JPH02270886A - Organosilicon compound and production thereof - Google Patents
Organosilicon compound and production thereofInfo
- Publication number
- JPH02270886A JPH02270886A JP9216389A JP9216389A JPH02270886A JP H02270886 A JPH02270886 A JP H02270886A JP 9216389 A JP9216389 A JP 9216389A JP 9216389 A JP9216389 A JP 9216389A JP H02270886 A JPH02270886 A JP H02270886A
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- expressed
- general formula
- atom
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title description 7
- 150000003961 organosilicon compounds Chemical class 0.000 title description 4
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 10
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- AZFVLHQDIIJLJG-UHFFFAOYSA-N chloromethylsilane Chemical compound [SiH3]CCl AZFVLHQDIIJLJG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 6
- 229910052740 iodine Inorganic materials 0.000 claims abstract 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- -1 (substituted)phenyl Chemical group 0.000 abstract description 25
- 239000003054 catalyst Substances 0.000 abstract description 6
- 125000000217 alkyl group Chemical group 0.000 abstract description 4
- 229910052794 bromium Inorganic materials 0.000 abstract description 3
- NTJUTXVQCPIWBN-UHFFFAOYSA-N 4-chlorobutyl-(4-chlorophenyl)-dimethylsilane Chemical compound ClCCCC[Si](C)(C)C1=CC=C(Cl)C=C1 NTJUTXVQCPIWBN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract description 2
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 239000003963 antioxidant agent Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 3
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000001819 mass spectrum Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 7
- 229910000077 silane Inorganic materials 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- NIDSRGCVYOEDFW-UHFFFAOYSA-N 1-bromo-4-chlorobutane Chemical compound ClCCCCBr NIDSRGCVYOEDFW-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000003747 Grignard reaction Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- HCJWWBBBSCXJMS-UHFFFAOYSA-J copper;dilithium;tetrachloride Chemical compound [Li+].[Li+].[Cl-].[Cl-].[Cl-].[Cl-].[Cu+2] HCJWWBBBSCXJMS-UHFFFAOYSA-J 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- PHHNNDKXQVKJEP-UHFFFAOYSA-N 1-bromo-5-chloropentane Chemical compound ClCCCCCBr PHHNNDKXQVKJEP-UHFFFAOYSA-N 0.000 description 1
- JTYUIAOHIYZBPB-UHFFFAOYSA-N 1-bromo-6-chlorohexane Chemical compound ClCCCCCCBr JTYUIAOHIYZBPB-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 1
- 125000004189 3,4-dichlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(Cl)C([H])=C1* 0.000 description 1
- 125000004211 3,5-difluorophenyl group Chemical group [H]C1=C(F)C([H])=C(*)C([H])=C1F 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 description 1
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- MFESCIUQSIBMSM-UHFFFAOYSA-N I-BCP Chemical compound ClCCCBr MFESCIUQSIBMSM-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 241000256011 Sphingidae Species 0.000 description 1
- UGKKOFVRPCHOHR-UHFFFAOYSA-J [Cu](Cl)(Cl)(Cl)Cl.[Li].[Li] Chemical compound [Cu](Cl)(Cl)(Cl)Cl.[Li].[Li] UGKKOFVRPCHOHR-UHFFFAOYSA-J 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- TWJVNKMWXNTSAP-UHFFFAOYSA-N azanium;hydroxide;hydrochloride Chemical compound [NH4+].O.[Cl-] TWJVNKMWXNTSAP-UHFFFAOYSA-N 0.000 description 1
- 239000012681 biocontrol agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- FWDXLPVOTHYLAA-UHFFFAOYSA-N chloromethyl-(4-chlorophenyl)-dimethylsilane Chemical compound ClC[Si](C)(C)C1=CC=C(Cl)C=C1 FWDXLPVOTHYLAA-UHFFFAOYSA-N 0.000 description 1
- WLPWONBNZDKSEN-UHFFFAOYSA-N chloromethyl-(4-fluorophenyl)-dimethylsilane Chemical compound ClC[Si](C)(C)C1=CC=C(F)C=C1 WLPWONBNZDKSEN-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は文献未載の新規な有機けい素化合物、及びその
製造方法に係り、詳しくは、医薬、農薬用の中間体等に
有用な、比較的長鎖のハロアルキル基がけい素原子に結
合したハロアルキルシラン化合物、及びグリニヤール反
応を利用したその製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel organosilicon compound that has not been published in any literature, and a method for producing the same. The present invention relates to a haloalkylsilane compound in which a relatively long-chain haloalkyl group is bonded to a silicon atom, and a method for producing the same using a Grignard reaction.
