CN86106933A - Agricultural chemical compound - Google Patents

Agricultural chemical compound Download PDF

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Publication number
CN86106933A
CN86106933A CN 86106933 CN86106933A CN86106933A CN 86106933 A CN86106933 A CN 86106933A CN 86106933 CN86106933 CN 86106933 CN 86106933 A CN86106933 A CN 86106933A CN 86106933 A CN86106933 A CN 86106933A
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phenyl
ring
trioxa
propyl
octanes
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CN 86106933
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Chinese (zh)
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约翰·爱德华·卡西达
克里斯托弗·约翰·帕尔默
约翰·帕特里克·拉金
伊恩·哈罗德·史密斯
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Wellcome Foundation Ltd
University of California
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Wellcome Foundation Ltd
University of California
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Priority claimed from US06/779,167 external-priority patent/US4772624A/en
Priority claimed from GB858523582A external-priority patent/GB8523582D0/en
Priority claimed from GB868600201A external-priority patent/GB8600201D0/en
Application filed by Wellcome Foundation Ltd, University of California filed Critical Wellcome Foundation Ltd
Publication of CN86106933A publication Critical patent/CN86106933A/en
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Abstract

Contain 2 or 3 ring hetero atoms that are selected from O, S and N, 1 by the 4-alkynyl phenyl replace, at 4 and at random at 3 and/or 5 substituted two rings [2,2,1]-heptane, two the ring [2,2,2] octane and two ring [2,2,3] nonanes, be valuable agricultural chemicals, in particular as sterilant and miticide.Compound that this compounds can replace by corresponding 4-iodophenyl and alkyne reaction or the compound dehydrobromination that replaces by corresponding 4-dibromo ethyl benzene base make.

Description

Agricultural chemical compound
The present invention relates to some new compounds, their preparation method, some prescriptions that comprise them and their application aspect Pest Control with insecticidal activity.More particularly, the present invention relates to the assorted bicyclic alkane of a class.
Some 2,6, the application of 7-trioxa two ring (2,2,2) octane compounds is open in European Patent Application No. 152229.The derivative of finding these compounds now has significant insecticidal activity.
By this, the invention provides down the compound of formula I
Wherein R is C 2-10Alkyl, alkenyl or alkynyl, they can replace arbitrarily or substituent methyl, these substituted radicals have: cyano group, halogen, C 3-4Cycloalkyl, C 1-4Alkoxyl group, or S(O) mR 4Base (R wherein 4Be C 1-4Alkyl, m value are 0,1 or 2); Or R is C 3-10Cycloalkyl, C 4-10Cycloalkenyl group or phenyl, every kind of group can at random further replaced by following groups: C 1-4Alkoxyl group, C 1-3Alkyl, C 2-4Alkynyl, halogen, cyano group or S(O as defined above) mR 4Group;
R 1And R 3, no matter identical or different, can be hydrogen, halogen, C 1-3Alkyl, C 2-3Alkenyl or alkynyl, these alkyl, thiazolinyl and alkynyl can be at random by halogen, cyano group or C 1-4Alkoxyl group further replaces; They also can be the carbalkoxys that contains 6 carbon atoms of as many as, or S(O as defined above) mR 4Base, or three C are arranged 1-4The alkane first, the alkynyl that alkyl tin groups, alkyl silane groups replaces; Perhaps R 1Be COOC 1-4Alkyl, cyano group, gem-dimethyl is together with dicyano, together with dihalo-, together with diacetylene, Spirocyclopropyl, volution oxidative ethane or spiro oxetane, the volution oxidative ethane of replacement or the spiro oxetane of replacement, oxygen or methylene radical can at random be replaced by cyanogen, halogen or trifluoromethyl; R 1Can also and R and their institute's banded carbon atoms together, form a C 5-7Carbocyclic ring, the ring on can be by C 1-3Alkyl, alkoxyl group or C 2-3Thiazolinyl at random further replaces;
R 2Be at 4-(C ≡ C) nR 5The phenyl that replaces, and on other position of phenyl ring, can at random replace, n is 1 or 2 here, R 5Be hydrogen, bromine, chlorine, iodine, S(O) mR 4xBase (R wherein 4xBe trifluoromethyl, perhaps R 4xBe exactly R 4, this R 4With m such as preceding definition); R 5Also can be fat or the alicyclic radical that contains any replacement of 9 carbon atoms of as many as ,-C * R 6Base (wherein * and be oxygen or sulphur, R 6Be C 1-6Alkyl or-oxyl can be replaced arbitrarily by fluorine or amino on it, and amino can be arbitrarily by one or two C 1-4Alkyl further replaces); R 5Can also be cyano group, or have three C 1-4The alkane silyl, or have two C 1-4An alkyl and a phenyl silica-based.
Y and Y 1Can be identical or inequality, they can be selected from oxygen and S(O) m(wherein m can be 0,1 or 2); Z is CH 2CH 2, CH 2CH 2O, sulphur, CH 2O, CH 2S, CHR 1xNR 7(R here 1xBe hydrogen, cyano group, halogen, CO 2R 4Or C 1-3Alkyl, C 2-3Alkenyl or alkynyl, these alkyl, thiazolinyl and alkynyl can be at random by halogen, cyanogen, C 1-4Alkoxyl group, the carbalkoxy or the S(O of 6 carbon atoms of as many as) mR 4Base institute further replaces, here m and R 4Define R as the front 7Be hydrogen, benzyl, C 1-4Alkyl, C(O) R 8, R here 8Be C 1-4Alkyl, alkoxyl group or NHR 9Base, R here 9Be C 1-4Alkyl, C 7-8Aralkyl or the phenyl that is replaced arbitrarily by halogen), Z also can be-COCH 2-or CH(OR 10) CH 2-, R here 10Be hydrogen, C 1-4Alkyl, C 1-4Acyl group or C 1-3Formamyl,
Remove R 5Be the silica-based of hydrogen or trialkyl replacement, and Y and Y 1Be that oxygen, Z are CH 2Beyond the O, R 1And R 3Must be hydrogen.
In the definition of Z, the atom of writing earlier is to be attached on 4 of bicyclic ring system.
Suitable R is propyl group, butyl, amyl group, C 2-5Alkenyl or alkynyl, C 5-7Cycloalkyl or phenyl, they can at random further be replaced by fluorine, chlorine, bromine.Only R is n-propyl, normal-butyl, isobutyl-, second butyl, tertiary butyl, and cyclopentyl or cyclohexyl, especially good R are n-propyl, normal-butyl, isobutyl-, tertiary butyl or cyclohexyl.
Suitable R 1Be hydrogen, cyano group, methyl or ethyl, can be further at random replaced on it by cyano group, methoxyl group, methylthio group, chlorine, bromine or fluorine institute.Only R 1Be hydrogen, methyl, cyano group, trifluoromethyl or ethyl.Especially good R 1Be hydrogen, methyl, cyano group or trifluoromethyl.
R 2Suitable substituents comprises halogen, cyano group, azido-, nitro, C on the middle phenyl ring 1-3Alkyl or alkoxyl group (can at random be replaced by halogen again on it), C 2-3Alkenyl or alkynyl (can at random be replaced by halogen again on it).Especially good halogen substituting group can be fluorine, chlorine or bromine).Preferably in the 3-position and/or 5 nearly two substituting groups are arranged, but also can be in 2-and/or 6-position for fluorine.
Suitable R 3Be hydrogen, methyl or trifluoromethyl.Only R 3Be hydrogen.
N value preferably 1.
Suitable R 5The methyl or the ethyl that are hydrogen, replace arbitrarily, cyano group, three C 1-4The alkane silyl or-COR 6Base, wherein R 6Be C 1-4Alkyl or alkoxyl group or by one to two C 1-4The amino that alkyl replaces.Work as R 5When being methyl or ethyl, suitable substituents comprises hydroxyl, OSO 2R 10xBase (R here 10xBe C 1-4Alkyl, phenyl or tolyl, C 1-4Alkoxyl group, C 1-4Acyloxy can be replaced by amino again on it, can be by one or two C on this is amino 1-4Alkyl replaces or is replaced by a phenyl, can also at random be replaced by one to three halogen atom on this phenyl) or SCOR 4Or S(O) mR 4, m here and R 4All as the front is defined, or-NR 11R 12Base, R here 11Be hydrogen or C 1-4Alkyl, R 12Be hydrogen, C 1-4Alkyl or-COR 13Base, R here 13Be C 1-4Alkyl or alkoxyl group, perhaps-NR 11R 12Be one five yuan or hexa-member heterocycle.Only R 5Be hydrogen, trimethyl silicon based or the methyl of replacement or the ethyl of replacement, substituting group is hydroxyl or methoxyl group here.
Suitable Z is-CH 2S-,-CH 2O-, or-CH 2CH 2-, best Z is-CH 2S-or-CH 2O.
Suitable Y and Y 1All be oxygen.
One group of above-claimed cpd is the compound of formula (I A):
Figure 86106933_IMG7
R wherein aBe C 2-7Alkyl, alkenyl or alkynyl, they are by cyano, halogen or C arbitrarily 1-4Alkoxyl group replaces, perhaps R aBe C 3-10Cycloalkyl, C 4-10Cycloalkenyl group or phenyl, they can be at random by C 1-4Alkoxyl group, C 1-3Alkyl, C 2-4Alkynyl, halogen or cyano group replace; R 1aBe hydrogen, C 1-3Alkyl, C 2-3Alkenyl or alkynyl, they are by cyano, C arbitrarily 1-4Alkoxyl group, C 1-4Alkylthio, the carbalkoxy or the halogen that contain 6 carbon atoms of as many as replace, perhaps R 1aBe cyano group, gem-dimethyl, perhaps R 1aAnd R aAnd form a C with the carbon atom that they connected 5-7Carbocyclic ring, also can be on it at random by C 1-3Alkyl or C 2-3Alkoxyl group or thiazolinyl replace; R 2aBe 4 quilts-C ≡ CR 5aThe phenyl that replaces, other position of phenyl ring also can at random be replaced, here R 5aBe a C who replaces arbitrarily 1-9The fat base, or-COR 6aBase, R here 6aBe C 1-6Alkyl or-oxyl, or by one or two C 1-4The amino that alkyl replaces arbitrarily; R 5aAlso can be cyano group, three C 1-4Alkane silylation, or the methyl-monosilane base of two alkyl and a phenyl; R 3aBe hydrogen, C 1-3Alkyl, C 2-3Alkenyl or alkynyl, they can be further by cyano group, C 1-4Alkylthio, C 1-4Alkoxy or halogen replaces arbitrarily; Y aAnd Y 1aCan be identical or different, they be selected from oxygen or S(O respectively) m, m is 0,1 or 2 here; Z aBe CH 2CH 2, CH 2CH 2O, sulphur, CH 2O, CH 2S, or CH 2NR 7a, R here 7aBe hydrogen, benzyl, C 1-4Alkyl or C(O) R 8aBase, R here 8aBe C 1-4Alkyl or alkoxyl group, Z aAlso can be-COCH 2-or-CH(OR 10a) CH 2-, R here 10aBe hydrogen, C 1-4Alkyl, C 1-4Acyl group or C 1-3Formamyl.
Suitable R aBe propyl group, butyl, amyl group, C 2-5Alkenyl or alkynyl, C 5-7Cycloalkyl or phenyl all can at random be replaced by fluorine, chlorine, bromine on it.Only R aBe n-propyl, isobutyl-, benzene dibutyl, tertiary butyl, cyclopentyl or cyclohexyl, especially good R is n-propyl, isobutyl-, tertiary butyl or cyclohexyl.
Suitable R 1aBe hydrogen, cyano group, methyl or ethyl, can be further replaced arbitrarily again on it by cyano group, methoxyl group, methylthio group, chlorine, bromine or fluorine.Only R 1aBe hydrogen, methyl, trifluoromethyl or ethyl.Especially good R 1aBe hydrogen, methyl or trifluoromethyl.
R 2aSuitable substituents comprises halogen, cyano group, azido-, nitro, C on the middle phenyl ring 1-3Alkyl or alkoxyl group (can be replaced arbitrarily by halogen on it), or C 2-3Alkenyl or alkynyl (also can be replaced arbitrarily on it) by halogen.Only halogenic substituent can be fluorine, chlorine or bromine.Preferably two substituting groups of as many as are in 3 and/or 5.
Suitable R 3aBe hydrogen, methyl or trifluoromethyl.Only R 3aBe hydrogen.
Suitable R 5aBe a methyl or an ethyl that replaces arbitrarily, or cyano group or three C 1-4The alkane silyl, or-COR 6aBase, R here 6aBe C 1-4Alkyl, alkoxyl group or amino can be at random by one or two C on the amino 1-4Alkyl replaces.Work as R 5aWhen being methyl or ethyl, suitable substituents comprises hydroxyl, C 1-4Alkoxyl group, C 1-4Acyloxy, C 1-4Alkylthio or-NR 11aR 12a, R here 11aBe hydrogen or C 1-4Alkyl, R 12aBe hydrogen, C 1-4Alkyl or-COR 11aBase, R here 11aDefinition the same, perhaps-NR 11aR 12aBe one five yuan or hexa-member heterocycle.Only R 5aBy the methyl of hydroxyl, methoxyl group or trimethyl silicon based replacement or ethyl.
Suitable Z aBe-CH 2S-,-CH 2O-, or-CH 2-CH 2-, Z preferably-CH 2S-or-CH 2O-, here heteroatoms be with by R 2aThe carbon atom that replaces is connected.
Suitable Y aAnd Y 1aAll be oxygen.
