,000, molecular weight distribution (Mw/Mn) is 2.1.
Embodiment 23
Except using two (dimethylamino) N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-the N-phenyl amine closes titanium and replaces dichloride N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-the N-phenyl amine closes outside the titanium, carries out polymerization with method similar to Example 19.As the polymeric result, every mole of titanium per hour generates 7.52 * 10 4The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 803,000, molecular weight distribution (Mw/Mn) is 1.8.
Embodiment 24
Except using two (dimethylamino) N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-the N-phenyl amine closes titanium and replaces dichloride N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-the N-phenyl amine closes titanium, churning time became outside 30 minutes by 24 minutes, carried out polymerization with method similar to Example 20.As the polymeric result, every mole of titanium per hour generates 4.48 * 10 5The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 766,000, molecular weight distribution (Mw/Mn) is 1.7.
Embodiment 25
Except using two (dimethylamino) N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-the N-phenyl amine closes zirconium and replaces dichloride N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-the N-phenyl amine closes outside the titanium, carries out polymerization with method similar to Example 19.As the polymeric result, every mole of titanium per hour generates 5.52 * 10 4The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 916,000, molecular weight distribution (Mw/Mn) is 37.1.
Embodiment 26
Except using dichloride N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-the N-phenyl amine closes zirconium and replaces dichloride N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-the N-phenyl amine closes outside the titanium, carries out polymerization with method similar to Example 19.As the polymeric result, every mole of titanium per hour generates 4.51 * 10 5The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 78,700, molecular weight distribution (Mw/Mn) is 5.8.
Embodiment 27
Except using dichloride N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-the N-phenyl amine closes zirconium and replaces dichloride N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-the N-phenyl amine closes outside the titanium, to carry out polymerization with embodiment 24 similar methods.As the polymeric result, every mole of titanium per hour generates 8.38 * 10 5The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 9,190, molecular weight distribution (Mw/Mn) is 2.3.
Embodiment 28
Except using dichloride N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-the N-phenyl amine closes zirconium and replaces dichloride N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-the N-phenyl amine closes titanium, churning time became outside 30 minutes by 21 minutes, to carry out polymerization with embodiment 21 similar methods.As the polymeric result, every mole of titanium per hour generates 6.44 * 10 5The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 10,600, molecular weight distribution (Mw/Mn) is 3.3.
" copolyreaction of ethene-hexene "
Embodiment 29
Under nitrogen atmosphere, pack in autoclave toluene (5.0mL) and hexene (5.00 μ L) make temperature-stable at 70 ℃.The ethene of packing into then makes pressure-stabilisation until being pressurized to 0.60MPa.To the hexane solution that wherein adds triisobutyl aluminium (100 μ L, 1.0M, Northeast chemistry), dichloride N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-the N-phenyl amine closes titanium (0.25 μ mol) and four (pentafluorophenyl group) boric acid triphenylcarbenium (0.75 μ mol), makes its polyase 13 0 minute.As the polymeric result, every mole of titanium per hour generates 1.06 * 10 6The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 873,000, molecular weight distribution (Mw/Mn) is 2.5.
Embodiment 30
Except replacing four (pentafluorophenyl group) boric acid triphenylcarbenium, to carry out polymerization with embodiment 29 similar methods with four (pentafluorophenyl group) boric acid dimethyl puratized agricultural spray.As the polymeric result, every mole of titanium per hour generates 1.07 * 10 6The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 492,000, molecular weight distribution (Mw/Mn) is 5.3.
Embodiment 31
Synthesizing of 2-(2,3,4,5-tetramethyl-ring pentadienyl) benzaldehyde-phenylhydrazone
Under nitrogen atmosphere, in the ethanolic soln (60.0mL) of 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl aldehyde (20.0mmol), drip phenylhydrazine (22.0mmol), this mixture was at room temperature stirred 2 hours.Decompression is heated up in a steamer and is desolvated, and with resistates recrystallization in hexane, obtains 2-(2,3,4,5-tetramethyl-ring pentadienyl) benzaldehyde-phenylhydrazones (4.8g, yield 76.3%).
1H-NMR(C 6D 6)：δ8.13-8.08(1H)，7.62-7.53(2H)，7.30-7.23(4H)，7.10-7.06(3H)，6.86-6.82(1H)，3.13-2.73(1H)，1.93-1.88(5H)，1.71-1.58(4H)，1.20-0.91(3H).
Embodiment 32
Synthesizing of complex compound 7
Complex compound 7
At-78 ℃, in toluene (5.3mL) solution of 2-(2,3,4,5-tetramethyl-ring pentadienyl) benzaldehyde-phenylhydrazone (1.0mmol), drip toluene (1.9mL) solution of four (dimethylamino) titanium (1.0mmol).This mixture was at room temperature stirred 1 hour, stirred 5 hours at 100 ℃ then, obtain red solution.Decompression is heated up in a steamer and is desolvated, and obtains the complex compound 7 (2.23g, yield 100%) into red solid.
1H-NMR(C 6D 6)：δ8.55(1H)，7.31-6.88(9H)，3.18(12H)，2.09(6H)，1.50(6H).
Embodiment 33
Synthesizing of complex compound 8
Figure G2006100046087D01482
Complex compound 8
At 0 ℃, in toluene (32.0mL) solution of complex compound 7 (5.0mmol), drip toluene (24.0mL) solution of trimethylsilyl chloride (55.0mmol), then this mixture was at room temperature stirred 16 hours.Decompression is heated up in a steamer and is desolvated, and adds hexane (25.0mL) in resistates.The solid that filtering-depositing goes out obtains the complex compound 8 (2.20g, yield 99.5%) into orange solids.
1H-NMR(C 6D 6)：δ8.05(1H)，7.63-7.61(2H)，7.13-6.84(7H)，2.11(6H)，1.59(6H).
Embodiment 34
Synthesizing of complex compound 9
Complex compound 9
At-78 ℃, to 2-(2,3,4,5-tetramethyl-ring pentadienyl) drips toluene (10.0mL) solution of four (dimethylamino) zirconium (3.0mmol) in toluene (15.0mL) solution of benzaldehyde-phenylhydrazone (3.0mmol), then this mixture was at room temperature stirred 1 hour, stirred 5 hours at 100 ℃ again, obtain yellow solution.Decompression is heated up in a steamer and is desolvated, and obtains the complex compound 9 (1.47g, yield 100%) into brown solid.
1H-NMR(C 6D 6)：δ8.15(1H)，7.28-6.90(9H)，3.00(12H)，2.09(6H)，1.79(6H).
Embodiment 35
Synthesizing of complex compound 10
Complex compound 10
At 0 ℃, in hexane (24.0mL) solution of complex compound 9 (3.0mmol), drip hexane (6.0mL) solution of trimethylsilyl chloride (33.0mmol), then this mixture was at room temperature stirred 20 hours.The solid that filtering-depositing goes out obtains the complex compound 10 (0.83g, yield 58.1%) into the yellow-green colour powder.
1H-NMR(C 6D 6)：δ7.94(1H)，7.44-7.42(2H)，7.16-6.86(7H)，2.10(6H)，1.64(6H).
Polyreaction
Embodiment 36
Under nitrogen atmosphere, the toluene (5.0mL) of packing in autoclave makes temperature-stable at 70 ℃.The ethene of packing into then makes pressure-stabilisation until being pressurized to 0.60MPa.To wherein adding MMAO (250 μ mol, 5.8wt%Al, Tosoh-Akzo company) and complex compound 2 (0.25 μ mol), make its polyase 13 0 minute.As the polymeric result, every mole of titanium per hour generates 1.07 * 10 6The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 453,000, molecular weight distribution (Mw/Mn) is 2.1.
Embodiment 37
Under nitrogen atmosphere, the toluene (5.0mL) of packing in autoclave makes temperature-stable at 70 ℃.The ethene of packing into then makes pressure-stabilisation until being pressurized to 0.60MPa.To the hexane solution that wherein adds triisobutyl aluminium (100 μ L, 1.0M, Northeast chemistry), complex compound 2 (0.25 μ mol) and four (pentafluorophenyl group) boric acid triphenylcarbenium (0.75 μ mol), make its polyase 13 0 minute.As the polymeric result, every mole of titanium per hour generates 1.11 * 10 6The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 658,000, molecular weight distribution (Mw/Mn) is 2.2.
Embodiment 38
Except replacing four (pentafluorophenyl group) boric acid triphenylcarbenium, to carry out polymerization with embodiment 37 similar methods with four (pentafluorophenyl group) boric acid dimethyl puratized agricultural spray.As the polymeric result, every mole of titanium per hour generates 1.07 * 10 6The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 611,000, molecular weight distribution (Mw/Mn) is 2.2.