(従来の技術)
従来、比較的長鎖のハロアルキル基がけい素原子に結合
したハロアルキルシランは知られていなかった。(Prior Art) Conventionally, haloalkylsilanes in which a relatively long-chain haloalkyl group is bonded to a silicon atom have not been known.
(発明の構成)
本発明者らは、モノクロロメチルシランの反応について
種々研究を行っている際、モノクロロメチルシランから
誘導されるグリニヤール試薬とへロブロモアルカンとを
、触媒、好ましくは1価または2価の銅触媒例えばジリ
チウムテトラクロロ銅(TI)、の存在下に反応させる
ことにより、文献未載の新規なハロアルキルシランが収
率よく得られることを見出し、さらに検討を重ねて本発
明を完成するに至ったものである。(Structure of the Invention) While conducting various studies on the reaction of monochloromethylsilane, the present inventors discovered that a Grignard reagent derived from monochloromethylsilane and a herobromoalkane were used as a catalyst, preferably a monovalent or divalent They discovered that a novel haloalkylsilane, which has not been described in any literature, can be obtained in high yield by reacting it in the presence of a valent copper catalyst such as dilithium tetrachlorocopper (TI), and after further studies, they completed the present invention. This is what I came to do.
この出願の第1の発明は、一般式I
R’
R2−3i→CH21X
H3
[式中、R1はフェニル基または置換基を有するフェニ
ル基(ただし該置換基はハロゲン基、低級アルキル基、
低級アルコキシ基、低級ハロアルキル基および低級ハロ
アルコキシ基から選ばれる基)を表し、R2は炭素数1
〜3の炭化水素基を表し、Xは塩素原子または臭素原子
を表し、nは5〜20の整数を表す。]で示されるハロ
アルキルシラン化合物を要旨とするものであり、
第2の発明は前記のハロアルキルシラン化合物を製造す
る方法の発明であって、−1Q9式2%式%
[式中、R1はフェニル基または置換基を有するフェニ
ル基(ただし該置換基はハロゲン基、低級アルキル基、
低級アルコキシ基、低級ハロアルキル基および低級ハロ
アルコキシ基から選ばれる基)を表し、R2は炭素数1
〜3の炭化水素基を表す。]で示されるモノクロロメチ
ルシランを相当するグリニヤール試薬に変換し、これと
一般式3%式%
(式中、Xは塩素原子または臭素原子を表し、Yは塩素
原子、臭素原子またはヨウ素原子を表し、nは5〜20
の整数を表す。)で示されるジハロアルカンとを触媒の
存在下に反応させることを特徴とする、一般式I
R”5t−(CHzhX
ll3
0式中、R’、R2、X、nは前記に同じ。)で示され
るハロアルキルシラン化合物の製造方法を要旨とするも
のである。The first invention of this application is based on the general formula I R' R2-3i→CH21
(a group selected from a lower alkoxy group, a lower haloalkyl group, and a lower haloalkoxy group), and R2 has 1 carbon number.
~3 hydrocarbon group, X represents a chlorine atom or a bromine atom, and n represents an integer of 5 to 20. The second invention is an invention of a method for producing the haloalkylsilane compound represented by -1Q9 formula 2% formula% [wherein R1 is a phenyl group] or a phenyl group having a substituent (however, the substituent is a halogen group, a lower alkyl group,
(a group selected from a lower alkoxy group, a lower haloalkyl group, and a lower haloalkoxy group), and R2 has 1 carbon number.
~3 hydrocarbon group. ] is converted into the corresponding Grignard reagent, and this is combined with the general formula 3% formula% (wherein, , n is 5 to 20
represents an integer. ) with the general formula I R''5t-(CHzhXll30, where R', R2, X, and n are the same as above) The gist is a method for producing the haloalkylsilane compound shown.
以下に本発明の詳細な説明する。The present invention will be explained in detail below.