The present invention's compound preferably comprises:
1-(the trimethyl silicon based ethynyl of 3-nitro-4-(2-) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
The 1-(4-ethynyl phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
The 1-(4-ethynyl phenyl)-and 4-normal-butyl-2,6,7-trioxa two ring (2,2,2) octanes
The 1-(4-ethynyl phenyl)-and 4-isobutyl--2,6,7-trioxa two ring (2,2,2) octanes
The 1-(4-ethynyl phenyl)-and 4-n-pentyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-n-pentyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 3-chloro-4-(2-) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-normal-butyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-isobutyl--2,6,7-trioxa two ring (2,2,2) octanes
1-(4-(3-second chloro third-1-alkynyl) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
4-methoxyl group-1-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl fourth-1-alkynes
1-(4-(3-methoxyl group-third-1-alkynyl) phenyl)-and 4-isobutyl--2,6,7-trioxa two ring (2,2,2) octanes
N-(3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl) Propargyl) ethanamide
The 1-(4-ethynyl phenyl)-and 4-(2, the 2-dimethyl propyl)-2,6,7-trioxa two ring (2,2,2) octanes
3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl)-third-2-acetylenic acid methyl esters
1-(3-chloro-4-ethynyl phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(3-nitro-4-ethynyl phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
The 1-(4-ethynyl phenyl)-and 4-tertiary butyl-2,6,7-trioxa two ring (2,2,2) octanes
The 1-(4-ethynyl phenyl)-and 4-cyclohexyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-and 4-tertiary butyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-cyclohexyl-2,6,7-trioxa two ring (2,2,2) octanes
The 1-(4-ethynyl phenyl)-and 4-ethyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-tertiary butyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(3-chloro-4-(3-methoxyl group-third-1-alkynyl) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
4-cyclohexyl-1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-2,6,7-trioxa two ring (2,2,2) octanes
4-normal-butyl-1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-2,6,7-trioxa two ring (2,2,2) octanes
4-n-pentyl-1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-2,6,7-trioxa two ring (2,2,2) octanes
4-n-propyl-3-Trifluoromethyl-1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-2,6,7-trioxa two ring (2,2,2) octanes
4-n-propyl-3-cyano group-1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-2,6,7-trioxa two ring (2,2,2) octanes
4-(2, the 2-dimethyl propyl)-1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-2,6,7-trioxa two ring (2,2,2) octanes
4-(2, the 2-dimethyl propyl)-1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-2,6,7-trioxa two ring (2,2,2) octanes
3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl) third-2-alkynes N-methyl carbamate
3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) octyl groups) phenyl) third-2-alkynes-1-alcohol
3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl) third-2-alkynes acetic ester
1-(4-(third-1-alkynyl) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-and 4-n-propyl-2,6-Er Evil-7-thiophene two ring (2,2,2) octanes
1-(4-(2-tertiary butyl dimethyl-silicon ethyl-acetylene base) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl) third-2-alkynes methanesulfonate ester
N-methyl-3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-2-yls) phenyl) third-2-alkynyl amide
N-methyl-3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl) third-2-alkynes thioamides
1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-and 3-trifluoromethyl-4-normal-butyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(4-(penta-1-alkynyl) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
The 1-(4-ethynyl phenyl)-and 4-phenyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-phenyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-n-propyl-2,6 ,-Er Evil-7-thiophene two ring (2,2,2) octanes
1-(4-ethynyl phenyl-4-n-propyl-2,6-Er Evil-7-thiophene-two ring (2,2,2) octane
Term " alkyl " is meant alkyl, thiazolinyl (comprise cyclic alkyl and thiazolinyl and by the alkyl of cyclic alkyl and alkenyl substituted and thiazolinyl), alkynyl, aryl and aralkyl."-oxyl " is meant that the alkyl of above-mentioned definition and oxygen link the group that forms.
Further, the present invention also provides the method for the compound of these formula I of preparation, and these methods comprise any method of known preparation similar compound in this professional domain, for example:
(ⅰ) will be at-C ≡ C-R 2The position on contain the corresponding compounds and the compound H C ≡ CR of iodine 5Reaction, R here 5Described as defined above.What the requirement adding was suitable when this reaction was carried out is the known palladium catalyst of one of skill in the art, the cuprous halide of for example dual-triphenylphosphine palladium chloride, and catalytic amount, for example cuprous iodide.Reaction is carried out in basic solvent such as diethylamine or triethylamine usually, and is normal in the temperature of reaction, for example between-50 ℃ and 100 ℃, also can carry out in room temperature easily.The raw material iodophenyl bicyclic alkane of reaction (wherein Y and Y 1Be that oxygen, Z are CH 2O) can ring-closure reaction take place by the compound of following formula II when an acidic catalyst exists makes;
Figure 86106933_IMG8
Here R, R 1And R 3Define R as the front 2xIt is the phenyl that an iodine replaces.Boron fluoride etherate is a kind of specially suitable an acidic catalyst of this ring-closure reaction that carries out, and reaction can be carried out in such as halohydrocarbon at inert solvent, for example can select methylene dichloride easily for use; Temperature of reaction for example between-100 ℃ to 0 ℃, also can be selected between-70 ℃ to-50 ℃ below room temperature easily.
The compound of logical formula II can react and makes with formula III and formula IV compound:
（Ⅲ）R 2x-C（＝O）L （Ⅳ）
Here R 14It is radicals R 1, and R, R 1, R 2xAnd R 3All define as the front, L represents leavings group, for example halogen.This reaction can be easily in inert solvent, in the presence of the alkali, carry out at middle normal temperature.Halohydrocarbon for example methylene dichloride is specially suitable solvent, and pyridine is an alkali preferably, and reaction can be carried out between-50 ℃ to 100 ℃ easily, is preferably in 0 ℃.
The compound of formula III, compound that can through type (V):
Figure 86106933_IMG10
R wherein, R 1, and R 3Define Y and Y as the front 1Be oxygen, Z is CH 2OH, in the presence of highly basic such as potassium hydroxide and diethyl carbonate react and make.Be reflected in polar solvent such as the ethanol and carry out, temperature of reaction is higher, for example between 50 ℃ to 100 ℃.This is preparation formula III compound (R wherein 1=R 14=CF 3) method preferably.
In addition, the formula III compound also can pass through Grignard reagent R 1The compound of mgX and formula VI
Figure 86106933_IMG11
React and make.Here R, R 1And R 3Define as the front, X represents for example bromine or iodine of halogen atom.Reaction can be at inert solvent, and suitable is to carry out in ethers such as the ether, and is normal in the temperature of reaction, for example between-50 ℃ to 50 ℃, is preferably between-10 ℃ to 10 ℃.The compound of formula VI can be by the compound of formula III (R wherein 14Being hydrogen) oxidation makes.Oxidation can as halogenated hydrocarbon, for example be reacted in the methylene dichloride with oxalyl chloride and methyl-sulphoxide at a kind of inert solvent, then with alkali triethylamine for example.Perhaps, in halogenated hydrocarbon, for example methylene dichloride, carry out oxidation with pyridinium chloro-chromate at inert solvent.
The compound of formula III (R wherein 14Be hydrogen) can be by the compound of formula (V), according to being similar to the logical formula III compound of preparation (R wherein 14Be trifluoromethyl) method prepare.
Formula (V) triol can prepare by following method:
(ⅰ) in some cases, can be by the ester of the compound of formula (VII):
Figure 86106933_IMG12
Reduction and make the derivative of triol easily, wherein R 1, R 3Be hydrogen, one in the hydroxyl is protected.R 15Be hydroxyl protecting group such as benzyl, R 16Be C 1-4Alkyl.The most handy a kind of hydrogenation mixture of this reduction such as lithium aluminium hydride are carried out in inert solvent such as ether easily.The compound of formula (VII) can be by corresponding compounds RCH(CO 2R 16) 2With compounds X CH 2OR 15React in the presence of highly basic such as sodium hydride and make, X is a leavings group here, for example halogen.
(ⅱ) as the compound of a formula I of needs preparations (R wherein 3Be hydrogen), available compound with general formula (VIII):
Figure 86106933_IMG13
(R wherein, R 1, and R 16Define as the front) reduction and get.This reduction reaction can at inert solvent such as ethers, for example be carried out in the ether with a kind of hydrogenation mixture such as lithium aluminium hydride.
As R and R 1When being connected to form a carbocyclic ring, formula (VIII) compound can be easily by the compound and the X-CO of formula (IX) 2R 16The reaction and make:
Figure 86106933_IMG14
Here R, R 1And R 16Define as the front, X represents halogen such as chlorine.This reaction can at a kind of inert solvent such as ethers, for example be carried out in the tetrahydrofuran (THF) in the presence of Grignard reagent such as ethylmagnesium bromide easily.Other compound of formula (VIII) can pass through compound R CH(COOR 16) 2With compounds X COR 1Or trifluoroacetic anhydride (TFAA) reaction and making easily, R here, R 1, R 16Define with X such as front.This is reflected at highly basic such as metal hydride exists down, at non-polar solvent such as aromatic hydrocarbon, for example can carry out easily in benzene or the toluene.
-C ≡ C-R 5The locational iodide that contain of base also can be by corresponding bromide preparation.Can for example react in the ether with bromide and alkyl lithium compounds such as n-Butyl Lithium at inert solvent such as ethers for this reason.Normal in the temperature of reaction, for example between-80 ℃ to 20 ℃, can between-70 ℃ to 0 ℃, carry out easily, obtain corresponding lithium intermediate, again at inert solvent such as ethers, for example get final product with Iod R in the ether.Above-mentioned reaction can be easily a step carry out and the organolithium intermediate that need not to isolate.
Bromine compounds can be got by the compound cyclization of formula II, wherein R 2XBe the phenyl that bromine replaces, reaction conditions is identical with the condition of the corresponding iodine compound of above-mentioned preparation.In addition, can also following method make, that is, and can be by a compound that is similar to formula (V) (R wherein, R 1, R 3, Y, Y 1Identical with Z with the definition in the formula I), it and formula R 2XC(OR 17) 3Original carboxylic acid ester reaction, R here 2XBe the bromo phenyl, R 17Be C 1-4Alkyl, phenyl or C 7-8Arylalkyl.Suitable R 17Be methyl or ethyl, preferably methyl.Reaction is carried out in the presence of a kind of acid, for example mineral acid usually, can select hydrochloric acid, sulfonic acid for example toluenesulphonic acids or a kind of acidic resins easily for use, or in the presence of trialkylamine such as triethylamine, carry out, temperature of reaction is higher, for example between 50 ℃ to 200 ℃, can select for use easily between 120 ℃ to 170 ℃.Reaction can be not easily be carried out under the situation of solvent having, and if desired, can add a kind of suitable solvent yet.The preparation method of the two ring benzene alkane that this class bromophenyl replaces can be referring to the european patent application book NO152229 that has announced and our pending application book (N:40934(P5/6/15) and N:41116(P7/12)), these all have been incorporated in the reference paper of the present invention.
Work as R in (ⅱ) formula I compound 5When being hydrogen, also can be by corresponding 1, the dehydrobromination of 2-bromotrifluoromethane compound reacts and prepares, and promptly uses a kind of compound, R wherein 2By the displacement of (1, the 2-bromotrifluoromethane) phenyl.This reaction can be carried out in liquefied ammonia in the presence of sodium amide easily, and reaction also can be carried out in a kind of inert solvent such as ethers, for example tetrahydrofuran (THF), and at this moment temperature of reaction is normal in being, for example between-20 ℃ and 50 ℃, also can carry out easily in room temperature.
(ⅲ) formula I compound often can make by other mutual conversion that also has the compound of formula I easily, for example:
(ⅰ) R in the formula I compound of wanting to prepare 5When being not hydrogen, available corresponding formula I compound, R wherein 5Be hydrogen, go and R 5The X reaction, X is a halogen here, and R 5Not hydrogen.This reaction is particularly suitable for preparing those R 5Be C 1-4Alkyl or-COR 6The formula I compound of base, R here 6Be C 1-6Alkoxyl group.Reaction usually in the presence of highly basic such as lithium alkylide (can select butyllithium easily for use), in a kind of inert solvent such as ethers, for example tetrahydrofuran (THF), in normal temperature as-50 ℃ to 50 ℃ between (can select-10 ℃ to 30 ℃ easily for use) carry out.Used raw material, promptly unsubstituted alkynyl phenyl bicyclic alkane can be by the method preparation of top narration.
(ⅱ) R in the formula I compound of wanting to prepare 5When being hydrogen, available corresponding formula I compound, R wherein 5Be three C 1-4The alkane silyl takes off alkyl silyl reaction and makes.The known method of those of skill in the art is carried out in available professional domain of this reaction, for example use tetrabutyl ammonium fluoride at ethers, as tetrahydrofuran (THF) in, between middle normal temperature is as 0 ℃ to 70 ℃ or can at room temperature react easily.
The formula I compound can be used to control the procreation of arthropods such as insect and mite class.By this, the invention provides the arthropodan method of a kind of control, promptly to arthropods or the environment that their are multiplied is used arthropods is the formula I compound of significant quantity.The present invention also provides a kind of control and/or eradicates the arthropodan method of multiplying animal (comprising the people) on one's body, promptly animal is used the formula I compound of significant quantity, and then the invention provides into controlling the purpose of segmental appendage class insect, for people and the medicinal compound of beasts with formula I.
When using the formula I compound for the purpose of this class, can be directly with these compounds itself, also can be in the known manner with their formulation after dilution, such as preserved material, sprays, glued membrane agent, foaming agent, pulvis, powder, aqeous suspension, paste, gel, shampoo, finish, Flammable Solid Class 4.1, gasification disperse that agent, combustibility are coiled, poison bait, wettable powder, granule, aerosol, emulsible concentrated solution, oil suspension, oil solution, tamponade thing, through the article of soup infiltration or pour into prescription.The preserved material concentrated solution can not directly use, and needs first dilute with water, allows animal be immersed in then and is equipped with in this dipping bath that embathes liquid.Sprays can be with hand or by means of atomizer.Animal, plant or pending surface can the large volume drug administrations and saturated spraying, also can be slightly or the ultra-small volume drug administration, only slightly spray on the top layer.The usage of aqeous suspension is identical with preserved material or sprays.Pulvis can be with duster, when medication during in animal, can be contained in pulvis in the sack that is installed with quite a lot of eyelets, sack is hung in the tree or on the fence.Paste, shampoo and finish can be manipulation, or it is dispersed in a kind of surface of inert material, medicine transferred to its skin when animal and its friction.Pouring into prescription is the unit liquid packaging that is divided into low capacity, and it once is poured on the back of animal, and liquid all or major part all is retained on one's body the animal.