Embodiment 39
Except replacing the complex compound 2, to carry out polymerization with embodiment 36 similar methods with complex compound 1.As the polymeric result, every mole of titanium per hour generates 2.42 * 10 5The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 416,000, molecular weight distribution (Mw/Mn) is 2.1.
Embodiment 40
Except replacing the complex compound 2, to carry out polymerization with embodiment 37 similar methods with complex compound 4.As the polymeric result, every mole of titanium per hour generates 5.26 * 10 5The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 587,000, molecular weight distribution (Mw/Mn) is 13.0.
Embodiment 41
Except replacing the complex compound 2, to carry out polymerization with embodiment 38 similar methods with complex compound 4.As the polymeric result, every mole of titanium per hour generates 4.91 * 10 5The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 94,000, molecular weight distribution (Mw/Mn) is 17.3.
Embodiment 42
Synthesizing of 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-benzimide
To 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl aldehyde (8.86g, add in tetrahydrofuran solution 39.2mmol) (150.0mL) methoxamine hydrochloride (4.25g, 50.9mmol), sodium acetate (4.18g, 50.9mmol) and water, this mixture was at room temperature stirred 2 hours.
In this reaction mixture, add ethyl acetate (20.0mL) and water (20.0mL), organic layer is separated with water layer.Use the dried over sodium sulfate organic layer, distillation removes and desolvates then, obtains O-methyl-2-(2,3,4,5-tetramethyl-ring pentadienyl) benzaldoximes (8.85g, yield 88.5%), is yellow oil.
At-78 ℃, (drip the hexanaphthene/ethereal solution (60.0mL) of 1.5M phenyl lithium among the 4.00g, tetrahydrofuran solution 15.7mmol) (68.0mL) to gained O-methyl-2-(2,3,4,5-tetramethyl-ring pentadienyl) benzaldoxime.The temperature of this mixture is increased to room temperature, stirred 5 hours.
In reaction mixture, add toluene (30.0mL) and water (30.0mL), organic layer is separated with water layer.Use the dried over sodium sulfate organic layer, distillation removes and desolvates then, obtains 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-benzimide (4.40g, yield 93.2%), is brown oil.
1H-NMR(CDCl 3)：δ9.53(1H)，7.59-7.47(9H)，2.83-2.12(1H)，1.72(3H)，1.65(3H)，1.59(3H)，0.99-0.64(3H)；
MS(EI)m/z 301(M +)，286，270，256，165，77.
Embodiment 43
Synthesizing of 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-benzimide
According to embodiment 42 similar methods, synthetic O-methyl-2-(2,3,4,5-tetramethyl-ring pentadienyl) benzaldoxime.At-78 ℃, (drip the ethereal solution (60.0mL) of 1.02M tert-butyl lithium among the 1.28g, tetrahydrofuran solution 5.0mmol) (68.0mL) to O-methyl-2-(2,3,4,5-tetramethyl-ring pentadienyl) benzaldoxime.The temperature of this mixture is increased to room temperature, stirred 5 hours.
In reaction mixture, add toluene (30.0mL) and deionized water (30.0mL), organic layer is separated with water layer.Use the dried over sodium sulfate organic layer, distillation removes and desolvates then, obtains 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-benzimide (1.34g, yield 95.0%).
1H-NMR(CDCl 3)：δ9.53(1H)，7.36-7.02(4H)，3.00-2.58(1H)，1.85-1.83(3H)，1.70(3H)，1.67(3H)，1.10(9H)，0.83-0.80(3H)；
MS(EI)m/z 281(M +)，266，252，208，194，165.
Embodiment 44
Two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-benzimide closes the synthetic of titanium [complex compound 11]
At-30 ℃, (0.45g drips four (dimethylamino) titanium (0.34g, toluene 1.5mmol) (10.5mL) solution in toluene solution 1.5mmol) to 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-benzimide.This mixture was at room temperature stirred 30 minutes, stirred 5 hours at 110 ℃ then.Distillation removes and desolvates, and obtains two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-benzimide and closes titanium (0.50g, yield 76.9%).
1H-NMR(C 6D 6)：δ7.88-6.98(9H)，3.12(6H)，3.10(6H)，2.01(6H)，1.92(6H).
Embodiment 45
Dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-benzimide closes the synthetic of titanium [complex compound 12]
At 0 ℃, to two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-benzimide closes titanium (0.65g, 1.5mmol) hexane (15.9mL) solution in drip trimethylchlorosilane (1.63g, hexane 15.0mmol) (3.9mL) solution at room temperature stirred this mixture 15 hours.Form precipitation, filtration obtains dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-benzimide and closes titanium (0.50g, yield 79.4%) then.
1H-NMR(C 6D 6)：δ7.64-6.86(9H)，2.18(6H)，1.72(6H).
Embodiment 46
Two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-benzimide closes the synthetic of zirconium [complex compound 13]
At-30 ℃, (1.50g drips four (dimethylamino) zirconium (1.43g, toluene 5.3mmol) (3.5mL) solution in toluene 5.3mmol) (13.9mL) solution to 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-benzimide.This mixture was at room temperature stirred 30 minutes, stirred 5 hours at 110 ℃ then.Distillation removes and desolvates, and obtains two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-benzimide and closes zirconium (2.31g, yield 91.3%).
1H-NMR(C 6D 6)：δ7.96-6.98(9H)，2.92(12H)，2.01(6H)，1.91(6H).
Embodiment 47
Two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-benzimide closes the synthetic of titanium [complex compound 14]
At-30 ℃, (1.00g drips four (dimethylamino) titanium (0.80g, toluene 3.5mmol) (2.3mL) solution in toluene 3.5mmol) (9.2mL) solution to 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-benzimide.This mixture was at room temperature stirred 30 minutes, stirred 5 hours at 110 ℃ then.Distillation removes and desolvates, and obtains two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-benzimide and closes titanium (1.21g, yield 81.8%).
1H-NMR(C 6D 6)：δ7.77-6.92(4H)，3.11(12H)，2.04(6H)，1.84(6H)，1.45(9H).
Embodiment 48
Dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-benzimide closes the synthetic of titanium [complex compound 15]
At 0 ℃, to two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-benzimide closes titanium (0.83g, 2.0mmol) pentane (10.6mL) solution in drip trimethylchlorosilane (2.39g, pentane 22.0mmol) (2.7mL) solution at room temperature stirred this mixture 15 hours.Form precipitation, filtration obtains dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-benzimide and closes titanium (0.51g, yield 63.8%) then.
1H-NMR(C 6D 6)：δ7.56-6.88(4H)，2.18(6H)，1.62(6H)，1.23(9H).
Embodiment 49
Two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-benzimide closes the synthetic of zirconium [complex compound 16]
At-30 ℃, (2.37g drips four (dimethylamino) zirconium (2.25g, toluene 8.4mmol) (5.5mL) solution in toluene 8.4mmol) (21.9mL) solution to 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-benzimide.This mixture was at room temperature stirred 30 minutes, stirred 5 hours at 110 ℃ then.Distillation removes and desolvates, and obtains two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-benzimide and closes zirconium (3.12g, yield 80.8%).
1H-NMR(C 6D 6)：δ7.84-6.92(4H)，2.91(12H)，2.02(6H)，1.88(6H)，1.47(9H).
Embodiment 50
Dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-benzimide closes the synthetic of zirconium [complex compound 17]
At 0 ℃, to two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-benzimide closes zirconium (1.00g, 2.2mol) pentane (12.8mL) solution in drip trimethylchlorosilane (2.60g, pentane 24.0mmol) (3.2mL) solution at room temperature stirred this mixture 28 hours.Form precipitation, filtration obtains dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-benzimide and closes zirconium (0.35g, yield 36.5%) then.
1H-NMR(C 6D 6)：δ7.64-6.78(4H)，2.22(3H)，2.18(3H)，1.94(3H)，1.92(3H)，1.46(9H).
Embodiment 51
[polyreaction]
Under nitrogen atmosphere, the toluene (5.0mL) of packing in autoclave makes temperature-stable at 70 ℃.The ethene of packing into then makes pressure-stabilisation until being pressurized to 0.60MPa.To the hexane solution that wherein adds triisobutyl aluminium (100 μ L, 1.0M, Northeast chemistry), four (pentafluorophenyl group) boric acid triphenyl methyl esters (0.375 μ mol) and two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-benzimide closes titanium (0.125 μ mol), makes its polyase 13 0 minute.As the polymeric result, every mole of titanium per hour generates 4.08 * 10 4The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 897,000, molecular weight distribution (Mw/Mn) is 2.3.