本発明のハロアルキルシラン化合物は、−JU式%式%
で示され、式中のR1はフェニル基、またはハロゲン基
、低級アルキル基、低級アルコキシ基、低級ハロアルキ
ル基および低級ハロアルコキシ基から選ばれる基を置換
基として有するフェニル基とされるものであるが、この
置換基としてのハロゲンにはフッソ、塩素または臭素が
挙げられ、低級アルキル基としては、例えばメチル基、
エチル基、n−プロピル基、1so−プロピル基、n−
ブチル基、1so−ブチル基、tert−ブチル基、ロ
ーペンチル基、n−ヘキシル基が挙げられ、低級アルコ
キシ基としては、例えばメトキシ基、エトキシ基、n−
プロポキシ基、n−ブトキシ基、tert−ブトキシ基
が挙げられ、低級ハロアルキル基としては、例えばフル
オロメチル基、ジフルオロメチル基、トリフルオロメチ
ル基、2−クロロエチル基、2−フルオロメチル基、2
,2.2−トリフルオロメチル基、3,3.3−トリフ
ルオロプロピル基が挙げられ、低級ハロアルコキシ基と
しては、例えばジフルオロメトキシ基、トリフルオロメ
トキシ基が挙げられる。The haloalkylsilane compound of the present invention is represented by -JU formula % formula %, where R1 is a phenyl group, or a group selected from a halogen group, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, and a lower haloalkoxy group. is considered to be a phenyl group having as a substituent, halogen as a substituent includes fluorine, chlorine, or bromine, and lower alkyl groups include, for example, a methyl group,
Ethyl group, n-propyl group, 1so-propyl group, n-
Examples include butyl group, 1so-butyl group, tert-butyl group, low pentyl group, and n-hexyl group. Examples of lower alkoxy groups include methoxy group, ethoxy group, n-
Examples of the lower haloalkyl group include propoxy group, n-butoxy group, and tert-butoxy group. Examples of lower haloalkyl group include fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2-chloroethyl group, 2-fluoromethyl group,
, 2.2-trifluoromethyl group, and 3,3.3-trifluoropropyl group, and examples of the lower haloalkoxy group include difluoromethoxy group and trifluoromethoxy group.
このような置換基を有するフェニル基としてのR’には
、例えば4−フルオロフェニル基、3−フルオロフェニ
ル基、4−クロロフェニル基、3−クロロフェニル基4
−ブロモフェニル基、3.4−ジフルオロフェニル基3
,5−ジフルオロフェニル基、3,4−ジクロロフェニ
ル基、3.5−ジクロロフェニル基、4−メチルフェニ
ル基、3−メチルフェニル基、3,4−ジメチルフェニ
ル基、3.5−ジメチルフェニル基、4−エチルフェニ
ル基、4−プロピルフェニル基、4−t−ブチルフェニ
ル基、4−クロロ−3−メチルフェニル基、3−クロロ
−4−メチルフェニル基、4−メトキシフェニル基、3
−メトキシフェニル基、2−メトキシフェニル基、4−
工!・キシフェニル基、4−n−プロポキシフェニル基
、4−n−ブトキシフェニル基、4−トリフルオロメチ
ルフェニル基、3−トリフルオロメチルフェニル基等が
挙げられるが、これらに限定されるものではない。R' as a phenyl group having such a substituent includes, for example, 4-fluorophenyl group, 3-fluorophenyl group, 4-chlorophenyl group, 3-chlorophenyl group 4
-Bromophenyl group, 3,4-difluorophenyl group 3
, 5-difluorophenyl group, 3,4-dichlorophenyl group, 3.5-dichlorophenyl group, 4-methylphenyl group, 3-methylphenyl group, 3,4-dimethylphenyl group, 3.5-dimethylphenyl group, 4 -ethylphenyl group, 4-propylphenyl group, 4-t-butylphenyl group, 4-chloro-3-methylphenyl group, 3-chloro-4-methylphenyl group, 4-methoxyphenyl group, 3
-methoxyphenyl group, 2-methoxyphenyl group, 4-
Engineering! - Examples include, but are not limited to, xyphenyl group, 4-n-propoxyphenyl group, 4-n-butoxyphenyl group, 4-trifluoromethylphenyl group, and 3-trifluoromethylphenyl group.
また、R2は炭素数1〜3の炭化水素基であり、これに
はメチル基、エチル基、プロピル基、ビニル基、シクロ
プロピル基等が例示される。Further, R2 is a hydrocarbon group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a vinyl group, a cyclopropyl group, and the like.
Xは塩素原子または臭素原子とされるものである。X is a chlorine atom or a bromine atom.
そしてnは5〜20の整数とされるものである。And n is an integer of 5 to 20.
本発明のハロアルキルシラン化合物は、モノクロロメチ
ルシランから誘導されるグリニヤール試薬とジハロアル
カンとを、触媒例えばジリチウムテトラクロロ銅(II
)の存在下に反応させることにより得られるものである
が、これは下記の反応経路で示される。The haloalkylsilane compound of the present invention is prepared by combining a Grignard reagent derived from monochloromethylsilane and a dihaloalkane with a catalyst such as dilithium tetrachlorocopper (II).
), which is shown in the reaction route below.