The formula I compound can be mixed with the prescription that can be directly used in animal, plant or surface, also can be mixed with needs the prescription that dilutes before the dispenser, but the mixture behind the thorough mixing that two kinds of formulations all are formula I compound and one or more carriers or thinner.Carrier can be liquid, solid or gas, or the mixture of this class material, and whether needs further dilute according to filling a prescription, and formula I compound concentration therein is from 0.025% to 99%W/V(weight/volume).
Contained formula I compound in pulvis, powder and granule, be and a kind of powdery solid inert support, suitable for mixture fully such as clay, kaolin, talcum powder, mica, white dirt, gypsum, plant vector, starch, diatomite.
The sprays of formula I compound, be a kind of solution that in organic solvent (as following listed those), forms, or in this professional domain by the water colour emulsion (for embathing or hydro-peening) of a kind of emulsible concentrated solution (otherwise be called can be miscible fluid) preparation with water, it also can be used for the purpose of embathing.This concentrated solution is with or without the mixture that a kind of organic solvent and one or more emulsifying agents are formed preferably by active constituent.Solvent can in wide range, change but preferably account for composition 0 to the 90%W/V(weight/volume), select in other solvent that solvent for use can be used from kerosene, ketone, alcohols, dimethylbenzene, aromatic series petroleum naphtha and prescription field.The concentration of emulsifying agent can change in wide range, but preferably 5% to the 25%W/V(weight/volume) in the scope.Used emulsifying agent can be selected nonionic surface active agent easily for use, comprise the polyglycol ether of alkylphenol and the polyoxyethylene deriv of hexitan, and anion surfactant, comprise the sodium salt and the calcium salt of sodium laurylsulfonate, Fatty Alcohol(C12-C14 and C12-C18) sulfonic acid ether, alkyl aryl sulphonic acid and alkyl sulfo-succinic acid.
But the wet-milling pulvis comprises a kind of inert solid carrier, and one or more tensio-active agents can also have stablizer and/or oxidation inhibitor in addition.
Emulsible concentrated solution comprises emulsifying agent, and a kind of organic solvent such as kerosene, ketone, alcohols, dimethylbenzene are usually arranged, aromatic series petroleum naphtha and other solvent as known in the art.
Wettable powder and emulsible concentrated solution contain the active ingredient of 5% to 95% weight percentage usually, and (as water) is its dilution before use.
The glued membrane agent comprises the solution that active constituent forms in a kind of organic solvent, and resin and softening agent.
Embathing liquid not only can be by emulsible concentrated solution preparation, also can be by wettable powder, with preserved material and aqeous suspension is that the soap of matrix prepares, and this preserved material and aqeous suspension are formed by formula I compound and dispersion agent and one or more tensio-active agent thorough mixing.
The aqeous suspension of formula I compound is the suspension that it forms with suspension agent, stablizer or other reagent in water.This suspension or solution can directly be used, and use after also can making diluent in the known manner again.
Finish (or ointment) can be made together by vegetables oil, synthetic fatty acid ester or lanolin and a kind of inert base such as Vaseline.The formula I compound preferably is evenly dispersed in the mixture in solution or the suspension.Finish also can be by emulsible concentrated solution by making with the dilution of ointment matrix.
Paste and shampoo also are semisolid preparations, and wherein the formula I compound can be evenly dispersed in a kind of suitable matrix such as Vaseline or the white oil, also can be dispersed in a kind of non-greasing base such as glycerine, viscose glue or a kind of suitable soap.Because finish, shampoo and paste be not further dilution in use usually, so the formula I compound that is suitable for treating the percentage composition that needs should be arranged in them.
Aerosol can be made the simple solution of active constituent in aerosol propellant and secondary solvent such as halogenated alkane, used solvent referring to foregoing those.Pour into prescription and can be made into solution or the suspension of formula I compound in liquid medium.A bird or mammiferous host, also can by means of with on flooding formula I plastics compound, that cast suitable shape and reaching the purpose that prevents the parasitic procreation of acarian.This based article comprises necklace, hoop, band mo(u)lding, the cover list of the soup that infiltrated, slat etc., and they can be fixed to the suitable position of animal body.Suitable plastic has polyvinyl chloride (PVC).
The formula I compound concentrations that is used for animal, will be according to the character of selected pitch time with compound, medication, prescription and situation about spreading and decide, but generally in prescription, should account for 0.001% to 20.0%W/V(weight/volume), preferably in the prescription 0.01% to 10% formula I compound is arranged.Be deposited on the amount of the animal formula I compound on one's body multiple and the character of prescription and changing will be along with the concentration of compound (I) in application method, animal size, the used prescription, prescription dilution the time, but it is general in 0.0001% to 0.5% scope, only some undiluted prescriptions are as pouring into prescription, its deposition concentration generally between 0.1% to 20.0%, is preferably between 0.1% to 10%.
The formula I compound also can be used for the prevention and the treatment of insect pest of the plant, promptly imposes desinsection or to kill mite be the active constituent of effective dose.The dispenser rate will change along with selected concrete formula I compound, the character of prescription, the mode of dispenser, the kind of plant, the density of plant, situation about spreading and other factors, but in general, to the dispenser rates of farm crop in 0.001 to 3 kilogram of/hectare scope, preferably in 0.01 to 1 kilogram of/hectare scope.Contain the formula I compound between 0.0001% to 50% in the representative formula for the agricultural use, also can select the prescription of the content of formula I compound easily for use in 0.1 to 15% weight percentage.
Concrete farm crop comprise cotton, wheat, corn, rice, Chinese sorghum, soybean, grape, tomato, potato, fruit tree and dragon spruce.
The prescription of dust agent, finish, paste and aerosol is usually with the top various mode dispensers of saying.The formula I compound concentrations can be selected 0.001% to 20%W/V(weight/volume for use in these prescriptions).
Found that the formula I compound has anti-house fly effect.In addition, some compounds with logical formula I also have activity to other segmental appendage class pest, comprise cotton spider mites, diamond-back moth, culex and blatta germanica.Therefore the formula I compound is being useful aspect the procreation of control segmental appendage class insect and acarian, and it can be used for having in any environment that these insects haunt, such as agricultural, livestock industry, public health control and home environment etc.
Harmful insect comprises that some members of Coleoptera (belong to as death watch beetle, Tribolium, grain weevil belongs to, the chrysomelid genus of cucumber strip, flower resembles genus, or Anthrenus, lepidopteran (belongs to as meal moth, Plutella, straw borer spp, Heliothis, Spodoptera or curtain rain moth belong to), Diptera is (as Musca, Aedes, Culex, Glossina, Stomoxys, the east horn fly belongs to, Gadfly, Hydrotaea, Lucilia, Carysomyia, Callitroga, the skin fly belongs to, Hypoderma, liriomyza bryoniae belongs to, and Melophagus), Anoplura, Mallophaga: belong to as Damalinia and Anoplura, as Linognathus, Haematopinus, Hemiptera is (as Aphis, uncle's Aleyrodes, Aleyrodes, or bedbug), Orthoptera (belonging to or deceive cricket spp) as desert locust, Neuroptera (belongs to as Ji Lian, Periplaneta, or
Figure 86106933_IMG15
Lian belongs to), Hymenoptera (belonging to) as Solenopsis, honey ant, Isoptera (as Reticulitermes) Siphonaptera (belonging to) Thysanura (belonging to) as silverfish as Ctenocephalus or flea, Dermaptera (belonging to) as ball Sou, and Pscoptera order such as Peripsocus mite pest comprise following each some member that belong to of acarina: Boophilus, Rh, Amblyomma, Hyalomma, hard tick genus, Haemaphysalis, Anocentor and some mite classes and sarcoptic mite such as Tetranychus, Psoroptes, Notoedres, Psoroptes and Demodex.
The compounds of this invention can with mixing such as one or more other active ingredients (for example pyrethroid, carbamate, Organophosphonate etc.) and/or attractive substance.Find also that in addition the activity of The compounds of this invention can strengthen with adding synergistic agent or reinforcer, for example, a kind of synergistic agent of oxidase inhibitor class such as piperonyl butoxide or 2-propynyl phenyl-phosphonic acid propyl ester; Or add second compound among the present invention; Or a kind of pyrethroid Pesticidal compound.When having oxidase inhibitor class synergistic agent in the prescription of the present invention, synergistic agent in 25: 1 to 1: 25 scopes, or approximately is 10: 1 to the ratio of formula I compound.
The stablizer that adds for the contingent any chemical degradation of compound that prevents among the present invention, comprise that oxidation inhibitor is (as tocopherol, butyl hydroxyanisole and butylhydroxy toluene) and scavenging agent (as 3-chloro-1, the 2-propylene oxide), organic or inorganic alkali, for example trialkylamine such as triethylamine also can be used as stablizer and scavenging agent.
The following examples have been explained example preferably of the present invention, but the present invention is not limited to the scope described in these examples.Temperature in the experiment all refers to ceslius scale.
Example 1
4-ethyl-1-(the trimethyl silicon based ethynyl of 4-(2-)-phenyl)-2,6,7-trioxa two ring (2,2,2) octanes
(ⅰ) 2-ethyl-2-methylol-1; (its preparation method is similar to preparation 2-n-propyl-2-methylol-1 to ammediol (13.4 gram); ammediol; example 3(ⅰ)) diethyl carbonate (12; 3 milliliters); the reaction mixture that potassium hydroxide (0.1 gram) is formed in dry ethanol (1 milliliter) is heated to leniently under the nitrogen gas stream protection and refluxes, and heats 30 minutes (oil bath temperature 110-120 ℃).(oil bath temperature 130-140 ℃ of the ethanol of formation is removed in distillation under atmospheric pressure after the reaction, head temperature is no more than 76 ℃), 20mm mercury column then reduces pressure, and oil bath temperature is adjusted to 230 ℃, can steam 3-ethyl-3-methylol-trimethylene oxide, be colourless liquid (9.1 grams, 150 ℃ of head temperature).
(g, l.c): the OV-210 post peak occurs at 100 ℃ to gas-liquid chromatograph.
Nuclear magnetic resonance spectrum (N.M.R) data are as follows: ' H(is followed successively by with TMS and makes interior mark, and solvent is CDCl 3Chemical displacement value p.p.m, the corresponding H number of integrated value, the division number at peak, and coupling constant fourth value the hertz number): 4.40,4H, S; 3.70,2H, m; 1.7,2H, q, 8; 0.9,3H, t, 8.
(ⅱ) at 0 ℃, 4-iodobenzene formyl chloride (11.5 gram) formed solution in dry ether (50 milliliters), be added in the solution that the 3-ethyl-3-methylol-trimethylene oxide (5 gram) that stirring and pyridine (3.5 milliliters) form in ether (100 milliliters).The reaction mixture that obtains is warmed to room temperature and stirred 24 hours.Water and salt solution wash this mixture then.Organic extracting solution anhydrous magnesium sulfate drying, concentrating under reduced pressure.Resistates is purified by silicagel column (with the pre-wash-out of hexane that contains 1% triethylamine), with the hexane wash-out that contains 5% ethyl acetate.Obtain 3-ethyl-3-(4-iodobenzene methanoyl methyl) trimethylene oxide colorless oil (8.1 gram).
Nuclear magnetic resonance spectrum (N.M.R) data are as follows: it is CDCl that ' H(is followed successively by with mark, solvent in the TMS work 3Chemical displacement value p.p.m, the corresponding H number of integrated value, the division number at peak, and coupling constant fourth value the hertz number): 7.60,4H, S; 4.60-4.35,6H, m; 1.8,2H, q, 8; 0.95,3H, q, 8.
(ⅲ) under-70 ℃ and nitrogen, boron trifluoride etherate (0.44 milliliter) being added to 3-ethyl-3-(4-iodobenzene methanoyl methyl) trimethylene oxide (4.9 gram) is in the solution of exsiccant methylene dichloride (30 milliliters).The reaction mixture that obtains is warming to room temperature and stirred 20 hours.Add triethylamine (2 milliliters) then.Reaction mixture washes with water, organic layer Anhydrous potassium carbonate drying, concentrating under reduced pressure then.Resistates is purified with alumina column layer folding, and the methylene dichloride that contain 40% hexane saturated with ammonia comes wash-out.Obtain 4-ethyl-1-(4-iodophenyl)-2,6,7-trioxa two ring (2,2,2) octane white solids (2.9 gram)
Gas-liquid chromatograph (g.l.c): OV-210 obtains a peak at 230 ℃.
Nuclear magnetic resonance spectrum (N.M.R) data are as follows: it is CDCl that ' H(is followed successively by with mark, solvent in the TMS work 3Chemical displacement value p.p.m, the corresponding H number of integrated value, the division number at peak, and coupling constant fourth value the hertz number): 7.60,2H, d, 8; 7.30,2H, d, 8; 4.05,6H, S; 1.5-0.7,5H, m.
(ⅳ) under nitrogen, two-triphenylphosphine palladium chloride (60 milligrams) and cuprous iodide (10 milligrams) are added to the 4-ethyl-1-(4-iodophenyl of stirring)-2,6,7-San Yang Evil two rings (2,2,2) octane is in (1.5 gram) and the solution of trimethyl silicane ethyl-acetylene (0.92 milliliter) in exsiccant diethylamine (40 milliliters).The mixture that obtains was stirring at room 16 hours.Under reduced pressure boil off solvent then, the resistates ether extraction, ethereal solution washes with water, uses anhydrous magnesium sulfate drying, concentrating under reduced pressure.Resistates is purified with alumina column chromatography, with the saturated hexane wash-out that contains 30% methylene dichloride of ammonia.In hexane, obtain 4-ethyl-1-(the trimethyl silicon based ethynyl of 4-(2-)-phenyl again behind the recrystallization)-2,6,7 trioxas two ring (2,2,2) octanes (1.2 gram) pale solid.
Gas-liquid chromatograph (g.l.c.): the OV-210 post 230 ℃ one unimodal.