Embodiment 52
Except replacing four (pentafluorophenyl group) boric acid triphenyl methyl esters, to carry out polymerization with embodiment 51 similar methods with four (pentafluorophenyl group) boric acid dimethyl puratized agricultural spray (0.375 μ mol).As the polymeric result, every mole of titanium per hour generates 4.88 * 10 4The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 657,000, molecular weight distribution (Mw/Mn) is 2.5.
Embodiment 53
Except using dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-benzimide closes titanium (0.125 μ mol) and replaces two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-benzimide closes outside the titanium, to carry out polymerization with embodiment 51 similar methods.As the polymeric result, every mole of titanium per hour generates 5.70 * 10 5The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 968,000, molecular weight distribution (Mw/Mn) is 2.6.
Embodiment 54
Except using dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-benzimide closes titanium (0.125 μ mol) and replaces two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-benzimide closes titanium, replace outside four (pentafluorophenyl group) boric acid triphenyl methyl esters, with four (pentafluorophenyl group) boric acid dimethyl puratized agricultural spray (0.375 μ mol) to carry out polymerization with embodiment 51 similar methods.As the polymeric result, every mole of titanium per hour generates 4.98 * 10 5The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 1,150,000, molecular weight distribution (Mw/Mn) is 2.6.
Embodiment 55
Except using two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-benzimide closes titanium (0.125 μ mol) and replaces two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-benzimide closes outside the titanium, to carry out polymerization with embodiment 51 similar methods.As the polymeric result, every mole of titanium per hour generates 7.60 * 10 4The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 1,370,000, molecular weight distribution (Mw/Mn) is 3.9.
Embodiment 56
Except using two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-benzimide closes titanium (0.125 μ mol) and replaces two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-benzimide closes titanium, replace outside four (pentafluorophenyl group) boric acid triphenyl methyl esters, with four (pentafluorophenyl group) boric acid dimethyl puratized agricultural spray (0.375 μ mol) to carry out polymerization with embodiment 51 similar methods.As the polymeric result, every mole of titanium per hour generates 5.68 * 10 4The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 1,250,000, molecular weight distribution (Mw/Mn) is 3.3.
Embodiment 57
Except using dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-benzimide closes titanium (0.125 μ mol) and replaces two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-benzimide closes outside the titanium, to carry out polymerization with embodiment 51 similar methods.As the polymeric result, every mole of titanium per hour generates 6.23 * 10 5The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 1,830,000, molecular weight distribution (Mw/Mn) is 1.7.
Embodiment 58
Except using dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-tertiary butyl-benzimide closes titanium (0.125 μ mol) and replaces two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-phenyl-benzimide closes titanium, replace outside four (pentafluorophenyl group) boric acid triphenyl methyl esters, with four (pentafluorophenyl group) boric acid dimethyl puratized agricultural spray (0.375 μ mol) to carry out polymerization with embodiment 51 similar methods.As the polymeric result, every mole of titanium per hour generates 3.81 * 10 5The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 814,000, molecular weight distribution (Mw/Mn) is 2.0.
Embodiment 59
Synthesizing of O-methyl-2-(2,3,5-trimethylammonium cyclopentadienyl) benzaldoxime
At 25 ℃, to 2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl aldehyde (11.32g, 50.0mmol) THF (170.0mL) solution in add O-methyl hydroxylamine base hydrochloride (5.43g, 65.0mmol), (5.33g 65.0mmol) and water (50.0mL), stirs this mixture 30 minutes sodium acetate.After the reaction, to wherein adding ethyl acetate and water.Mixture separation is removed water layer.With the organic layer of dried over sodium sulfate gained, decompression is heated up in a steamer and is desolvated, and obtains O-methyl-2-(2,3,5-trimethylammonium cyclopentadienyl) benzaldoximes (12.77g, yield 100%).
1H-NMR(CDCl 3)：δ7.97-7.90(1H)，7.39-7.06(4H)，3.94(3H)，3.08-2.70(1H)，1.90(3H)，1.84(3H)，1.68(3H)，0.88(3H)；
MS(EI)m/z 255(M +)，240，224，209，194.
Synthesizing of 2-(2,3,4,5-trimethylammonium cyclopentadienyl) benzonitrile
At-78 ℃, to Diisopropylamine (1.52g, drip in THF 15.0mmol) (17.5mL) solution 1.59M n-Butyl Lithium (9.4mL, 15.0mmol).The temperature of this mixture is increased to 20 ℃, preparation diisopropylaminoethyl lithium.This reaction soln is cooled to-78 ℃, to wherein dripping O-methyl-2-(2,3,5-trimethylammonium cyclopentadienyl) benzaldoxime (1.28g, tetrahydrofuran (THF) 5.0mmol) (4.3mL) solution.
After mixture temperature is elevated to room temperature, add toluene and water quencher reaction.Reaction mixture separates, and removes water layer.With dried over sodium sulfate gained organic layer, decompression is heated up in a steamer and is desolvated, and obtains 2-(2,3,4,5-tetramethyl-ring pentadienyl) benzonitriles (1.12g, yield 100%).
1H-NMR(CDCl 3)：δ7.66(1H)，7.52(1H)，7.33-7.23(2H)，3.38(1H)，1.92(3H)，1.90(3H)，1.87(3H)，0.93(3H)；
MS(EI)m/z 223(M +)，208，193，180，165.
Embodiment 60
At-78 ℃, to Diisopropylamine (0.96g, drip in tetrahydrofuran (THF) 9.5mmol) (34.5mL) solution 1.59M n-Butyl Lithium (6.0mL, 9.5mmol).Temperature with this mixture is increased to 20 ℃ then, preparation diisopropylaminoethyl lithium.This reaction soln is cooled to-78 ℃, to wherein dripping O-methyl-2-(2,3,5-trimethylammonium cyclopentadienyl) benzaldoxime (2.55g, tetrahydrofuran (THF) 10.0mmol) (8.6mL) solution.Make the temperature of reaction soln be elevated to room temperature.According to gas chromatographic analysis, the yield with 63.9% has made 2-(2,3,4,5-tetramethyl-ring pentadienyl) benzonitrile.
The comparative example 1
To 2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl aldehyde (1.13g, add in 5.0mmol) acetate (22.60g), sodium acetate (1.64g, 20.0mmol) and azanol base hydrochloride (1.39g, 20.0mmol).With this mixture heating up to 110 ℃, and stirred 3 hours.By the gas chromatographic analysis reaction soln, do not generate 2-(2,3,4,5-tetramethyl-ring pentadienyl) benzonitrile.
The comparative example 2
To 2-(2,3,5-trimethylammonium cyclopentadienyl) phenyl aldehyde (1.13g, add in 5.0mmol) formic acid (17.0g) and azanol base hydrochloride (0.45g, 6.5mmol).With this mixture heating up to 110 ℃, and stirred 30 minutes.By the gas chromatographic analysis reaction soln, do not generate 2-(2,3,4,5-tetramethyl-ring pentadienyl) benzonitrile.
Embodiment 61
Two (dimethylaminos) [2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl] phenyl methyl alkoxy radical closes the synthetic of titanium [complex compound 18]
At-78 ℃, (1.00g adds four (dimethylamino) titanium (0.74g, toluene 3.2mmol) (2.3mL) solution in toluene 3.2mmol) (9.2mL) solution to [2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl] phenyl methanol.This mixture was at room temperature stirred 30 minutes, stirred 5 hours at 110 ℃ then.Distillation removes and desolvates, and obtains two (dimethylamino) [2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl] phenyl methyl alkoxy radicals and closes titanium (1.23g, yield 86.6%).
1H-NMR(C 6D 6)：δ7.16-6.96(4H)，6.45(1H)，3.09(6H)，3.04(6H)，2.07(3H)，1.97(3H)，1.88(3H)，1.85(3H)；
13C-NMR(C 6D 6)：δ147.9-121.4(aroma)，86.0(CH)，48.7，47.5(NMe 2)12.1，11.9，11.1(CH 3).
Embodiment 62
Dichloride [2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl] phenyl methyl alkoxy radical closes the synthetic of titanium [complex compound 19]
At 0 ℃, [2-(2,3 to two (dimethylaminos), 4,5-tetramethyl-ring pentadienyl) phenyl] the phenyl methyl alkoxy radical closes titanium (0.7g drips tetramethyl-chlorosilane (1.91g, pentane 17.6mmol) (2.2mL) solution in pentane 1.6mmol) (8.9mL) solution.This mixture was at room temperature stirred 15 hours, obtain dichloride [2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl] phenyl methyl alkoxy radical and close titanium (526.6mg, yield 78.6%), be yellow solid.