Use aforesaid method, selecting suitable aryl iodide and trimethyl silicane ethyl-acetylene is raw material, has prepared following compounds:
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-ethyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-normal-butyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-tertiary butyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 3-(2-) phenyl)-and 4-tertiary butyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-isobutyl--2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-n-pentyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 3-chloro-4-(2-) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 3-nitro-4-(2-) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-phenyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-cyclohexyl-2,6,7-trioxa two ring (2,2,2) octanes
Used raw material 3-chloro-4-iodo-benzoic acid and 3-nitro-4-iodo-benzoic acid are to prepare according to the method for Hodgson and Beard (referring to J.Chem.Soc., 1927,20).
Example 2
3-(4-(4-ethyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl)-the 2-ethyl propiolate
(ⅰ) tetrabutyl ammonium fluoride solution (3.3 milliliters 1M tetrahydrofuran solutions) is added to 1-(the trimethyl silicon based ethynyl of the 4-(2-)-phenyl that is stirring)-4-ethyl-2,6,7-trioxa two rings (2,2,2)-solution of octane (0.87 gram) in tetrahydrofuran (THF) (15 milliliters) in, mixture subtracts after 30 minutes in stirring at room and boils off solvent, and resistates is transferred in the ether, water and salt solution washing.The ethereal solution anhydrous magnesium sulfate drying, concentrating under reduced pressure obtains the 1-(4-ethynyl phenyl with the hexane recrystallization)-4-ethyl-2,6,7-trioxa two ring (2,2,2) octanes, off-white color solid (0.66 gram).
Gas-liquid chromatograph (g.l.c.): the OV-210 post produces a peak at 230 ℃.
Nuclear magnetic resonance spectrum (N.M.R) data are as follows: it is CDCl that ' H(is followed successively by with mark, solvent in the TMS work 3Chemical displacement value p.p.m, the corresponding H number of integrated value, the division number at peak): 7.50,4H, m; 4.1,6H, S; 3.1,1H, S; 1.6-0.7,5H, m.
(ⅱ) under 0 ℃ and nitrogen, n-butyllithium solution (0.67 milliliter, the solution of 1.6M in hexane) is added to the 1-(4-ethynyl phenyl that is stirring)-4-ethyl-2,6, in the solution of 7-trioxa two ring (2,2,2) octanes (200 milligrams) in tetrahydrofuran (THF) (5 milliliters).Solution kept 10 minutes at 0 ℃, added purified Vinyl chloroformate (0.1 milliliter) then, and solution slowly was warming to room temperature in 1.5 hours.Add entry (1 milliliter) reaction terminating, removal of solvent under reduced pressure, resistates are transferred in the ether, water and salt water washing.Ethereal solution anhydrous magnesium sulfate drying, concentrating under reduced pressure then.Resistates ebullient hexane extraction, cooling obtain 3-(4-(4-ethyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl)-the 2-ethyl propiolate, canescence crystalline solid.
Gas-liquid chromatograph (g.l.c.): the OV-17 post produces a peak at 230 ℃.
With the method described in above-mentioned (ⅰ), make raw material with the suitable trimethyl silicon based ethynyl analogue that makes in the example 1, can prepare following compounds:
The 1-(4-ethynyl phenyl)-and 4-ethyl-2,6,7-trioxa two ring (2,2,2) octanes
The 1-(4-ethynyl phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
The 1-(4-ethynyl phenyl)-and 4-normal-butyl-2,6,7-trioxa two ring (2,2,2) octanes
The 1-(4-ethynyl phenyl)-and 4-isobutyl--2,6,7-trioxa two ring (2,2,2) octanes
The 1-(4-ethynyl phenyl)-and 4-n-pentyl-2,6,7-trioxa two ring (2,2,2) octanes
The 1-(4-ethynyl phenyl)-and 4-(2, the 2-dimethyl propyl)-2,6,7-trioxa two ring (2,2,2) octanes
1-(3-
Figure 86106933_IMG16
-4-ethynyl phenyl)-and 4-n-propyl-2,6,7 ， trioxas, two ring (2,2,2) octanes
1-(3-nitro-4-ethynyl phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
The 1-(4-ethynyl phenyl)-and 4-phenyl-2,6,7-trioxa two ring (2,2,2) octanes
The 1-(3-ethynyl phenyl)-and 4-tertiary butyl-2,6,7-trioxa two ring (2,2,2) octanes
The 1-(4-ethynyl phenyl)-and 4-tertiary butyl-2,6,7-trioxa two ring (2,2,2) octanes
With the method described in above-mentioned (ⅱ), by the 1-(4-ethynyl phenyl)-4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes and
Figure 86106933_IMG17
Methyl-formiate has synthesized 3-(4-(4-ethyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl)-2-propynoic acid methyl esters.
The NMR data of these products all in the table of back, unlisted 1-(3-ethynyl phenyl in the table)-4-tertiary butyl-2,6,7-trioxa two ring (2,2,2) octanes, its NMR spectrum data are as follows: mark, solvent were CDCl in ' H(was followed successively by and does with TMS 3Chemical displacement value p.p.m, the corresponding H number of integrated value, the division number at peak): 7.75-7.20,4H, m; 4.15,6H, S; 3.0,1H, S; 0.90,9H, S.
Example 3
1-(4-(3-methoxyl group propine-1-yl)-phenyl)-and 4-propyl group-2,6,7-trioxa two ring (2,2,2) octanes
(ⅰ) in the mixture of valeraldehyde that is stirring (172 gram) and water (2 liters), add solid hydrogen calcium oxide (112 gram) and formaldehyde solution (1.4 liter 40% the aqueous solution).Temperature of reaction maintains below 40 ℃, adds calcium hydroxide and about 45 minutes required of time of formaldehyde, and reaction mixture was kept 5 hours at 60 ℃ then.Reaction solution is passed through diatomite filtration, and filtrate decompression concentrates, and resistates is handled with hot methanol (2 liters), and mixture is again through diatomite filtration, and filtrate decompression concentrates, and gets a heavy-gravity oily matter (458 gram), purifies by following operation:
With the solution of crude product and acetic acid (200 milliliters) in stirring at room, add aceticanhydride (1.2 liters) in 4 hours, temperature rises to 65 ℃, continues to stir 12 hours, under agitation reaction mixture slowly was added in 3 hours in the water (3 liters), and continues to stir 3 hours.The aqueous mixture ether extraction, extracting solution washs one by one with sodium bicarbonate aqueous solution and salt solution, uses anhydrous magnesium sulfate drying, then concentrating under reduced pressure.
Distillation promptly gets 2-n-propyl-2-methylol-1.3-propylene glycol triacetate (238 gram), colorless oil.(boiling point 120-140 ℃/1.5mm).
Nuclear magnetic resonance spectrum (NMR) data are as follows: ' H(is followed successively by with TMS and makes interior mark, and solvent is CDCl 3Chemical displacement value p.p.m, the corresponding H number of integrated value, the division number at peak): 4.00,6H, S; 2.10,9H, S; 1.40,4H, m; 1.00,3H, m.
Sodium (0.5 gram) is added in the solution of above-mentioned triacetate (238 gram) in methyl alcohol (2.5 liters) that is stirring, and mixture refluxes and stirred 72 hours.Concentrating under reduced pressure then.
Obtain 2-n-propyl-2-methylol-1.3-propylene glycol (87 gram) colourless crystallization (93 ℃ of fusing points)
Consult W.E.Conrad, L.A.Levasseur, R.F.Murphy, N.L.Hare and H.E.Conrad, the J.Org.Chem magazine was rolled up the 2227th page in 1962 the 27th.
With the similar approach of above-mentioned Synthetic 2-n-propyl-2-methylol-1.3-propylene glycol, can prepare corresponding 2-normal-butyl-2-methylol-1.3-propylene glycol and 2-n-pentyl-2-methylol-1.3-propylene glycol by n-hexyl aldehyde and enanthaldehyde respectively.
With Synthetic 2-(2, the 2-dimethyl propyl)-and the method (seeing example 5) of 2-methylol-1.3-propylene glycol, can prepare corresponding 2-cyclohexyl-2-methylol-1.3-propylene glycol and 2-isobutyl--2-methylol-1.3-propylene glycol by cyclohexyl diethyl malonate and iso-butyl diethyl malonate respectively.
2-tertiary butyl-2-methylol-1.3-propylene glycol can be according to Y.Ozoe and M.Eto at Agric.Biol.Chem., and magazine nineteen eighty-two the 46th volume 411-8 page or leaf method makes.
(ⅱ), can make the 1-(4-iodophenyl by 2-n-propyl-2-methylol-1.3-propylene glycol and 4-iodobenzene formyl chloride with the described method of step (ⅰ)-(ⅲ) in the example 1)-4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes.
Gas-liquid chromatograph (g.l.c.): the OV-210 post presents a peak at 230 ℃.
Nuclear magnetic resonance spectrum (N.M.R) data are as follows: it is CDCl that ' H(is followed successively by with mark, solvent in the TMS work 3Chemical displacement value p.p.m, the corresponding H number of integrated value, the division number at peak, and the He Zhi number of coupling constant fourth value): 7.65,2H, d, 8; 7.30,2H, d, 8; 4.1,6H, S; 1.5-0.8,7H, m.
(ⅲ) be added to the 1-(4-iodophenyl that is stirring at following two-triphenylphosphine palladium chloride (15 milligrams) of nitrogen and cuprous iodide (5 milligrams))-4-n-propyl-2,6,7-trioxa two rings (2,2,2) in octane (0.25 gram) and the solution of methyl propargyl ether (0.09 milliliter) in exsiccant diethylamine (5 milliliters).The mixture that obtains at room temperature stirred 20 hours.Pressure reducing and steaming solvent then, the resistates ether extraction.Ethereal solution washes with water, with anhydrous magnesium sulfate drying, concentrating under reduced pressure.Resistates is purified with alumina column chromatography, with the saturated hexane wash-out that contains 30% methylene dichloride of ammonia.Behind the hexane recrystallization, obtain 1-(4-(3-methoxyl group-propine-1-yl) phenyl)-4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes, pale solid (67 milligrams).
Gas-liquid chromatograph (g.l.c.): the OV-17 post presents a peak at 240 ℃.
Use similar method, by the 1-(4-iodophenyl)-4-n-propyl-2,6,7-trioxa two ring (2,2,2) octane and various acetylene-derivatives (specified in the bracket) have prepared following compounds:
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes (trimethyl silicane ethyl-acetylene)
3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) octyl groups) phenyl)-third-2-alkynes-1-alcohol (propargyl alcohol)
1-(4-(2-phenylacetylene base) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes (phenylacetylene)
1,1-dimethyl-3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl)-third-2-alkynes-1-alcohol (1,1-dimethyl propylene-2-alkynes-1-alcohol)
4-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) octyl groups) phenyl) fourth-3-alkynes-1-alcohol (fourth-3-alkynes-1-alcohol)
1-(4-(2-tertiary butyl ethynyl) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes (3,3-dimethyl butyrate-1-alkynes)
Use similar method, by suitable 4-replace-the 1-(4-iodophenyl)-2,6,7-trioxa two ring (2,2,2) octanes and corresponding acetylene-derivative (specified in the bracket) have prepared following compounds:
1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-and 4-tertiary butyl-2,6,7-trioxa two ring (2,2,2) octanes (methyl propargyl ether)
1-(3-chloro-4(3-methoxy propyl-1-alkynyl) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes (methyl propargyl ether)
1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-and 4-cyclohexyl-2,6,7-trioxa two ring (2,2,2) octanes (methyl propargyl ether)
1-(4-(3-ethoxy-c-1-alkynyl) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes (EPE)
4-methoxyl group-1-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl) fourth-1-alkynes (4-methoxyl group fourth-1-alkynes)
1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-and 4-isobutyl--2,6,7-trioxa two ring (2,2,2) octanes (methyl propargyl ether)
N-(3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl) Propargyl)-and ethanamide (N-Propargyl ethanamide, referring to Chem.Abs., 54 volumes 3178 h)
1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-and 4-normal-butyl-2,6,7-trioxa two ring (2,2,2) octanes (methyl propargyl ether)
1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-and 4-n-pentyl-2,6,7-trioxa two ring (2,2,2) octanes (methyl propargyl ether)
1-(4-(penta-1-alkynyl) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes (penta-1-alkynes)
Example 4
1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-and 3-trifluoromethyl-4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
(ⅰ) sodium hydride (8.0 gram 60% in oil dispersive reagent) is added to the diethyl n-propyl (40 gram) that stirring in dry benzene in the solution of (200 milliliters), the mixture holding temperature stirred 1 hour at 60 ℃.Add trifluoro-acetic anhydride (28 milliliters) carefully after the mixture cooling, reaction mixture was stirring at room 2 hours.Add entry, aqueous reaction mixture ether extraction, the ether extracting solution washes with water, uses anhydrous magnesium sulfate drying, then concentrating under reduced pressure.
Underpressure distillation promptly provides 2-n-propyl-2-trifluoroacetyl group diethyl malonate, and colorless oil (73 ℃ of boiling points/0.2mm), (35 gram).
Gas-liquid chromatograph (g.l.c.): the OV-210 post presents a peak at 130 ℃.
Nuclear magnetic resonance spectrum (N.M.R) data are as follows: 1It is CDCl that H(is followed successively by with mark, solvent in the TMS work 3Chemical displacement value p.p.m, the corresponding H number of integrated value, the division number at peak, and the He Zhi number of coupling constant fourth value): 4.30,4H, q, 8; 2.00,2H, m; 1.50-0.70,11H, m.
(ⅱ) at 0 ℃; under the nitrogen gas stream; be stirred in lithium aluminium hydride in the dry ether (200 milliliters) (5.5 gram) and add the solution of 2-n-propyl-2-trifluoroacetyl group diethyl malonate (25.0 gram) in dry ether (50 milliliters); and with this mixture stirring at room 3 hours, reflux again and stirred 4 hours.(150 milliliters) solution discharges water to add sodium hydroxide (20 gram) and potassium hydrogen phosphate (20 gram) after the reaction mixture cooling carefully.Leach solid and at air drying.Filtrate evaporated under reduced pressure is to doing.Merge all solids, with hot chloroform extraction 48 hours (using the Sha Shi extractor).The extracting solution concentrating under reduced pressure obtains 3.3-two (methylol)-1,1, the 1-trifluoro oneself-oily matter (11.0 gram) of the yellow thickness of 2-alcohol, needn't further purify and can use.
Infrared spectra (IR), liquid film:
3340(is strong and wide), 1155(is strong), 1100(is strong), among the 1040(), among the 1020()
Nuclear magnetic resonance spectrum (NMR) data are as follows: 1It is CDCl that H(is followed successively by with mark, solvent in the TMS work 3Chemical displacement value p.p.m, the corresponding H number of integrated value, the division number at peak): 4.20,1H, m; 4.00-3.10,7H, m; 1.30,4H, m; 0.90,3H, m.
(ⅲ) under nitrogen gas stream, 3,3-two (methylol)-1,1, the 1-trifluoro oneself-110 ° of mixture reflux oil baths in 30 minutes leniently that 2-alcohol (2.8 gram), diethyl carbonate (1.6 milliliters), potassium hydroxide (0.1 gram) and dry ethanol (4.0 milliliters) are formed, distill and remove ethanol, redistillation promptly obtains 3-(1-hydroxyl-2,2, the 2-trifluoroethyl)-3-n-propyl-trimethylene oxide (1.7 gram), colorless oil.(112 ℃ of boiling points/20-25mm)
Gas-liquid chromatograph (g.l.c.): the OV210 post presents a peak at 120 ℃.
Infrared spectra (IR) (liquid film):
3450(is strong, wide), 1300(is strong), 1170(is strong), 1130(is strong), 1045(is strong).
(ⅳ) at 0 ℃ the solution of 4-iodobenzene formyl chloride (2.1 gram) in exsiccant methylene dichloride (25 milliliters), be added to the 3-(1-hydroxyl-2 that is stirring, 2, the 2-trifluoroethyl)-3-n-propyl-trimethylene oxide (1.55 gram) and the solution of pyridine (1.0 milliliters) in the exsiccant methylene dichloride in, reaction mixture was stirring at room 24 hours.In reaction mixture impouring water, aqueous mixture ether extraction.The ether extracting solution washes with water, uses anhydrous magnesium sulfate drying, concentrating under reduced pressure, and resistates is purified with silica column layer folding, with the hexane wash-out that contains 1% triethylamine.
Obtain 3-(1-(4-iodobenzene methanoyl)-2,2, the 2-trifluoroethyl)-3-n-propyl-trimethylene oxide (2.4 gram) colorless oil.
Gas-liquid chromatograph (g.l.c.): the OV210 post presents a peak at 200 ℃.
Nuclear magnetic resonance spectrum (NMR) data are as follows: 1It is CDCl that H(is followed successively by with mark, solvent in the TMS work 3Chemical displacement value p.p.m, the corresponding H number of integrated value, the division number at peak):
7.70，4H，m;4.80-4.20，5H，m;2.20-0.80，7H，m。
(ⅴ) at 70 ℃, boron trifluoride etherate (0.54 milliliter) is added to the 3-(1-(4-iodobenzene methanoyl)-2 that is stirring, 2,2-trifluoroethyl)-solution of 3-n-propyl-trimethylene oxide (2.3 gram) in exsiccant methylene dichloride (50 milliliters) in.The room temperature that mixture is warming at leisure stirred 12 hours then.Add triethylamine (1.0 milliliters), and in the reaction mixture impouring water.Aqueous mixture ether extraction, the ether extracting solution washes with water, uses anhydrous magnesium sulfate drying, then concentrating under reduced pressure.Resistates is purified with alumina column chromatography, uses 1: 4 saturated methylene dichloride of ammonia: the hexane solvent wash-out.
Obtain the 1-(4-iodophenyl)-3-trifluoromethyl-4-n-propyl-2,6,7-trioxa two ring (2,2,2) octane colorless solids (0.53 gram)
Gas-liquid chromatograph (g.l.c.): the OV210 post presents a peak at 220 ℃.
Nuclear magnetic resonance spectrum (N.M.R) data are as follows: 1It is CDCl that H(is followed successively by with mark, solvent in the TMS work 3Chemical displacement value p.p.m, the corresponding H number of integrated value, the division number at peak, and the He Zhi number of coupling constant J value):
7.70，2H，d，8;7.30，2H，d，8;4.80-3.80，5H，m;1.40，4H，m;1.00，3H，m。
(ⅵ) with the method described in the example 3, by the 1-(4-iodophenyl)-3-trifluoromethyl-4-n-propyl-2,6,7-trioxa two rings (2,2,2) octane and methyl propargyl ether have made 1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-2,6,7-trioxa two ring (2,2,2) octanes.
With being similar to synthetic 1-(4-(3-methoxy propyl-1-alkynyl) phenyl) 3-trifluoromethyl-4-n-propyl-2,6, the method of 7-trioxa two ring (2,2,2) octanes, begin by diethyl butylmalonate, 4-normal-butyl-3-Trifluoromethyl-1-(4-(3-methoxy propyl-1-alkynyl phenyl-2,6,7-trioxa two rings (2 have been made, 2,2) octane.
Example 5
1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-and 4-(2, the 2-dimethyl propyl)-2,6,7-trioxa two ring (2,2,2) octanes
(ⅰ) under 0 ℃ and nitrogen, 2, (4.0 restrain 2-dimethyl propyl diethyl malonate (18.8 gram) (referring to Brandstrom Acta.Chem.Scsnd., volume was the 615th page in 1958 the 13rd) to be added to the sodium hydride that is stirring; In 60% the suspension of dispersion agent in exsiccant tetrahydrofuran (THF) (150 milliliters) in oil, mixture refluxes and stirred one hour.Mixture is cooled off, drip benzyl chloride methyl ether (13.3 gram) solution of (50 milliliters) in the exsiccant tetrahydrofuran (THF).Reaction mixture stirs 24 hours then in the impouring cold water.Aqueous mixture extracts with ether, and the ether extracting solution washes with water, uses anhydrous magnesium sulfate drying, removal of solvent under reduced pressure.
Obtain 2-benzyloxymethyl-2-(2, the 2-dimethyl propyl)-diethyl malonate oily matter (28.8 gram), needn't further purify and can use.
(ⅱ) at 0 ℃, under the nitrogen, 2-benzyloxymethyl-2-(2, the 2-dimethyl propyl)-solution of diethyl malonate (15 gram) in exsiccant ether (50 milliliters), be added drop-wise at leisure in the suspension of lithium aluminium hydride (7.0 gram) in exsiccant ether (200 milliliters) that is stirring.Reaction mixture adds aqueous sodium hydroxide solution (25 milliliter 10% solution) carefully stirring at room 12 hours.Mixture is filtered, and solid is washed with ether, and filtrate is used anhydrous magnesium sulfate drying, concentrating under reduced pressure then, and resistates is purified with the silicon-dioxide column chromatography, with 1: 4 ethyl acetate: the hexane wash-out.Obtain 2-benzyloxymethyl-2-(2, the 2-dimethyl propyl)-1, ammediol colorless oil (5.5 gram)
(ⅲ) at-70 ℃, 2-benzyloxymethyl-2-(2, the 2-dimethyl propyl)-1, the solution of ammediol (5.5 gram) in dry ether (50 milliliters) is added in the liquefied ammonia, under agitation adds sodium (2.5 gram), maintains-70 ℃ and continues to stir 1 hour, allow reaction mixture be warming to-30 ℃ then, and add solid ammonium chloride (15 gram) carefully, feed nitrogen gas stream removing deammoniation, and in the reaction solution that is stirring, add methyl alcohol (25 milliliters) to remove residual sodium.Add methylene dichloride (400 milliliters), mixture is filtered.Filtrate decompression concentrates, and obtains 2-(2, the 2-dimethyl propyl)-2-methylol-1, ammediol colorless solid (3.5 gram).
Nuclear magnetic resonance spectrum (NMR) data are as follows: 1It is CDCl that H(is followed successively by with mark, solvent in the TMS work 3Chemical displacement value p.p.m, the division tuple at corresponding H number of integrated value and peak):
4.20,3H, broad peak, available D 2The O exchange; 3.80,6H, S; 1.40,2H, S; 1.20,9H, S.
(ⅳ) the former phenylformic acid trimethyl of 4-bromo-(1.5 gram) (referring to McElv-ain and Venerable J.Amer.Chem.Soc., nineteen fifty the 72nd rolls up the 1661st page and is added to 2-(2, the 2-dimethyl propyl)-2-methylol-1, in the ammediol (1.0 gram), add a concentrated hydrochloric acid, under nitrogen gas stream, 140 ℃ kept 1 hour, and volatile components is removed in decompression (1.0mm) under this temperature.
Resistates is purified with aluminum oxide (Woelm TSC aluminum oxide) column chromatography, and use 1: 20 methylene dichloride of nitrification: the hexane wash-out obtains the 1-(4-bromophenyl)-4-(2, the 2-dimethyl propyl)-2,6,7-trioxa two rings (2,2,2) octane colorless solid (0.70 gram)
Gas-liquid chromatograph (g.l.c.): the OVlol post presents a peak at 250 ℃.
Nuclear magnetic resonance spectrum (NMR) data are as follows: 1H(is followed successively by with TMS and makes interior mark, and solvent is CDCl 3Chemical displacement value p.p.m, the corresponding H number of integrated value, the division number at peak):
7.50，4H，S;4.20，6H，S;1.20，2H，S;1.00，9H，S。
Mass spectrum (M.S.), chemical ionization source:
M+1 peak 341,343
(ⅴ) at-70 ℃, under the nitrogen gas stream, n-Butyl Lithium (hexane solutions of 5.0 milliliters of 1.6M) is added to the 1-(4-bromophenyl that is stirring)-4-(2, the 2-dimethyl propyl)-2,6,7-trioxa two rings (2,2,2) in the solution of octane (0.5 gram) in dry ether (50 milliliters).Reaction mixture is warming to room temperature at leisure.Monitor with vapour-liquid chromatography in the reaction process, when all raw materials have all reacted, in the reaction mixture that is stirring, add the solution of iodine (1.0 gram) in dry ether (50 milliliters).The aqueous solution that adds Sulfothiorine (3 grams are in 40 ml waters) after 10 minutes.Aqueous mixture extracts with ether, and the ether extracting solution washes with water, uses anhydrous magnesium sulfate drying, then concentrating under reduced pressure.Resistates is purified with alumina column chromatography, with 5% saturated methylene dichloride of ammonia: the hexane wash-out.Obtain the 1-(4-iodophenyl)-4-(2, the 2-dimethyl propyl)-2,6,7-trioxa two ring (2,2,2) octane colorless solids.
Nuclear magnetic resonance spectrum (NMR) data are as follows: 1It is CDCl that H(is followed successively by with mark, solvent in the TMS work 3Chemical displacement value p.p.m, the division number at corresponding H number of integrated value and peak):
7.70，2H，d，7;7.35，2H，d，7;4.20，6H，S;1.30，2H，S;1.00，9H，S。
Mass spectrum (M.S.), chemical ionization source:
M+1 peak 389
(ⅵ) with the method described in the example 3, by the 1-(4-iodophenyl)-4-(2, the 2-dimethyl propyl)-2,6,7-trioxa two ring (2,2,2) octanes and methyl propargyl ether have prepared 1-(4-(3-methoxy third-1-alkynyl) phenyl)-4-(2, the 2-dimethyl propyl)-2,6,7-trioxa two rings (2,2,2) octane.
(ⅶ) with the method described in the example 1, by the 1-(4-iodophenyl)-4-(2, the 2-dimethyl propyl)-2,6,7-trioxa two rings (2,2,2) octane and trimethyl silicane ethyl-acetylene have prepared 1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-4-(2, the 2-dimethyl propyl)-2,6,7-trioxa two ring (2,2,2) octanes.
Example 6
3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) octyl groups) phenyl) Propargyl N-methyl carbamate
3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) octyl groups) phenyl) third-2-alkynes-1-alcohol (0.5 gram), methyl isocyanate (0.2 gram) and the solution of triethylamine (0.1 gram) in dry benzene (50 milliliters) refluxed 6 hours.Solution cooling back concentrating under reduced pressure.
Resistates is purified with alumina column chromatography, uses 1: 5 saturated methylene dichloride of ammonia: the hexane wash-out.
Obtain 3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl) Propargyl N-methyl-carbamate colorless solid (0.25 gram, 136.2 ℃ of fusing points).
Example 7
3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl) Propargyl acetic ester
At 0 ℃, under the nitrogen, Acetyl Chloride 98Min. (0.33 milliliter) is added to the 3-that stirring (4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) octyl groups) phenyl) in third-2-alkynes-1-alcohol (1.1 gram) and the solution of triethylamine (0.8 milliliter) in dry ether.Mixture is stirring at room 12 hours then in the impouring water, the water mixture ether extraction, and the ether extracting solution washes with water, uses anhydrous magnesium sulfate drying, concentrating under reduced pressure.
Resistates is purified with alumina column chromatography, uses 3: 2 saturated methylene dichloride of ammonia: the hexane wash-out.
Obtain 3-(4-(4-n-propyl-2,6,7-trioxa two rings (2,2,2) phenyl suffering-1-yl))-Propargyl acetic ester colourless crystallization (0.90 gram, 98.0 ℃ of fusing points) similar methods, from the 1-(4-ethynyl phenyl) 4-n-propyl-2,6,7-trioxa two rings (2,2,2) octane and dimethylcarbamyl chloride and dimethyl sulphide are for urea chloride, prepared corresponding N, N-dimethyl-3-(4-(4-n-propyl-2,6,7-trioxa two rings (2,2,2) phenyl suffering-1-yl))-and third-2-alkynyl amide and N, N-dimethyl-3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl)-third-2-alkynes thioamides.
Example 8
1-(4-(third-1-alkynyl) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
At 0 ℃, under the nitrogen, n-Butyl Lithium (solution of 0.79 milliliter of 1.6M in hexane) is added to the 1-(4-ethynyl phenyl that is stirring)-4-n-propyl-2,6, in the solution of 7-trioxa two ring (2,2,2) octanes (0.25 gram) in the exsiccant tetrahydrofuran (THF).Being reflected at 0 ℃ stirred 10 minutes.Add methyl iodide (90 microlitre), and mixture stirring at room 5 hours.Removal of solvent under reduced pressure.