1H-NMR(C 6D 6)：δ6.85-7.22(4H)，6.32(1H)，2.15(3H)，2.10(3H)，1.69(3H)，1.65(3H)；
MS(EI)m/z 420(M +)，304，286，167，113.
Embodiment 63
Two (dimethylaminos) [2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl] phenyl methyl alkoxy radical closes synthetic [complex compound 20] of zirconium
At-78 ℃, (0.97g drips four (dimethylamino) titanium (0.85g, toluene 3.1mmol) (2.2mL) solution in toluene 3.1mmol) (9.0mL) solution to [2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl] phenyl methyl alcohol.This mixture was at room temperature stirred 30 minutes, stirred 5 hours at 110 ℃ then.Distillation removes and desolvates, and obtains two (dimethylamino) [2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl] phenyl methyl alkoxy radicals and closes zirconium (1.02g, yield 67.1%).
1H-NMR(C 6D 6)：δ6.98-7.37(4H)，6.35(1H)，2.87(6H)，2.85(6H)，2.03(3H)，1.96(3H)，1.89(3H)，1.85(3H)；
13C-NMR(C 6D 6)：δ147.3-117.6(aroma)，83.2(CH)，48.7，43.3(NMe 2)，11.1，10.8，10.6(CH 3).
Embodiment 64
N-[2-(1-indenyl) phenyl methyl]-N-aniline synthetic
Under nitrogen atmosphere, in ethanol (19.4mL) solution of 2-(1-indenyl) phenyl aldehyde (7.0mmol), drip aniline (7.3mmol).At room temperature stir this mixture.After vapor-phase chromatography determined that aldehyde disappears, decompression was heated up in a steamer and is desolvated.After adding ethanol (19.4mL), sodium borohydride (4.5mmol) in the solution, mixture was at room temperature reacted 3 hours.In reaction mixture, add entry and toluene then.The dry organic layer that concentrates.Gained oily matter by purification by silica gel column chromatography, is obtained N-[2-(1-indenyl) phenyl methyl]-N-aniline (1.48g, yield 24.0%), be yellow oil.
1H-NMR(CDCl 3)：δ7.56-7.52(3H)，7.36-7.07(6H)，6.73-6.62(2H)，6.51-6.47(3H)，4.26(2H)，3.91-3.69(1H)，3.51(2H)；
MS(EI)m/z 297(M +)，204，77.
Embodiment 65
Two (dimethylamino) N-[2-(1-indenyl) phenyl methyl]-N-aniline closes the synthetic of titanium [complex compound 21]
At-78 ℃, to N-[2-(1-indenyl) phenyl methyl]-drip toluene (10.0mL) solution of four (dimethylamino) titanium (2.8mmol) in toluene (15.2mL) solution of N-aniline (2.8mmol).This mixture was at room temperature stirred 1 hour, stirred 5 hours at 100 ℃ then, obtain red solution.Underpressure distillation removes desolvates, and obtains two (dimethylamino) N-[2-(1-indenyl) phenyl methyls]-N-aniline closes titanium (1.21g), is red solid.
1H-NMR(C 6D 6)：δ7.41-7.00(14H)，6.28-6.19(1H)，5.84(1H)，4.43(1H)，2.74(6H)，2.48(6H).
Embodiment 66
Dichloride N-[2-(1-indenyl) phenyl methyl]-N-aniline closes the synthetic of titanium [complex compound 22]
At 0 ℃, to two (dimethylamino) N-[2-(1-indenyl) phenyl methyl]-the N-phenyl amine closes pentane (12.0mL) solution that drips trimethylsilyl chloride (30.8mmol) in pentane (17.5mL) solution of titanium (2.8mmol).This mixture was at room temperature stirred 16 hours.The solid that filtering-depositing goes out obtains dichloride N-[2-(1-indenyl) phenyl methyl]-N-aniline closes titanium (0.24g, yield 20.9%), is orange solids.
1H-NMR(C 6D 6)：δ7.41-7.00(14H)，6.18(1H)，5.21(1H)，4.23(1H)；
MS(EI)m/z 413(M +)，377，297，204.
Embodiment 67
N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-(3, the 5-3,5-dimethylphenyl) amine synthetic
Under nitrogen atmosphere, in ethanol (44.6mL) solution of 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl aldehyde (15.0mmol), drip 3,5-xylidine (15.8mmol) and acetate (1.5mmol).At room temperature stir this mixture.After vapor-phase chromatography determines that aldehyde disappears, in solution, add sodium borohydride (19.5mmol), at room temperature reacted 3 hours.In reaction mixture, add entry and toluene then.The dry organic layer that concentrates.Gained oily matter by purification by silica gel column chromatography, is obtained N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-(3, the 5-3,5-dimethylphenyl) amine (4.88g, yield 73.3%), be yellow oil.
1H-NMR(CDCl 3)：δ7.46-6.15(7H)，4.30-4.08(2H)，3.87-3.79(1H)，3.18-2.72(1H)，2.33-0.95(18H)；
MS(EI)m/z 331(M +)，210，195.
Embodiment 68
Two (dimethylamino) N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-(3, the 5-3,5-dimethylphenyl) amine closes the synthetic of titanium [complex compound 23]
At-78 ℃, to N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-drip toluene (12.2mL) solution of four (dimethylamino) titanium (4.0mmol) in toluene (18.4mL) solution of N-(3, the 5-3,5-dimethylphenyl) amine (4.0mmol).This mixture was at room temperature stirred 1 hour, stirred 5 hours at 100 ℃ then, obtain red solution.Underpressure distillation removes desolvates, synthetic two (dimethylamino) N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyls]-N-(3, the 5-3,5-dimethylphenyl) amine closes titanium (2.08g, yield 100%), is red solid.
1H-NMR(C 6D 6)：δ7.66-6.74(7H)，4.48(2H)，3.05(12H)，1.94(6H)，1.74(6H).
Embodiment 69
Dichloride N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-(3, the 5-3,5-dimethylphenyl) amine closes the synthetic of titanium [complex compound 24]
At 0 ℃, to two (dimethylamino) N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-(3, the 5-3,5-dimethylphenyl) amine closes pentane (19.0mL) solution that drips trimethylsilyl chloride (44.0mmol) in pentane (29.1mL) solution of titanium (4.0mmol).This mixture was at room temperature stirred 16 hours.The solid that filtering-depositing goes out obtains dichloride N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-(3, the 5-3,5-dimethylphenyl) amine closes titanium (0.31g, yield 15.6%), is orange solids.
1H-NMR(C 6D 6)：δ7.42-6.67(7H)，4.73(2H)，2.13(6H)，2.05(6H)，1.86(6H)；
MS(EI)m/z 447(M +)，411，209.
Embodiment 70
N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenylmethylene]-N-(2,4, the 6-trimethylphenyl) amine synthetic
Under nitrogen atmosphere, in ethanol (30.0mL) solution of 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl aldehyde (10.0mmol), drip acetate (1.0mmol) and 2 (10.5mmol).At room temperature stir this mixture.After vapor-phase chromatography determined that aldehyde disappears, decompression was heated up in a steamer and is desolvated, and obtains N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenylmethylene]-N-(2,4, the 6-trimethylphenyl) amine (3.43g, yield 100%).
1H-NMR(CDCl 3)：δ8.37-8.32(1H)，8.21(1H)，7.58-7.11(3H)，6.86(1H)，3.15-2.67(1H)，2.27(3H)，2.12-0.94(18H).
Embodiment 71
N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-(2,4, the 6-trimethylphenyl) amine synthetic
To N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenylmethylene]-add sodium borohydride (13.0mmol) in acetate (7.0mL) solution of N-(2,4, the 6-trimethylphenyl) amine (10.0mmol).This mixture was at room temperature stirred 1 hour.In reaction mixture, add entry and toluene.The dry organic layer that concentrates.Gained oily matter by purification by silica gel column chromatography, is obtained N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-(2,4, the 6-trimethylphenyl) amine (2.74g, yield 69.5%), be yellow oil.
1H-NMR(CDCl 3)：δ7.67-7.04(4H)，6.82-6.78(2H)，3.91-3.77(2H)，3.10-2.62(1H)，3.00-2.85(1H)，2.28-0.88(21H)；
MS(EI)m/z 345(M +)，210，195.