Add entry, the water mixture ether extraction, the ether extracting solution washes with water, uses anhydrous magnesium sulfate drying, concentrating under reduced pressure.
Obtain 1-(4-(third-1-alkynyl) phenyl)-4-n-propyl-2,6,7-trioxa two ring (2,2,2) octane colourless crystallizations (0.20 gram is by the dichloromethane/hexane recrystallization).
Example 9
1-(4-(3-methoxy propyl-1-alkynyl) phenyl 3-cyano group-4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
(ⅰ) at following 2-n-propyl-2-methylol-1 of nitrogen gas stream protection, ammediol (24.6 gram), diethyl carbonate (20.1 milliliters), the mixture of potassium hydroxide (0.3 restrains) and exsiccant ethanol (2 milliliters) be reflux 30 minutes leniently.Then normal pressure down distillation remove (oil bath temperature 130-140 ℃ of the ethanol of formation, 76 ℃ of head temperature), 20mm mercury column and oil bath temperature is adjusted to 230 ℃ reduces pressure, steam 3-methylol-3-n-propyl trimethylene oxide promptly with colourless liquid shape thing (16.7 grams, column top temperature 120-126 ℃).
Gas-liquid chromatograph (g.l.c): the OV-210 post presents a peak at 120 ℃.
(N.M.R) is as follows for nuclear magnetic resonance data: 1H(is followed successively by with TMS and makes interior mark, CDCl 3Be the chemical displacement value p.p.m of solvent, the division number at corresponding H number of integrated value and peak):
4.35，4H，S;3.60，2H，m;1.8-0.7，7H，m。
(ⅱ) at-70 ℃, under the nitrogen,, be added in the solution of oxalyl chloride (7.4 milliliters) in methylene dichloride (25 milliliters) that is stirring the solution of methyl-sulphoxide (12 milliliters) in dry methylene chloride (4.0 milliliters).After adding, reaction mixture was-70 ℃ of restir 5 minutes.In 10 minutes, drip the solution of 3-methylol-3-n-propyl trimethylene oxide (10.0 gram) in methylene dichloride (25 milliliters) then.The reaction mixture restir that obtains 30 minutes added purified triethylamine (54 milliliters) then in about 30 minutes.Reaction mixture slowly was warmed up to room temperature in 3 hours, in its impouring water, tells organic phase then, water layer further extracts with fresh methylene dichloride.The organic extracting solution that merges washs one by one with dilute hydrochloric acid, saturated sodium bicarbonate and salt solution, the organic phase anhydrous magnesium sulfate drying of washing, and concentrating under reduced pressure promptly obtains the 3-formyl radical-3-n-propyl-trimethylene oxide (10.5 restrain) of yellow oily.
Gas-liquid chromatograph (g.l.c): the OV-210 post presents a peak at 120 ℃
Infrared spectra (IR) (liquid film): 1730cm -1
Nucleus magnetic resonance (N.M.R) data are as follows: 1H(is followed successively by with TMS and makes interior mark, and solvent is CDCl 3Chemical displacement value p.p.m, the corresponding H number of integrated value, peak splitted number, the He Zhi number of coupling constant fourth value):
9.0，1H，S;4.90，2H，d，6;4.60，2H，d，6;2.30-1.0，7H，m。
(ⅲ) under nitrogen; the solution of sodium cyanide (1.6 gram) in water (2.0 milliliters); be added in the 3-formyl radical-3-n-propyl trimethylene oxide (3.0 gram) and the solution of 4-iodobenzene formyl chloride (6.2 gram) in ether (75 milliliters) that is stirring; and reaction mixture stirred spend the night; (50 milliliters) in the reaction mixture impouring water; the water mixture ether extraction, the ether extracting solution is with anhydrous sodium sulfate drying concentrating under reduced pressure then.Resistates is purified with the silicon-dioxide column chromatography, and the triethylamine pre-treatment of this post is used 1: 3 hexane: the chloroform wash-out then.
Obtain 3-(alpha-cyano-methylol)-the 4-iodo-benzoic acid ester colorless solid of 3-n-propyl-trimethylene oxide (6.5 grams, 90 ℃ of fusing points).
Nucleus magnetic resonance (NMR) data are as follows: 1It is CDCl that H(is followed successively by with mark, solvent in the TMS work 3Chemical displacement value p.p.m, the corresponding H number of integrated value, the division tuple at peak, and the He Zhi number of coupling constant J value):
7.90，2H，d，7;7.80，2H，d，7;5.70，1H，S;4.65，4H，m;1.95，2H，m;1.50，2H，m;1.00，3H，t，6.
Mass spectrum (M.S.), chemical ionization source:
M+1 peak 386
(ⅳ) with the described method of step (ⅲ) in the example 1, by 3-(alpha-cyano-methylol)-the 4-iodo-benzoic acid ester of 3-propylidene-trimethylene oxide made the 1-(4-iodophenyl)-3-cyanogen-4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes, (colourless crystallization, 129 ℃ of fusing points).
Nuclear magnetic resonance spectrum (NMR) data are as follows: 1It is CDCl that H(is followed successively by with mark, solution in the TMS work 3Chemical displacement value p.p.m, the corresponding H number of integrated value, the He Zhi number of the division tuple at peak and coupling constant J value):
7.75，2H，d，7;7.35，2H，d，7;4.95，1H，d，2;4.40，1H，m;4.15，3H，m;1.60-1.40，4H，m;1.00，3H，t，6.
Mass spectrum (M.S.) chemical ionization source:
M+1 peak 386
(ⅴ) with the method described in the embodiment 3, by the 1-(4-iodophenyl)-3-cyanogen-4-n-propyl-2,6,7-trioxa two rings (2,2,2) octane has prepared 1-(4-(3-methoxy propyl-1-alkynyl) phenyl) 3-cyanogen-4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes.
Example 10
1-(4-(3-methoxy propyl-1-alkynyl) phenyl) 4-n-propyl-2,6-Er Evil-7-thiophene-two ring (2,2,2) octane
(ⅰ) under nitrogen, diethyl n-propyl (20.0 gram) is added in the suspension of sodium hydride (4.8 grams, 50% dispersion agent in oil) in exsiccant toluene (200 milliliters) that is stirring.Mixture stirred 1 hour at 80 ℃, the cooling back adds benzyl chloride methyl thioether (rolling up the 267th page referring to J.L.Wood and V.du Vigneaud J.Biol.Chem.1939 the 131st) (16.0 gram) solution in dry toluene, and reaction mixture stirred 2 hours at 80 ℃.In the cooling hypsokinesis entry, aqueous mixture ether extraction, the ether extracting solution washes with water, uses anhydrous magnesium sulfate drying, then concentrating under reduced pressure.Obtain 2-benzyl thiomethyl-2-diethyl n-propyl yellow oil, need not further purification can use.
(ⅱ) at 0 ℃, under the nitrogen,, be added to the lithium aluminium hydride (7.0 gram) that stirring in the suspension of dry ether (400 milliliters) the solution of 2-benzyl thiomethyl-2-diethyl n-propyl (30.0 gram) in dry ether (60 milliliters).Mixture is stirring at room 3 hours, and then refluxes and stirred 3 hours.Adding 10% aqueous sodium hydroxide solution (25 milliliters) very carefully after the mixture cooling.Mixture filters, and solid is washed with ether, and filtrate is used anhydrous magnesium sulfate drying, concentrating under reduced pressure.Obtain 2-benzyl thiomethyl-2-n-propyl-1, ammediol colorless solid (20 gram), need not further purification can use.
(ⅲ)-70 ℃ 2-benzyl thiomethyl-2-n-propyl-1, the solution of (150 milliliters) is added to (150 milliliters) in the liquefied ammonia to ammediol (7.0 gram) in dry ether.Under agitation add sodium (1.8 gram), maintain-70 ℃ and stirred 1 hour.Reaction mixture is warming to-30 ℃ and adds solid ammonium chloride (10 gram) then carefully.
With nitrogen gas stream by removing deammoniation in the reaction mixture, resistates exsiccant washed with dichloromethane, filtrate decompression is concentrated.Obtain 2, the colourless oily matter frowzy of 2-dihydroxymethyl penta-1-mercaptan (3,2 gram), need not further purification can use.
(ⅳ) with being similar to the described method of step in the example 5 (ⅳ), 2, the former phenylformic acid trimethyl reaction of 2-dihydroxymethyl penta-1-mercaptan and 4-bromo-, provide the 1-(4-bromophenyl)-4-n-propyl-2,6-Er Evil-7-thiophene-two ring (2,2,2) octanes (colorless solid).
Gas-liquid chromatograph (g.l.c.): the OV-210 post presents a peak at 200 ℃.
Nuclear magnetic resonance spectrum (NMR) data are as follows: 1H(is followed successively by with TMS and makes interior mark, and solvent is CDCl 3Chemical displacement value p.p.m, the division tuple at corresponding H number of integrated value and peak):
7.50，4H，S;4.20，4H，m;3.20，2H，m;1.40，4H，m;1.00，3H，m。
Infrared spectra (IR) (paraffin oil paste): 1080(is strong), 1040(is strong) among the 1020().
Mass spectrum (MS), chemical ionization source:
M+1 peak 329,331.
(ⅴ) at-70 ℃, under the nitrogen, n-Butyl Lithium (hexane solutions of 16 milliliters of 1.6M) is added to the 1-(4-bromophenyl that is stirring)-4-n-propyl-2,6-Er Evil-7-thiophene-two ring (2,2,2) in the solution of octane (1.7 gram) in exsiccant ether (150 milliliters).Reaction mixture is warming to room temperature at leisure, and comes monitoring reaction course with vapour-liquid chromatography.After all raw materials disappear, add the solution of iodine (6.6 gram) in dry ether (50 milliliters), and and then add sodium thiosulfate solution (10 grams are in 70 ml waters).The reaction mixture ethyl acetate extraction, organic layer washes with water, uses anhydrous magnesium sulfate drying, the pressure reducing and steaming solvent.
Resistates is purified in (Woelm TSC aluminum oxide) with alumina column chromatography, uses 1: 10 saturated methylene dichloride of ammonia: the hexane wash-out.
Obtain the 1-(4-iodophenyl)-4-n-propyl-2,6-Er Evil-7-thiophene-two ring (2,2,2) octane colourless crystallization (0.8 gram, fusing point 128-132 ℃).
Nuclear magnetic resonance spectrum (NMR) data are as follows: 1H(is followed successively by with TMS and makes interior mark CDCl 3Be the chemical displacement value p.p.m of solvent, the corresponding H number of integrated value, the He Zhi number of the division tuple at peak and coupling constant J value):
7.70，2H，d，7;7.40，2H，d，7;4.15，4H，m;3.10，2H，m;1.30，4H，m;0.95，3H，m。
Mass spectrum (MS), chemical ionization source:
M+1 peak 377
(ⅵ) at following 4-n-propyl-1-(4-iodophenyl of nitrogen)-2,6-Er Evil-7-thiophene two rings (2,2,2) octane (0.20 gram), methyl propargyl ether (67 microlitre), two-(triphenylphosphine) Palladous chloride (II) (50 milligrams) and cuprous iodide (25 gram) mixture in exsiccant triethylamine (10 milliliters) was stirring at room 24 hours.
The pressure reducing and steaming solvent.The resistates ether extraction, the ether extracting solution washes with water, behind anhydrous magnesium sulfate drying, the pressure reducing and steaming solvent.
Resistates is purified in (Woelm TSC aluminum oxide) with alumina column chromatography, uses 1: 5 saturated methylene dichloride of ammonia: the hexane solvent wash-out.
Obtain 1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-4-n-propyl-2,6-Er Evil-7-thiophene two ring (2,2,2) octanes are a colorless solid (20 milligrams).
Nuclear magnetic resonance spectrum (NMR) data are as follows: 1It is CDCl that H(is followed successively by with mark, solvent in the TMS work 3Chemical displacement value p.p.m, the corresponding H number of integrated value, the division tuple at peak, and the He Zhi number of coupling constant J value):
7.60，2H，d，6;7.45，2H，d，6;4.30，2H，S;4.20，4H，m;3.50，3H，S;3.10，2H，m;1.30，4H，m;0.95，3H，m。
Mass spectrum (MS), chemical ionization source:
M+1 peak 319
Use aforesaid method, but replace triethylamine to make solvent with diethylamine, by the 1-(4-iodophenyl)-4-n-propyl-2,6-two Evil-7-thiophene two ring (2,2,2) octanes and trimethyl silicane ethyl-acetylene have prepared 1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-4-n-propyl-2,6-Er Evil-7-thiophene two rings (2,2,2) octane, the product that obtains are colourless crystallization shape solid.
Nuclear magnetic resonance spectrum (NMR) data are as follows: 1It is CDCl that H(is followed successively by with mark, solvent in the TMS work 3Chemical displacement value p, p, m, the corresponding H number of integrated value, the He Zhi number of the division tuple at peak and coupling constant J value):
7.50，4H，m;4.20，4H，m;3.15，2H，m;1.35，4H，m;1.05，3H，m;0.40，9H，m。
Mass spectrum (MS), chemical ionization source:
M+1 peak 347
With the described method of step (ⅰ) in the example (2), by 1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-4-n-propyl-2,6-Er Evil-7-thiophene two rings (2,2,2) octane has prepared the 1-(4-ethynyl phenyl)-4-n-propyl-2,6-Er Evil-7-thiophene two rings (2,2,2) octane, the product that obtains are colorless solid.
Nuclear magnetic resonance spectrum (NMR) data are as follows: 1H(is followed successively by with TMS and makes interior mark, and solvent is CDCl 3Chemical displacement value p, p, m, the corresponding H number of integrated value, the He Zhi number of the division tuple at peak and coupling constant J value):
7.50，4H，m;4.20，4H，m;3.20，3H，m;1.30，4H，m;1.00，3H，m。
Mass spectrum (MS) chemical ionization source:
M+1 peak 275
Example 11
The 1-(4-ethynyl phenyl)-and 4-tertiary butyl-2,6,7-trioxa two ring (2,2,2) octanes
(I) stirs down, Br at 0 ℃ 2(35 mmole) solution in chloroform is added to right-vinyl benzoic acid (5 grams, 34 mmoles) in the solution of chloroform (50 milliliters).Mixture placed spend the night, evaporate to dryness then, that stay is crude product 4-(1,2-two bromotrifluoromethanes) and phenylformic acid, 10.4 grams (99% yield).It is suspended in the exsiccant benzene (100 milliliters), adds thionyl chloride (8.3 gram), with the abundant reflux of mixture 3 hours.The solution evaporate to dryness, the acyl chlorides that obtains is a solid.