Embodiment 72
Two (dimethylamino) N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-(2,4, the 6-trimethylphenyl) amine closes the synthetic of zirconium [complex compound 25]
At-78 ℃, to N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-drip toluene (7.4mL) solution of four (dimethylamino) titanium (3.1mmol) in toluene (11.1mL) solution of N-(2,4, the 6-trimethylphenyl) amine (3.1mmol).This mixture was at room temperature stirred 1 hour, stirred 5 hours at 100 ℃ then, obtain yellow solution.Underpressure distillation removes desolvates, and obtains two (dimethylamino) N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyls]-N-(2,4, the 6-trimethylphenyl) amine closes zirconium (1.65g, yield 100%), is faint yellow solid.
1H-NMR(C 6D 6)：δ7.37-6.85(6H)，4.34(2H)，2.68(12H)，2.16(3H)，2.01(6H)，1.99(12H)；
MS(EI)m/z 521(M +)，476，432，210.
Embodiment 73
Dichloride N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-(2,4, the 6-trimethylphenyl) amine closes the synthetic of zirconium [complex compound 26]
At 0 ℃, to two (dimethylamino) N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-(2,4, the 6-trimethylphenyl) amine closes pentane (9.0mL) solution that drips trimethylsilyl chloride (27.5mmol) in pentane (13.6mL) solution of zirconium (2.5mmol).This mixture was at room temperature stirred 16 hours.The solid that filtering-depositing goes out obtains dichloride N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-(2,4, the 6-trimethylphenyl) amine closes zirconium (0.97g, yield 77.0%), is white solid.
1H-NMR(C 6D 6)：δ7.42-7.09(3H)，6.94-6.89(1H)，6.80(2H)，4.35(2H)，2.15(6H)，2.07(6H)，2.00(3H)，1.86(6H).
Embodiment 74
N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenylmethylene]-N-(2, the 6-diisopropyl phenyl) amine synthetic
Under nitrogen atmosphere, in ethanol (30.0mL) solution of 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl aldehyde (10.0mmol), drip acetate (1.0mmol) and 2,6-diisopropyl aniline (10.5mmol).At room temperature stir this mixture.After vapor-phase chromatography determined that aldehyde disappears, decompression was heated up in a steamer and is desolvated, and obtains N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenylmethylene]-N-(2, the 6-diisopropyl phenyl) amine (3.85g, yield 100%).
1H-NMR(CDCl 3)：δ8.45-8.28(1H)，8.14-8.10(1H)，7.50-6.80(6H)，3.76-3.00(1H)，3.00-2.85(3H)，1.85-0.83(24H).
Embodiment 75
N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-(2, the 6-diisopropyl phenyl) amine synthetic
To N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenylmethylene]-add sodium borohydride (13.0mmol) in acetate (7.0mL) solution of N-(2, the 6-diisopropyl phenyl) amine (10.0mmol).This mixture was at room temperature stirred 1 hour.In reaction mixture, add entry and toluene.The dry organic layer that concentrates.Gained oily matter by purification by silica gel column chromatography, is obtained N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-(2, the 6-diisopropyl phenyl) amine (3.19g, yield 82.4%), be yellow oil.
1H-NMR(CDCl 3)：δ7.68-7.06(7H)，3.91-3.77(2H)，3.30-2.68(1H)，3.28-3.08(2H)，3.08-2.91(1H)，1.88-0.88(24H)；
MS(EI)m/z 387(M +)，210，195.
Embodiment 76
Two (dimethylamino) N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-(2, the 6-diisopropyl phenyl) amine closes the synthetic of zirconium [complex compound 27]
At-78 ℃, to N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-drip toluene (8.1mL) solution of four (dimethylamino) titanium (3.0mmol) in toluene (12.2mL) solution of N-(2, the 6-diisopropyl phenyl) amine (3.0mmol).This mixture was at room temperature stirred 1 hour, stirred 5 hours at 100 ℃ then, obtain yellow solution.Underpressure distillation removes desolvates, and obtains two (dimethylamino) N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyls]-N-(2, the 6-diisopropyl phenyl) amine closes zirconium (1.81g, yield 100%), is faint yellow solid.
1H-NMR(C 6D 6)：δ7.31-6.83(7H)，4.43(2H)，3.17(2H)，2.64(s，12H)，2.00(6H)，1.98(6H)，1.13(6H)，1.00(6H)；
MS(EI)m/z 563(M +)，518，473，431，387，210.
Embodiment 77
Dichloride N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-(2, the 6-diisopropyl phenyl) amine closes the synthetic of zirconium [complex compound 28]
At 0 ℃, to two (dimethylamino) N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-(2, the 6-diisopropyl phenyl) amine closes pentane (10.0mL) solution that drips trimethylsilyl chloride (27.5mmol) in pentane (14.7mL) solution of zirconium (2.5mmol).This mixture was at room temperature stirred 16 hours.The solid that filtering-depositing goes out obtains dichloride N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-(2, the 6-diisopropyl phenyl) amine closes zirconium (0.30g, yield 22.0%), is white solid.
1H-NMR(C 6D 6)：δ7.20-6.76(7H)，4.64(2H)，3.01(2H)，2.06(6H)，1.87(6H)，1.43(6H)，0.93(6H)；
MS(EI)m/z 547(M +)，386，319，255，210，174.
Embodiment 78
N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenylmethylene]-N-pentafluorophenyl group amine synthetic
Thionyl chloride (50.0mmol) and penta fluoro benzene amine (5.0mmol) are mixed under nitrogen atmosphere, room temperature, and volatile constituent is heated up in a steamer in decompression.At room temperature, in this mixture, drip toluene (13.8mL) solution of 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl aldehyde (5.0mmol).At room temperature stir this mixture.After vapor-phase chromatography determined that aldehyde disappears, decompression was heated up in a steamer and is desolvated, and obtains N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenylmethylene]-N-pentafluorophenyl group amine (2.10g, yield 100%).
MS(EI)m/z 391(M +)，209，193，179，167，77.
Embodiment 79
N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-pentafluorophenyl group amine synthetic
To N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenylmethylene]-add sodium borohydride (5.2mmol) in acetate (4.9mL) solution of N-pentafluorophenyl group amine (4.0mmol).This mixture was at room temperature reacted 3 hours.In this reaction mixture, add the 5.0M NaOH aqueous solution and ether then.The dry organic layer that concentrates.Gained oily matter by purification by silica gel column chromatography, is obtained N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-pentafluorophenyl group amine (0.72g, yield 34.2%), be yellow oil.
1H-NMR(CDCl 3)：δ7.48-7.06(4H)，4.43-4.27(2H)，3.85-3.70(1H)，3.00-2.70(1H)，1.89-0.90(12H)；
MS(EI)m/z 393(M +)，210，195，180，165.
Embodiment 80
Two (dimethylamino) N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-pentafluorophenyl group amine closes the synthetic of titanium [complex compound 29]
At-78 ℃, to N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-drip toluene (5.0mL) solution of four (dimethylamino) titanium (1.3mmol) in toluene (7.5mL) solution of N-pentafluorophenyl group amine (1.3mmol).This mixture was at room temperature stirred 1 hour, stirred 5 hours at 100 ℃ then, obtain red solution.Underpressure distillation removes desolvates, and obtains two (dimethylamino) N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyls]-N-pentafluorophenyl group amine closes titanium (0.72g), is red solid.
Embodiment 81
Dichloride N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-the N-phenyl amine closes the synthetic of titanium [complex compound 30]
At 0 ℃, to two (dimethylamino) N-[2-(2 that obtain by above-mentioned reaction, 3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-pentafluorophenyl group amine closes pentane (7.0mL) solution that drips trimethylsilyl chloride (15.1mmol) in pentane (10.4mL) solution of titanium (1.3mmol).This mixture was at room temperature stirred 16 hours.The solid that filtering-depositing goes out concentrates gained solution.In enriched material, add pentane.The solid that filtering-depositing goes out obtains dichloride N-[2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-pentafluorophenyl group amine closes titanium (0.12g, yield 17.4%), is orange solids.
1H-NMR(C 6D 6)：δ7.46-7.43(2H)，7.20-6.85(7H)，4.64(2H)，2.07(6H)，1.83(6H)；
MS(EI)m/z 509(M +)，473，392，209.
Embodiment 82
Synthesizing of 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl aldehyde penta fluoro benzene hydrazone
Under nitrogen atmosphere, in ethanol (60.0mL) solution of 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl aldehyde (10.0mmol), drip penta fluoro benzene hydrazine (11.0mmol).This mixture was at room temperature stirred 2 hours.Decompression is heated up in a steamer and is desolvated, and with resistates recrystallization in hexane, obtains 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl aldehyde penta fluoro benzene hydrazones (4.00g, yield 97.0%).