(II) is at 0 ℃, under the nitrogen, with the 4-(1 that makes above, 2-dibromo ethyl benzene formyl chloride (5 grams, 16 mmoles) solution is added in the solution of 3-tertiary butyl-3-methylol trimethylene oxide (2.16 grams, 15 mmoles) in exsiccant methylene dichloride (30 milliliters) that is stirring.Reaction mixture is warmed to room temperature and stirs and spend the night.The solution with water that obtains is washed, and uses dried over sodium sulfate, boils off solvent and promptly obtains oxetane, 6.5 grams.Product can be used the NMR(300 megacycle, at CDCl 3In the solution) identify: δ 1.05,9H, S; 3.95～4.1,2H, m; 4.45,2H, S; 4.6,4H, dofd; 5.15,1H, dofd; 7.5,2H, d; 8.1,2H, d;
At-70 ℃, under the nitrogen, boron trifluoride etherate (1 milliliter) is added in the solution of oxetane (6.5 grams, 15 mmoles) in exsiccant methylene dichloride (35 milliliters) that is stirring.Reaction solution is warming to room temperature and stirs and spend the night.Adding triethylamine makes reaction terminating and is evaporated to dried.Resistates is told organic layer in water and methylene dichloride two alternate distribution, uses K 2CO 3Drying boils off solvent and promptly stays crude product 1-(4-(1,2-two bromotrifluoromethanes) phenyl)-4-tertiary butyl-2,6,7-trioxa two ring (2,2,2) octanes.This compound can be identified (300 megacycles, CDCl with NMR 3): δ 0.9,9H, S; 3.9～4.05,2H, m; 4.15,6H, S; 5.11H, dofd; 7.35,2H, d; 7.6,2H, d;
The sodium that adds small pieces in the liquefied ammonia until blue look keeps not taking off, adds iron nitrate (100 milligrams) and also stirs this solution.When solution becomes when colourless, divide small pieces to add sodium (6 gram).Add sodium blue decoloration after 30 to 35 minutes, at this moment toward wherein adding the solution of above-mentioned dibromo ethyl benzene base bicyclooctane in tetrahydrofuran (THF).Placement is spent the night ammonia is evaporated, and resistates distributes between ether and ice/water.Tell organic layer, use K 2CO 3Drying, evaporating solvent, what stay is crude product 1-(4-ethynyl phenyl)-4-tertiary butyl-2,6,7-trioxa two ring (2,2,2) octanes.(use NH with the alumina column chromatography purification 3Make alkalize), and, use hexane-methylene dichloride recrystallization again with methylene dichloride-hexane (1: 4) wash-out.
Use above-mentioned schedule of operation, prepared (I) by corresponding trimethylene oxide: the 1-(4-ethynyl phenyl)-4-cyclohexyl-2,6,7-trioxa two rings (2,2,2) octane and (II): the 1-(4-ethynyl phenyl)-4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes.
That is, with the method for example 11,3-cyclohexyl-3-methylol trimethylene oxide and 3-n-propyl-3-methylol trimethylene oxide respectively and 4-(1, and 2-two bromotrifluoromethanes) the Benzoyl chloride reaction.The product that obtains is identified (300 megacycles, CDCl with NMR 3).
The ester of the trimethylene oxide that obtains so promptly obtains (I) 1-(4-(1 more as mentioned above and boron fluoride etherate reaction, 2-two bromotrifluoromethanes) phenyl)-4-encircles ethyl-2,6,7-trioxa two rings (2,2,2) octane and (II) 1-(4-(1,2-two bromotrifluoromethanes) phenyl)-and 4-n-propyl-2,6,7-trioxa two rings (2,2,2) octane.Product can be identified (300 megacycles, CDCl with NMR 3): (I) δ 0.9～1.3 and 1.5～1.9,11H, m; 3.9～4.1,2H, m; 4.1,6H, S; 5.1,1H, dofd; 7.35,2H, d; 7.6,2H, d; (II) δ 0.9,3H, t; 1.15～1.35,4H, m; 3.9～4.1,2H, m; 4.1,6H, S; 5.1,1H, dofd; 7.35,2H, d; The fragrance proton; 7.6,2H, d;
These dibromo ethyl benzene base bicyclic compounds as stated above engaging vibrating bromize hydrogen and produce desired 1-(4-ethynyl phenyl)-2,6,7-trioxa two ring (2,2,2) octanes.
Example 12
1-(4-(2-tertiary butyl dimethyl-silicon ethyl-acetylene base) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
At 0 ℃, under the nitrogen, n-Butyl Lithium (solution of 0.79 milliliter of 1.6M in hexane) is added to the 1-(4-ethynyl phenyl that is stirring)-4-n-propyl-2,6, in the solution of 7-three quinolines, two ring (2,2,2) octanes (0.25 gram) in exsiccant tetrahydrofuran (THF) (15 milliliters).Reaction mixture stirred 10 minutes at 0 ℃.Add the silica-based muriate of tertiary butyl dimethyl (0.23 gram), mixture was stirring at room 6 hours.Concentrating under reduced pressure adds water, aqueous mixture ether extraction, and the ether extracting solution washes with water, uses anhydrous magnesium sulfate drying, then concentrating under reduced pressure.Residue is purified in (Woelm TSC aluminum oxide) with alumina column chromatography, and with 2: 3 saturated methylene dichloride of ammonia: the hexane wash-out.Obtain 1-(4-(2-levies butyl dimethyl-silicon ethyl-acetylene base) phenyl)-4-n-propyl-2,6, the faint yellow crystallization of 7-trioxa two ring (2,2,2) octanes (0.32 gram).
Use aforesaid method, by the 1-(4-ethynyl phenyl)-4-n-propyl-2,6,7-trioxa two rings (2,2,2 octanes and methyl thiosulfonic acid S-methyl esters (Fluka A.G) have prepared 1-(4-(2-methylmercaptan ethyl alkynyl) phenyl)-4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes.
Example 13
N-methyl-3 (4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl)-third-2-alkynyl amide
At 0 ℃, under the nitrogen, n-Butyl Lithium (hexane solutions of 1.6 milliliters of 1.6M) is added to the 1-(4-ethynyl phenyl that is stirring)-4-n-propyl-2,6, in the solution of 7-trioxa two ring (2,2,2) octanes (0.5 gram) in exsiccant tetrahydrofuran (THF) (15 milliliters).Mixture stirred 10 minutes at 0 ℃, added methyl isocyanate (0.17 milliliter).After 1 hour the reaction mixture concentrating under reduced pressure.Add water, aqueous mixture ether extraction, the ether extracting solution washes with water, uses anhydrous magnesium sulfate drying, and concentrating under reduced pressure.
Resistates is purified in (Woelm TSC aluminum oxide) with alumina column chromatography, uses 1: 4 saturated methylene dichloride of ammonia: the hexane wash-out.
Obtain N-methyl-3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl)-third-2-alkynyl amide colourless crystallization (0.095 gram).
With being similar to synthetic N-methyl-3-(4-(4-n-propyl-2,6,7-trioxa two rings (2,2,2) phenyl suffering-1-yl))-method of third-2-alkynyl amide, by the 1-(4-ethynyl phenyl)-4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes and Trapex have prepared N-methyl-3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl)-third-2-alkynes sulfuration acid amides.
Example 14
3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl)-the Propargyl methanesulfonate ester.
At 0 ℃, under the nitrogen, Methanesulfonyl chloride (0.19 milliliter) is added to 3-(the 4-(4-n-propyl-2 that is stirring, 6,7-trioxa two rings (2,2,2) phenyl suffering-1-yl))-solution of third-2-alkynes-1-alcohol (0.6 gram) in exsiccant pyridine (0.34 milliliter) and exsiccant methylene dichloride (20 milliliters) in.Reaction mixture stirred 1 hour at 0 ℃.In mixture impouring water, aqueous mixture ether extraction, the ether extracting solution washes with water, uses anhydrous magnesium sulfate drying, then concentrating under reduced pressure.
Residue is purified in (Woelm TSC aluminum oxide) with alumina column chromatography, uses 1: 1 saturated methylene dichloride of ammonia: the hexane wash-out.
Obtain 3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl) Propargyl methanesulfonate ester clear crystal (0.18 gram).
Example 15
1-(4-(3-ethylmercapto group third-1-alkynyl) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
At 0 ℃, under the nitrogen, in the solution of dry tetrahydrofuran (20 milliliters), add n-Butyl Lithium (hexane solution of 0.45 milliliter of 1.6M) to sulfur alcohol (0.053 milliliter).Solution stirring drips 3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl after 10 minutes) solution of Propargyl methanesulfonate ester (0.25 gram) in exsiccant tetrahydrofuran (THF) (5 milliliters).After 2 hours with the reaction mixture concentrating under reduced pressure.Add water, aqueous mixture ether extraction, the ether extracting solution washes with water, uses anhydrous magnesium sulfate drying, then concentrating under reduced pressure.
Residue is purified in (Woelm TSC aluminum oxide) with alumina column chromatography, uses 1: 1 saturated methylene dichloride of ammonia: the hexane wash-out.
Obtain 1-(4-(3-ethylmercapto group-third-1-alkynyl) phenyl)-4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes are the cured shape solid of an off-white color (0.21 gram).
Example 16
1-(4-(3-second sulfinyl third-1-alkynyl) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(4-(3-ethylmercapto group third-1-alkynyl) phenyl)-4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes (0.20 gram) and the solution of 3-chloro-peroxidation phenylformic acid (0.16 restrains) in methylene dichloride (25 milliliters) were stirring at room 30 minutes.Use saturated sodium bicarbonate aqueous solution, water and salt solution thorough washing then successively.Dichloromethane solution with anhydrous magnesium sulfate drying after concentrating under reduced pressure.
Residue is purified in (TSC aluminum oxide) with alumina column chromatography, uses 1: 1 saturated methylene dichloride of ammonia: the hexane wash-out.
Obtain 1-(4-(3-second sulfinyl third-1-alkynyl) phenyl)-4-n-propyl-2,6,7-trioxa two ring (2,2,2) octane off-white color solids (0.08 gram).
With aforesaid method by 1-(4-(2-methylmercaptan ethyl alkynyl) phenyl)-4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes have prepared 1-(4-(2-methyl-sulfinic acid ethyl-acetylene base) phenyl)-4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes.
Following table has been listed the various spectrum and the nuclear magnetic resonance spectrum data of all cpds of the present invention.
Figure 86106933_IMG19
Figure 86106933_IMG20
Figure 86106933_IMG21
Figure 86106933_IMG22
Figure 86106933_IMG24
Figure 86106933_IMG25
Biological activity
A. to the lethal effect of housefly
Compound among the present invention is for not anaesthetizing female housefly (Musca domestica(WRL kind)) activity, can be confirmed by the solution of test compound in butanone is locally applied to tested insect.
The activity of tested compound also can be measured with the topical application of synergistic agent piperonyl butoxide (every insect with 6 microgram piperonyl butoxides (write a Chinese character in simplified form and make PB)).After 24 hours and 48 hours, add up mortality ratio.
The compound of following column number is activated when being lower than 30 micrograms/every housefly:
1，2，3，13，14，15，16，17，19，20，21，22，23，26，27
The compound of following column number is activated when being lower than 1 microgram/every housefly:
8，11
B. to the lethal effect of blatta germanica
The male blatta germanica (Blattella germanica(WRL kind) of compound among the present invention to having anaesthetized) activity can be confirmed by the solution of test compound in butanone is locally applied to tested insect.
The activity of the compound of test with synergistic agent piperonyl butoxide (every insect with 10 microgram piperonyl butoxides) topical application estimate.Use after 24 hours and 48 hours and add up mortality ratio.
The compound of following column number is activated when being lower than 50 micrograms/every insect:
1，7，8，11，13，17，20
The compound of following column number is activated when being lower than 5 micrograms/every insect:
2，3，15，16，19，21
C is to the lethal effect of grain weevil (Sitophilus granarius)
By the acetone soln of test compound is added on the cereal, allow insect be infected with then, determine the effect of compound of the present invention with this to the grain weevil adult.Dispenser was added up mortality ratio after 6 days.
The compound of following column number is activated when the concentration of its acetone soln is lower than 200P.P.m:
8，11，15，20，21，22，23，26
The compound of following column number is activated when the concentration of its acetone soln is lower than 50P.P.m:
2，14，16，19，27
D is to the lethal effect of culex (Culex quinquefasciatus)
Compound among the present invention can confirm by the solution in the OPD/ methylene dichloride of 0.5 milliliter of test compound of direct spraying the activity of female culex (Culex) adult.Spray and add up mortality ratio after 24 hours.
It is activated that the compound of following column number is lower than at 1% o'clock in concentration:
1，14，19，21，23，26，27
E is to mammiferous toxicity
When giving test mice (Charles River CDI) oral the compound that is numbered 2, the Lethal Dose 50 LD that records 50Value be about 20 milligrams/kg body weight.