1H-NMR(CDCl 3)：δ8.03-8.00(1H)，7.71-6.91(5H)，3.17-2.71(1H)，1.94-0.86(12H)；
MS(EI)m/z 406(M +)，277，244，209.
Embodiment 83
Synthesizing of complex compound 31
Figure G2006100046087D01691
Complex compound 31
At-78 ℃, in toluene (19.0mL) solution of 2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl aldehyde penta fluoro benzene hydrazone (4.6mmol), drip toluene (13.0mL) solution of four (dimethylamino) titanium (4.6mmol).This mixture was at room temperature stirred 1 hour, stirred 5 hours at 100 ℃ then, obtain red solution.Underpressure distillation removes and desolvates, and obtains the complex compound 28 (2.37g, yield 100%) into red solid.
1H-NMR(C 6D 6)：δ8.03-8.21(1H)，7.71-6.99(4H)，3.27(12H)，2.77(6H)，2.60(6H).
Embodiment 84
Synthesizing of complex compound 32
Complex compound 32
At 0 ℃, in pentane (34.2mL) solution of complex compound 31 (4.4mmol), drip toluene (23.0mL) solution of trimethylsilyl chloride (48.0mmol).Then this mixture was at room temperature stirred 16 hours.The solid that filtering-depositing goes out obtains the complex compound 29 (0.72g, yield 31.3%) into orange solids.
1H-NMR(C 6D 6)：δ8.53-8.50(1H)，7.42-6.91(4H)，2.16(6H)，1.61(6H).
MS(EI)m/z 522(M +)，406，342，222，209.
Embodiment 85
Synthesizing of 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-(2,4, the 6-trimethylphenyl)-benzimide
Under-78 ℃, nitrogen atmosphere, in tetrahydrofuran (THF) (25.5mL) solution of 2-(2,3,4,5-tetramethyl-ring pentadienyl) benzonitrile (6.3mmol), drip 2,4, tetrahydrofuran (THF) (55.6mL) solution of 6-trimethylphenyl lithium (12.5mmol).The temperature of this mixture is increased to room temperature, stirred 5 hours.In this reaction mixture solution, add toluene and water, organic layer is separated with water layer.Dry organic layer, distillation removes and desolvates, and obtains 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-(2,4, the 6-trimethylphenyl)-benzimide (2.34g), is brown oil.
MS(EI)m/z 342，328，312，262.
Embodiment 86
Two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-(2,4, the 6-trimethylphenyl)-benzimide closes the synthetic of titanium [complex compound 33]
At-78 ℃, in toluene (4.0mL) solution of 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-(2,4, the 6-trimethylphenyl)-benzimide (1.0mmol), drip toluene (2.0mL) solution of four (dimethylamino) titanium (1.0mmol).This mixture was at room temperature stirred 1 hour, stirred 5 hours at 100 ℃ then, obtain red solution.Underpressure distillation removes and desolvates, and obtains two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-(2,4, the 6-trimethylphenyl)-benzimide and closes titanium (0.47g).
Embodiment 87
Dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-(2,4, the 6-trimethylphenyl)-benzimide closes the synthetic of titanium [complex compound 34]
At 0 ℃, to two (dimethylamino) 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-(2,4, the 6-trimethylphenyl)-benzimide closes pentane (5.0mL) solution that drips trimethylsilyl chloride (11.0mmol) in pentane (6.9mL) solution of titanium (1.0mmol).This mixture was at room temperature stirred 16 hours.The solid that filtering-depositing goes out obtains dichloride 2-(2,3,4,5-tetramethyl-ring pentadienyl)-α-(2,4, the 6-trimethylphenyl)-benzimide and closes titanium (0.19g, yield 44.0%), be orange solids.
1H-NMR(C 6D 6)：δ7.45-6.67(6H)，2.43(6H)，2.15(3H)，2.08(6H)，1.67(6H)；
MS(EI)m/z 458(M +)，423，340，278.
Polyreaction
Embodiment 88＜polymeric reaction condition A-1 〉
Under nitrogen atmosphere, the toluene (5.0mL) of packing in autoclave makes temperature-stable at 40 ℃.The ethene of packing into then makes pressure-stabilisation until being pressurized to 0.60MPa.Close titanium (0.10 μ mol) to wherein adding MMAO (250 μ mol, 5.8wt%Al, Tosoh-Akzo company) (100 μ mol) and dichloride [2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl] phenyl methyl alkoxy radical, make its polyase 13 0 minute.As the polymeric result, every mole of titanium per hour generates 4.00 * 10 5The g polymkeric substance.
Embodiment 89＜polymeric reaction condition B-1 〉
Except hexane solution (40 μ L, 1.0M, Northeast chemistry) and pentafluorophenyl group borine (0.30 μ mol) with triisobutyl aluminium replace outside the MMAO, to carry out polymerization with embodiment 88 similar methods.As the polymeric result, every mole of titanium per hour generates 1.00 * 10 5The g polymkeric substance.
Embodiment 90＜polymeric reaction condition C-1 〉
Except hexane solution (40 μ L, 1.0M, Northeast chemistry) and four (pentafluorophenyl group) boric acid dimethyl puratized agricultural spray (0.30 μ mol) with triisobutyl aluminium replace outside the MMAO, to carry out polymerization with embodiment 88 similar methods.As the polymeric result, every mole of titanium per hour generates 3.10 * 10 6The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 876,000, and molecular weight distribution (Mw/Mn) is 3.5, and Tm is 126.5 ℃.
Embodiment 91＜polymeric reaction condition D-1 〉
Except hexane solution (40 μ L, 1.0M, Northeast chemistry) and four (pentafluorophenyl group) boric acid triphenyl methyl esters (0.30 μ mol) with triisobutyl aluminium replace outside the MMAO, to carry out polymerization with embodiment 88 similar methods.As the polymeric result, every mole of titanium per hour generates 2.60 * 10 6The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 990,000, and molecular weight distribution (Mw/Mn) is 3.6, and Tm is 129.6 ℃.
Embodiment 92＜polymeric reaction condition A-2 〉
Under nitrogen atmosphere, the toluene (5.0mL) of packing in autoclave makes temperature-stable at 40 ℃.The ethene of packing into then makes pressure-stabilisation until being pressurized to 0.60MPa.Close titanium (0.10 μ mol), make its polyase 13 0 minute to wherein adding MMAO (250 μ mol, 5.8wt%Al, Tosoh-Akzo company) (100 μ mol) and dichloride [2-(2,3,4,5-tetramethyl-ring pentadienyl) phenyl methyl]-N-phenyl amine.As the polymeric result, every mole of titanium per hour generates 1.59 * 10 6The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 285,000, and molecular weight distribution (Mw/Mn) is 4.5, and Tm is 85.9 ℃.
Embodiment 93＜polymeric reaction condition A-3 〉
Except polymerization temperature is 70 ℃, to carry out polymerization with embodiment 92 similar methods.As the polymeric result, every mole of titanium per hour generates 1.01 * 10 7The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 121,000, and molecular weight distribution (Mw/Mn) is 3.2, and Tm is 90.6 ℃.
Embodiment 94＜polymeric reaction condition B-2 〉
Under nitrogen atmosphere, pack in autoclave toluene (5.0mL) and 1-hexene (0.50 μ L) make temperature-stable at 40 ℃.The ethene of packing into then makes pressure-stabilisation until being pressurized to 0.60MPa.To the hexane solution that wherein adds triisobutyl aluminium (40 μ L, 1.0M, Northeast chemistry), pentafluorophenyl group borine (0.30 μ mol) and dichloride N-[2-(1-indenyl) phenyl methyl]-the N-phenyl amine closes titanium (0.10 μ mol), makes its polyase 13 0 minute.As the polymeric result, every mole of titanium per hour generates 2.25 * 10 6The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 1,360,000, and molecular weight distribution (Mw/Mn) is 8.4, and Tm is 116.1 ℃.
Embodiment 95＜polymeric reaction condition B-3 〉
Except polymerization temperature is 70 ℃, to carry out polymerization with embodiment 94 similar methods.As the polymeric result, every mole of titanium per hour generates 1.35 * 10 7The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 817,000, and molecular weight distribution (Mw/Mn) is 19.3, and Tm is 122.2 ℃.