When being numbered 4 compound and giving test mice (charles River CDI) oral, the LD that records 50Value is greater than 200 milligrams/kg body weight
Prescription:
1. emulsible concentrated solution
The compound 10.00 of logical formula I
Ethylan KEO 20.00
Dimethylbenzene
Butylated hydroxyanisol 2.50
100.00
2. wettable powder
The compound 25.0 of logical formula I
Atlapulgite 69.50
Isopropyl benzene sodium sulfonate 0.50
The naphthalene sulfonate salt 0.50 of condensation
Butylated hydroxytoluene 2.50
100.00
3. dust agent
The compound 0.50 of logical formula I
Butylated hydroxyanisol 0.10
Talcum powder 99.40
100.00
4. malicious erbium
The compound 40.25 of logical formula I
Rock sugar 59.65
Butylated hydroxytoluene 0.10
100.00
5. spray paint
The compound 2.5 of logical formula I
Resin 5.0
Butylated hydroxyanisol 0.5
High fragrant petroleum solvent 92.0
100.00
6. aerosol
The compound 0.30 of logical formula I
Butylated hydroxyanisol 0.10
1 4.00
Tasteless kerosene 15.60
Freon-11/12 80.00
50∶50 M∶X 100.00
7. sprays
The compound 0.1 of logical formula I
Butylated hydroxyanisol 0.1
Dimethylbenzene 10.0
Tasteless kerosene 89.8
100.00
8. potent sprays
The compound 0.1 of logical formula I
Piperonyl butoxide 0.5
Butylated hydroxyanisol 0.1
Dimethylbenzene 10.1
Tasteless kerosene 89.2
100.00
Errata
Figure 86106933_IMG26
Errata
Figure 86106933_IMG27
Errata

Claims (13)

1, a kind of preparation bicycloheptane, octane or nonane is characterized in that a kind of method with compound of logical formula I:
Wherein R is C 2-10Alkyl, alkenyl or alkynyl, they can replace arbitrarily, or substituent methyl, these substituted radicals have: cyano group, halogen, C 3-4Cycloalkyl, C 1-4Alkoxyl group or S (O) mR 4Base (R wherein 4Be C 1-4Alkyl, m value are 0,1 or 2); Or R is C 3-10Cycloalkyl, C 4-10Cycloalkenyl group or phenyl, every kind of group can at random further be replaced by following groups: C 1-4Alkoxyl group, C 1-3Alkyl, C 2-4Alkynyl, halogen, cyano group or S (O) as defined above mR 4Group;
R 1And R 3, no matter identical or different, can be hydrogen, halogen, C 1-3Alkyl, C 2-3Alkenyl or alkynyl, these alkyl, thiazolinyl and alkynyl can be at random by halogen, cyano group or C 1-4Alkoxyl group further replaces; They also can be to contain the alcoxyl carbon back of 6 carbon atoms of as many as or S (O) as defined above mR 4Base or quilt are had three C 1-4The alkynyl that the trialkylsilkl of alkyl replaces; Perhaps R 1Be CO 2C 1-4Alkyl, cyano group, gem-dimethyl, together with dicyano, together with dihalo-, together with diacetylene, Spirocyclopropyl, volution oxidative ethane or spiro oxetane, the volution oxidative ethane of replacement or spiro oxetane, oxygen or the methylene radical of replacement can at random be replaced by cyanogen, halogen or trifluoromethyl; R 1Can also and R and carbon atom that they were connected together, formation C 5-7Carbocyclic ring, can be on it by C 1-3Alkyl, alkoxyl group or C 2-3Thiazolinyl at random further replaces;
R 2Be at 4 quilts-(C ≡ C) nR 5, the phenyl of replacement, and on other position of phenyl ring, can at random be replaced, n is 1 or 2 here, R 5Be hydrogen, bromine, chlorine, iodine, S (O) mR 4XBase (R wherein 4XBe trifluoromethyl or R 4XBe exactly R 4, this R 4Defined with m such as front); R 5Also can be to contain the fat of any replacement of 9 carbon atoms of as many as or alicyclic radical, C * R 6(wherein X is oxygen or sulphur to base, R 6Be C 1-6Alkyl or-oxyl can be replaced arbitrarily by fluorine or amino on it, and amino can be arbitrarily by one or two C 1-4Alkyl further replaces); R 5Can also be cyano group or have three C 1-4The alkane silyl, or have two C 1-4An alkyl and a phenyl silica-based,
Y and Y 1Can be identical or inequality, they can be selected from oxygen and S (O) m(wherein m can be 0,1 or 2); Z is CH 2CH 2, CH 2CH 2O, sulphur, CH 2O, CH 2S, CHR 1XNR 7, (R here 1XBe hydrogen, cyano group, halogen, CO 2R 4Or C 1-3Alkyl, C 2-3Alkenyl or alkynyl, these alkyl, thiazolinyl and alkynyl can be at random by halogen, cyanogen, C 1-4The carbalkoxy of alkoxyl group, 6 carbon atoms of as many as or S (O) mR 4Base institute further replaces, here m and R 4Define R as the front 7Be hydrogen, benzyl, C 1-4Alkyl, C (O) R 8, R here 8Be C 1-4Alkyl, alkoxyl group or-NHR 9Base, R here 9Be C 1-4Alkyl, C 7-8Arylalkyl or the phenyl that is replaced arbitrarily by halogen), Z also can be-COCH 2-or-CH (OR 10) CH 2-(R here 10Be hydrogen, C 1-4Alkyl, C 1-4Acyl group, or C 1-3Formamyl), in the definition of Z, the atom of writing earlier is to be connected on 4 of bicyclic ring system;
If R 3Be the silica-based of hydrogen or trialkyl replacement, Y and Y 1Be oxygen, Z is CH 2During O, so, R 1And R 3Must be hydrogen,
General formula (I) compounds process for production thereof is having CH ≡ C-R 5The compound of formula (R wherein 5Definition and preceding described) and have the compound reaction of following formula (IB):
Figure 86106933_IMG2
R wherein, R 1, R 3, Y, Y 1Described as defined above with Z, R 2XBe one and R 2The group that group definition is identical, but 4 substituting group is an iodine on the phenyl ring: perhaps work as the R in the compound (I) 5Be hydrogen, the n value is 1 o'clock, also can be by following compound with formula (IC):
Figure 86106933_IMG3
Dehydrobromination and making, R here, R 1, R 3, Y, Y 1Described as defined above with Z, R 2yBe one and R 2The group that group definition is identical, but 4 substituting group is 1 on the phenyl ring, 2-two bromotrifluoromethanes.
2, in accordance with the method for claim 1, it is characterized in that R is n-propyl, normal-butyl, isobutyl-, tertiary butyl or cyclohexyl.
3,, it is characterized in that R ' is hydrogen, methyl, trifluoromethyl or cyano group according to claim 1 or 2 described methods.
4, according to the method described in aforementioned any claim, it is characterized in that R 5Be hydrogen, trimethyl silicon based, the methyl that replaces or the ethyl of replacement, have at least one to be hydroxyl or methoxyl group in the substituting group.
5, according to the method described in aforementioned any claim, it is characterized in that the n value is 1, and at phenyl R 2On 3 and/or 5 go up and further to be replaced by following groups: halogen, cyano group, azido-, nitro, C 1-3Alkyl or alkoxyl group (on it again can by halogen arbitrarily than replacing), C 2-3Alkenyl or alkynyl (can at random be replaced by halogen again on it
6, according to the method described in aforementioned any claim, it is characterized in that R 3Be hydrogen, methyl or trifluoromethyl.
7, according to the method described in aforementioned any claim, it is characterized in that Y is an oxygen, Y 1Be oxygen, Z is CH 2O or CH 2S.
8,, it is characterized in that the compound that is produced is the compound with following formula I A according to the method described in the claim 1:
R wherein aBe C 2-7Alkyl, alkenyl or alkynyl, they are by cyano, halogen or C arbitrarily 1-4Alkoxyl group replaces, perhaps R aBe C 3-10Cycloalkyl, C 4-10Cycloalkenyl group or phenyl, they can be at random by C 1-4Alkoxyl group, C 1-3Alkyl, C 2-4Alkynyl, halogen or cyano group replace: R 1aBe hydrogen, C 1-3Alkyl, C 2-3Alkenyl or alkynyl, they are by cyano, C arbitrarily 1-4Alkoxyl group, C 1-4Alkylthio, the carbalkoxy or the halogen that contain 6 carbon atoms of as many as replace, perhaps R 1aBe cyano group, gem-dimethyl, perhaps R 1aAnd R aAnd the carbon atom that they connected forms a C together 5-7Carbocyclic ring, also can be arbitrarily on it than by C 1-3Alkyl, C 2-3Alkoxyl group or thiazolinyl replace; R 2aBe 4 quilts-C ≡ CR 5aThe phenyl that replaces, other position of phenyl ring also can at random be replaced, here R 5aBe a C who replaces arbitrarily 1-9The fat base or-COR 6aBase, R here 6aBe C 1-6Alkyl or-oxyl, or by one or two C 1-4The amino that alkyl replaces arbitrarily; R 5aAlso can be cyano group, three C 1-4The alkane silyl, or two alkyl and a phenyl replacement is silica-based; R 3aBe hydrogen, C 1-3Alkyl, C 2-3Alkenyl or alkynyl, they can be further by cyano group, C 1-4Alkylthio, C 1-4Alkoxy or halogen replaces arbitrarily; Y aAnd Y 1aCan be identical or inequality, they be selected from oxygen or S(O respectively) m, m is 0,1 or 2 here; Z aBe CH 2CH 2, CH 2CH 2O sulphur, CH 2O, CH 2S or CH 2NR 7a, R here 7aBe hydrogen,
Figure 86106933_IMG5
Base, C 1-4Alkyl or C(O) R 8aBase, R here 8aBe C 1-4Alkyl or alkoxyl group, Z also can be-COCH 2-or-CHCOR 10a) CH 2-, R here 10aBe hydrogen, C 1-4Alkyl, C 1-4Acyl group or C 1-3Formamyl.
9,, it is characterized in that prepared compound is according to the method described in the claim 1:
1-(the trimethyl silicon based ethynyl of 3-nitro-4-(2-) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
The 1-(4-ethynyl phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
The 1-(4-ethynyl phenyl)-and 4-normal-butyl-2,6,7-trioxa two ring (2,2,2) octanes
The 1-(4-ethynyl phenyl)-and 4-isobutyl--2,6,7-trioxa two ring (2,2,2) octanes
The 1-(4-ethynyl phenyl)-and 4-n-pentyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-n-pentyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 3-chloro-4(2-) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-normal-butyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-isobutyl--2,6,7-trioxa two ring (2,2,2) octanes
1-(4-(3-ethoxy-c-1-alkynyl) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
4-methoxyl group-1-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl) fourth-1-alkynes
1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-and 4-isobutyl--2,6,7-trioxa two ring (2,2,2) octanes
N-(3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) sufferings-1-base phenyl) Propargyl) ethanamide
The 1-(4-ethynyl phenyl)-and 4-(2, the 2-dimethyl propyl)-2,6,7-trioxa two ring (2,2,2) octanes
3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl)-third-2-acetylenic acid methyl esters
1-(3-chloro-4-ethynyl phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(3-nitro-4-ethynyl phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
The 1-(4-2 alkynyl phenyl)-and 4-tertiary butyl-2,6,7-trioxa two ring (2,2,2) octanes
The 1-(4-ethynyl phenyl)-and 4-cyclohexyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-and 4-tertiary butyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(4-(3-methoxyl group-third-1-alkynyl) phenyl)-and 4-cyclohexyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(3-chloro-4-(3-methoxyl group-third-1-alkynyl) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-and 4-normal-butyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-and 4-n-pentyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-and 3-trifluoromethyl-4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-and 3-cyano group-4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-and 4-(2, the 2-dimethyl propyl)-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-(2, the 2-dimethyl propyl)-2,6,7-trioxa two ring (2,2,2) octanes
3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2)-1-yls) phenyl) Propargyl N-methyl carbamate
3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) octyl groups) phenyl) third-2-alkynes-1-alcohol
3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl) Propargyl acetic ester
1-(4-(third-1-alkynyl) phenyl-4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-and 4-n-propyl-2,6-Er Evil-7-thiophene-two ring (2,2,2) octane
1-(4-(2-tertiary butyl dimethyl-silicon ethyl-acetylene base) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl) Propargyl methanesulfonate ester
N-methyl-3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl) third-2-alkynyl amide
N-methyl-3-(4-(4-n-propyl-2,6,7-trioxa two ring (2,2,2) suffering-1-yls) phenyl) third-2-alkynes thioamides
1-(4-(3-methoxy propyl-1-alkynyl) phenyl)-and 3-trifluoromethyl-4-normal-butyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-tertiary butyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-cyclohexyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(4-(penta-1-alkynyl) phenyl)-and 4-n-propyl-2,6,7-trioxa two ring (2,2,2) octanes
The 1-(4-ethynyl phenyl)-and 4-ethyl-2,6,7-trioxa two ring (2,2,2) octanes
The 1-(4-ethynyl phenyl)-and 4-phenyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-phenyl-2,6,7-trioxa two ring (2,2,2) octanes
1-(the trimethyl silicon based ethynyl of 4-(2-) phenyl)-and 4-n-propyl-2,6-Er Evil-7-thiophene two ring (2,2,2) octanes
The 1-(4-ethynyl phenyl)-and 4-n-propyl-2,6-Er Evil-7-thiophene-two ring (2,2,2) octane.
10, a kind of sterilant or miticide are formed, and it is the mixture of a kind of active ingredient and a kind of carrier or thinner, it is characterized in that this active ingredient is claim 1 to 9 defined compound with logical formula I in any one.
11, a kind of synergic insecticidal formulation, it comprises synergistic agent and a kind of carrier or the thinner of a kind of active constituent as the formula I compound, it is characterized in that this active compound is the compound of claim 1 to 9 defined logical formula I in any one.
12, a kind of by the compound of claim 1 to 9 defined logical formula I in any one and the mixture that other sterilant is formed.
13, a kind of method of controlling insect pest, comprise the environment of insect or insect procreation is used a kind of compound or a kind of prescription, it is characterized in that said compound is claim 1 to 9 defined compound in any one, said prescription or mixture are claim 10 to 12 defined prescription or mixtures in any one.
CN 86106933 1985-09-23 1986-09-22 Agricultural chemical compound Pending CN86106933A (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
US779,167 1985-09-23
US06/779,167 US4772624A (en) 1985-01-23 1985-09-23 1,4-bis-substituted-2,6,7-trioxabicyclo(2.2.2)-octanes having ethynyl substituted phenyl group
GB858523582A GB8523582D0 (en) 1985-09-24 1985-09-24 Insecticidal compounds
US8523582 1985-09-24
GB868600201A GB8600201D0 (en) 1986-01-06 1986-01-06 Pesticidal compounds
US8600201 1986-01-06
US8606131 1986-03-12

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