Embodiment 96＜polymeric reaction condition C-2 〉
Under nitrogen atmosphere, pack in autoclave toluene (5.0mL) and 1-hexene (0.50 μ L) make temperature-stable at 40 ℃.The ethene of packing into then makes pressure-stabilisation until being pressurized to 0.60MPa.To the hexane solution that wherein adds triisobutyl aluminium (40 μ L, 1.0M, Northeast chemistry), [2-(2 for four (pentafluorophenyl group) boric acid dimethyl puratized agricultural spray (0.30 μ mol) and dichloride, 3,4,5-tetramethyl-ring pentadienyl) phenyl] the phenyl methyl alkoxy radical closes titanium (0.10 μ mol), makes its polyase 13 0 minute.As the polymeric result, every mole of titanium per hour generates 1.00 * 10 6The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 1,170,000, and molecular weight distribution (Mw/Mn) is 8.4, and Tm is 114.1 ℃.
Embodiment 97＜polymeric reaction condition C-3 〉
Except polymerization temperature is 70 ℃, to carry out polymerization with embodiment 96 similar methods.As the polymeric result, every mole of titanium per hour generates 1.50 * 10 6The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 530,000, and molecular weight distribution (Mw/Mn) is 7.7, and Tm is 116.0 ℃.
Embodiment 98＜polymeric reaction condition C-4 〉
Except polymerization temperature is 130 ℃, to carry out polymerization with embodiment 96 similar methods.As the polymeric result, every mole of titanium per hour generates 2.90 * 10 5The g polymkeric substance.
Embodiment 99＜polymeric reaction condition D-2 〉
Under nitrogen atmosphere, pack in autoclave toluene (5.0mL) and 1-hexene (0.50 μ L) make temperature-stable at 40 ℃.The ethene of packing into then makes pressure-stabilisation until being pressurized to 0.60MPa.To the hexane solution that wherein adds triisobutyl aluminium (40 μ L, 1.0M, Northeast chemistry), [2-(2 for four (pentafluorophenyl group) boric acid triphenyl methyl esters (0.30 μ mol) and dichloride, 3,4,5-tetramethyl-ring pentadienyl) phenyl] the phenyl methyl alkoxy radical closes titanium (0.10 μ mol), makes its polyase 13 0 minute.As the polymeric result, every mole of titanium per hour generates 1.30 * 10 6The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 1,363,000, and molecular weight distribution (Mw/Mn) is 10.5, and Tm is 115.8 ℃.
Embodiment 100＜polymeric reaction condition D-3 〉
Except polymerization temperature is 70 ℃, to carry out polymerization with embodiment 99 similar methods.As the polymeric result, every mole of titanium per hour generates 1.20 * 10 6The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 701,000, and molecular weight distribution (Mw/Mn) is 9.9, and Tm is 117.3 ℃.
Embodiment 101＜polymeric reaction condition D-4 〉
Except polymerization temperature is 130 ℃, to carry out polymerization with embodiment 99 similar methods.As the polymeric result, every mole of titanium per hour generates 2.00 * 10 5The g polymkeric substance.
The catalyst component of embodiment 102-237, polymerizing condition, catalyst activity, reaction result are listed in following table 1 in table 5.
The homopolymerization of table 1 ethene
Embodiment Complex compound Polymerizing condition Active (* 10 6g PE/mol-cat/hr)
91 2 D-1 1.29
102 3 A-1 1.23
103 3 C-1 1.83
104 3 D-1 3.66
105 4 A-1 12.87
106 4 B-1 4.35
107 4 C-1 9.09
108 4 D-1 4.17
109 7 C-1 1.38
110 7 D-1 1.47
111 8 A-1 2.76
Embodiment Complex compound Polymerizing condition Active (* 10 6g PE/mol-cat/hr)
112 8 C-1 6.05
113 8 D-1 6.37
114 5 A-1 1.32
115 6 C-1 5.97
116 6 D-1 7.22
117 12 C-1 5.97
118 12 D-1 7.22
119 15 C-1 1.89
120 15 D-1 2.13
121 10 C-1 2.91
122 10 D-1 3.36
123 18 C-1 3.12
124 18 D-1 2.61
125 30 A-1 4.05
126 30 C-1 22.50
127 30 D-1 21.16
128 22 A-1 26.05
129 22 B-1 8.95
130 22 C-1 6.32
131 22 D-1 5.61
Embodiment Complex compound Polymerizing condition Active (* 10 6g PE/mol-cat/hr)
Embodiment Complex compound Polymerizing condition Active (* 10 6g PE/mol-cat/hr)
132 25 A-1 5.58
133 25 C-1 7.49
134 25 D-1 13.50
135 27 A-1 3.72
136 27 C-1 17.59
137 27 D-1 19.52
138 26 A-1 8.81
139 26 C-1 15.34
140 26 D-1 6.82
141 28 A-1 5.73
142 28 C-1 23.63
143 28 D-1 34.66
144 24 A-1 4.47
145 24 B-1 3.12
146 24 C-1 7.50
147 24 D-1 9.29
148 31 A-1 1.98
149 31 C-1 2.91
150 31 D-1 3.33
Embodiment Complex compound Polymerizing condition Active (* 10 6g PE/mol-cat/hr)
151 34 C-1 12.13
152 34 D-1 7.55
The copolyreaction of table 2 ethene-hexene, promotor MMAO
Embodiment Complex compound Polymerizing condition Temperature, ℃ Active ＊ Mw Mw/Mn Tm，℃
153 3 A-2 40 1.35 3,085,000 4.7 123.2
154 3 A-3 70 1.92 1,132,000 4.8 121.1
155 4 A-2 40 1.59 285,000 4.5 85.9
156 4 A-3 70 10.19 121,000 3.2 90.6
157 8 A-2 40 2.70 1,444,000 4.7 117.4
158 8 A-3 70 1.95 1,173,000 10.1 119.4
159 5 A-3 70 1.92 163,000 9.5 126.9
160 6 A-2 40 19.94 435,000 10.3 118.8
161 6 A-3 70 54.53 66,000 5.8 106.5
162 30 A-2 40 3.42 1,624,000 7.4 109.9
163 30 A-3 70 4.87 1,486,000 39.7 112.3
164 22 A-2 40 10.88 1,759,000 10.5 107.8
165 22 A-3 70 32.77 778,000 22.1 110.1
166 25 A-2 40 4.59 336,000 4.3 118.9
167 25 A-3 70 19.13 93,000 3.8 125
Embodiment Complex compound Polymerizing condition Temperature, ℃ Active ＊ Mw Mw/Mn Tm，℃
168 27 A-2 40 4.65 130,000 2.9 126.7
Embodiment Complex compound Polymerizing condition Temperature, ℃ Active ＊ Mw Mw/Mn Tm，℃
169 27 A-3 70 27.21 44,000 3.6 123.9
170 26 A-2 40 14.23 246,000 3.2 125.9
171 26 A-3 70 39.04 124,000 3 124.5
172 28 A-2 40 9.12 123,000 3.2 128.6
173 28 A-3 70 58.76 46,000 2.9 125.5
174 24 A-2 40 3.42 1,596,000 8.7 125
175 24 A-3 70 6.44 689,000 6.7 121.7
** 10 6G polymkeric substance/mol-cat/hr
The copolyreaction of table 3 ethene-hexene, promotor TIBA/ (C 6F 5) 3B
Embodiment Complex compound Polymerizing condition Temperature, ℃ Active Mw Mw/Mn Tm，℃
176 4 B-3 70 1.29 380,000 2.6 83.5
96 22 B-2 40 2.25 1,360,000 8.4 116.1
97 22 B-3 70 13.51 817,000 19.3 122.2
** 10 6G polymkeric substance/mol-cat/hr
The copolyreaction of table 4 ethene-hexene, promotor TIBA/AB
Embodiment Complex compound Polymerizing condition Temperature, ℃ Active ＊ Mw Mw/Mn Tm，℃
177 3 C-2 40 1.20 3,103,000 3.8 94.6
178 3 C-3 70 1.71 2,066,000 5.6 118.1
179 4 C-2 40 37.94 567,000 4.6 130.3
180 4 C-3 70 75.10 202,000 3 108.5
181 4 C-4 130 47.57 178,000 3.2 100.2
182 7 C-2 40 1.23 1,526,000 5.8 117.3
183 7 C-3 70 1.32 1,041,000 3.9 119.3
184 8 C-2 40 8.24 1,204,000 4.4 116.6
185 8 C-3 70 4.07 1,337,000 5.3 117.4
186 6 C-2 40 14.23 46,000 5.9 140.3
187 6 C-3 70 93.44 18,000 3.5 198.2
188 6 C-4 130 19.12 114,000 6.3 119
189 12 C-3 70 1.71 1,636,000 19.9 121.8
190 15 C-2 40 1.65 1,926,000 4.5 116.5
191 15 C-3 70 1.05 1,061,000 26.7 112.9
192 10 C-2 40 4.08 417,000 115.3 119.2
Embodiment Complex compound Polymerizing condition Temperature, ℃ Active ＊ Mw Mw/Mn Tm，℃
193 18 C-2 40 0.99 1,170,000 8.4 114.1
194 18 C-3 70 1.47 530,000 7.7 116
Embodiment Complex compound Polymerizing condition Temperature, ℃ Active ＊ Mw Mw/Mn Tm，℃
195 30 C-2 40 5.79 1,517,000 2.4 97.5
196 22 C-2 40 6.08 973,000 17.7 113.6
197 22 C-3 70 61.03 603,000 23 118.2
198 22 C-4 130 0.96 460,000 6.7 124
199 25 C-2 40 8.29 157,000 4.2 123.8
200 25 C-3 70 33.76 133,000 3 124.2
201 27 C-2 40 14.46 489,000 4 123.8
202 26 C-2 40 19.89 156,000 3.4 128.1
203 26 C-3 70 46.80 117,000 2.7 124.7
204 28 C-2 40 31.26 376,000 4.4 123
205 28 C-3 70 42.77 967,000 2.5 121.6
206 24 C-2 40 4.89 749,000 21 121.4
207 24 C-3 70 3.72 943,000 5.4 122
** 10 6G polymkeric substance/mol-cat/hr
The copolyreaction of table 5 ethene-hexene, promotor TIBA/CB
Embodiment Complex compound Polymerizing condition Temperature, ℃ Active ＊ Mw Mw/Mn Tm，℃
208 3 D-2 40 1.89 3,187,000 4.3 118.5
209 3 D-3 70 2.01 2,470,000 10.3 119.1
210 4 D-2 40 50.69 561,000 4.1 116.3
Embodiment Complex compound Polymerizing condition Temperature, ℃ Active ＊ Mw Mw/Mn Tm，℃
211 4 D-3 70 70.02 208,000 3.6 111.0
212 4 D-4 130 56.70 304,000 8 107.8
213 7 D-2 40 0.99 1,766,000 8.5 119.0
214 8 D-2 40 6.58 1,537,000 5.4 115.8
215 8 D-3 70 3.27 1,569,000 9.1 118.5
216 6 D-2 40 75.52 97,000 15.6 119.0
217 6 D-3 70 147.27 49,000 7.1 119.6
218 6 D-4 130 1.26 58,000 8.6 118.2
219 12 D-3 70 1.26 1,649,000 8.1 123.2
220 15 D-2 40 1.11 1,975,000 5.9 115.0
221 15 D-3 70 0.90 1,174,000 20 116.4
222 10 D-2 40 3.00 696,648 14.2 120.9
223 10 D-3 70 3.81 5,000 3 121.7
224 18 D-2 40 1.29 1,363,000 10.5 115.8
225 18 D-3 70 1.23 700,000 9.9 117.3
226 22 D-2 40 19.49 1,132,000 13.3 115.2
227 22 D-3 70 78.06 548,000 11.5 113.2
228 22 D-4 130 1.17 564,000 6.3 123.3
229 25 D-2 40 11.39 167,000 4.4 130.3
Embodiment Complex compound Polymerizing condition Temperature, ℃ Active ＊ Mw Mw/Mn Tm，℃
Embodiment Complex compound Polymerizing condition Temperature, ℃ Active ＊ Mw Mw/Mn Tm，℃
230 25 D-3 70 27.03 138,000 3 124.2
231 27 D-2 40 29.16 520,000 3.9 125.7
232 26 D-2 40 27.44 152,000 3.7 126.1
233 26 D-3 70 55.61 108,000 2.8 125.3
234 28 D-2 40 107.08 346,000 4.4 123.6
235 28 D-3 70 28.23 232,000 3.8 121.3
236 24 D-2 40 5.07 773,000 22.1 124.0
237 24 D-3 70 3.09 969,000 3.9 121.7
** 10 6G polymkeric substance/mol-cat/hr
Embodiment 238
Under nitrogen atmosphere, the toluene (5.0mL) of packing in autoclave makes temperature-stable at 40 ℃.Propylene pack then into until being pressurized to 0.20MPa, make pressure-stabilisation.To the hexane solution that wherein adds triisobutyl aluminium (40 μ L, 1.0M, Northeast chemistry), four (pentafluorophenyl group) boric acid triphenyl methyl esters (0.30 μ mol) and dichloride N-[2-(1-indenyl) phenyl methyl]-the N-phenyl amine closes titanium (0.10 μ mol), makes its polymerization 20 minutes.As the polymeric result, every mole of titanium per hour generates 4.41 * 10 6The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 712,000, and molecular weight distribution (Mw/Mn) is 3.7, and Tm is 127.7 ℃.
Embodiment 239
Under nitrogen atmosphere, the toluene (5.0mL) of packing in autoclave makes temperature-stable at 40 ℃.Propylene pack then into until being pressurized to 0.20MPa, make pressure-stabilisation.To the hexane solution that wherein adds triisobutyl aluminium (40 μ L, 1.0M, Northeast chemistry), four (pentafluorophenyl group) boric acid dimethyl puratized agricultural spray (0.30 μ mol) and dichloride N-[2-(1-indenyl) phenyl methyl]-the N-phenyl amine closes titanium (0.10 μ mol), makes its polymerization 20 minutes.As the polymeric result, every mole of titanium per hour generates 2.10 * 10 6The g polymkeric substance, the molecular weight of this polymkeric substance (Mw) is 678,000, and molecular weight distribution (Mw/Mn) is 3.8, and Tm is 135.6 ℃.
Industrial applicibility
According to the present invention, the available part intermediate that can prepare more easily processing obtains transition metal complex, and need not to use to moisture-sensitive, is difficult to the silicon compound processed as key intermediate. Because described transition metal complex can be used as the catalytic component of the various olefin polymers of preparation, so the present invention particularly has outstanding contributions to existing olefin polymer preparation.

Claims (5)

1. carbonyl compound shown in the formula (1):
R wherein 1Expression hydrogen atom, C 1-10Alkyl or C 6-20Aryl;
R 2, R 3, R 4And R 5Identical or different, independent separately expression hydrogen atom, C 1-10Alkyl;
R 6, R 7, R 8And R 9Identical or different, independent separately expression hydrogen atom, C 1-10Alkyl, perhaps
R 2And R 3Be interconnected to form phenyl ring;
Condition is 1) position of two keys is arbitrarily in the cyclopentadiene ring, perhaps this cyclopentadiene ring is illustrated in the mixture and 2 that the optional position has the compound of two keys) R 2And R 3Perhaps R 4And R 5All can not be together with each other and cyclopentadiene ring formation fluorenes ring or indenes ring.
2. the carbonyl compound of claim 1, the R in its Chinese style (1) 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8And R 9Be C 1-10Alkyl.
3. claim 1 or 2 carbonyl compound, wherein R 2, R 3, R 4And R 5Identical or different, independent separately expression hydrogen atom or C 1-5Alkyl.
4. claim 1 or 2 carbonyl compound, wherein R 1Be hydrogen atom, C 1-5Alkyl or C 6-10Aryl.
5. method for preparing carbonyl compound shown in claim 1 Chinese style (1), this method is included in magnesium compound or organolithium compound exists down, make the reaction of cyclopentenone shown in halogen compounds shown in the formula (2) and the formula (3), obtain cyclopentenol shown in the formula (4), and with the described compound of acid treatment:
R wherein 1, R 6, R 7, R 8And R 9Have and following identical connotation,
R 10And R 11Identical or different, represent C separately 1-10Alkyl, perhaps they are connected with each other at its end, and the carbon atom that is connected with this Sauerstoffatom with Sauerstoffatom forms 5 or 6 yuan of rings, and
X represents chlorine, bromine or iodine atom;
R wherein 2, R 3, R 4And R 5Have the connotation identical with following definitions;
Figure F2006100046087C00023
R wherein 1Expression hydrogen atom, C 1-10Alkyl, C 6-20Aryl,
R 2, R 3, R 4And R 5Identical or different, represent hydrogen atom, C separately 1-10Alkyl,
R 6, R 7, R 8And R 9Identical or different, independent separately expression hydrogen atom, C 1-10Alkyl, C 6-20Aryl, perhaps
R 2And R 3Be interconnected to form phenyl ring;
R 10And R 11As above definition.
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