R’ R’
x−+CH2+T7T−Y R’R2−8i
−(CH21−TX
角虫媒イ列 L12CUCl4 CH
3(式中、R1、R2、X 、 Y 、 n ハ前記ニ
同シ。)まず始めに行われるモノクロロメチルシランの
相当するグリニヤール試薬への変換は、公知の方法によ
って行うことができる。すなわち、溶媒中に金属マグネ
シウムを懸濁し、これにモノクロロメチルシランを滴下
して反応させることにより行うことができる。用いられ
る溶媒としてはエチルエーテル、ブチルエーテル、テト
ラヒドロフランなどのエーテル系の溶媒が挙げられる。R'R' x-+CH2+T7T-Y R'R2-8i
-(CH21-TX Hornworm vector array L12CUCl4 CH
3 (In the formula, R1, R2, X, Y, n are the same as above.) The initial conversion of monochloromethylsilane to the corresponding Grignard reagent can be carried out by a known method. That is, it can be carried out by suspending metallic magnesium in a solvent and adding monochloromethylsilane dropwise thereto to cause a reaction. Examples of the solvent used include ether solvents such as ethyl ether, butyl ether, and tetrahydrofuran.
このようにして製造されたグリニヤール試薬は酸素及び
水分が遮断されていれば、通常の条件下では安定であり
、そのままで次の反応に用いられる。The Grignard reagent thus produced is stable under normal conditions as long as it is blocked from oxygen and moisture, and can be used as is in the next reaction.
次のグリニヤール試薬とジハロアルカンとの反応(カッ
プリング反応)もやはり同様のエーテル系の溶媒中で行
われる。すなわち、ジハロアルカンをこれらの溶媒の溶
液として、この溶液中にカップリング反応の触媒を溶解
または懸濁し、これにさきに製造したグリニヤール試薬
を滴下し、必要に応じて冷却または加熱することによっ
て反応を行う。ここで用いられる触媒としては、1価ま
たは2価の銅化合物例えばジリチウムテトラクロロ銅(
II)などが挙げられる。The next reaction (coupling reaction) between a Grignard reagent and a dihaloalkane is also carried out in a similar ether-based solvent. That is, the dihaloalkane is prepared as a solution of these solvents, the catalyst for the coupling reaction is dissolved or suspended in this solution, the Grignard reagent prepared earlier is added dropwise, and the reaction is carried out by cooling or heating as necessary. I do. The catalyst used here includes a monovalent or divalent copper compound such as dilithium tetrachlorocopper (
II), etc.
反応生成物の単離は通常のグリニヤール反応の場合と同
様にして行われ、冷却下、水、希塩酸または塩化アンモ
ニウム水溶液を加えて撹拌した後酢酸エチルまたはエチ
ルエーテルなどの水と混じり合わない溶媒で抽出し、抽
出液から減圧下溶媒をストリップし、残査を必要であれ
ば減圧蒸留またはクロマトグラフィーで分離することに
より目的のハロアルキルシランが単離される。Isolation of the reaction product is carried out in the same manner as in the case of the usual Grignard reaction. After adding water, dilute hydrochloric acid or ammonium chloride aqueous solution and stirring under cooling, the reaction product is isolated with a water-immiscible solvent such as ethyl acetate or ethyl ether. The desired haloalkylsilane is isolated by extraction, stripping the solvent from the extract under reduced pressure, and separating the residue by vacuum distillation or chromatography, if necessary.
本発明の有機けい素化合物の製造方法において原料とさ
れる一般式2で示されるモノクロロメチルシラン及び一
般式3で示されるジハロアルカンはともに公知のものを
用いることができる。As the monochloromethylsilane represented by general formula 2 and the dihaloalkane represented by general formula 3, which are used as raw materials in the method for producing an organosilicon compound of the present invention, known ones can be used.
本発明の有機けい素化合物は新規な化合物であり、これ
らの化合物自体が酸化防止剤、表面処理剤、接着促進剤
、生物制御剤として有用であるほか、他の有用物質用の
中間体、例えば医薬、農薬などの生理活性物質の合成の
ための中間体及びこれらのビルディングブロック合成の
ための中間体として有用である。The organosilicon compounds of the present invention are novel compounds, and these compounds themselves are useful as antioxidants, surface treatment agents, adhesion promoters, and biocontrol agents, as well as intermediates for other useful substances, such as It is useful as an intermediate for the synthesis of physiologically active substances such as medicines and agricultural chemicals, and as an intermediate for the synthesis of building blocks thereof.
また、本発明の製造方法はきわめて高収率であリ、広範
囲の鎖長のハロアルキル基を有するシラン化合物を合成
することができる。Further, the production method of the present invention has an extremely high yield and can synthesize silane compounds having haloalkyl groups with a wide range of chain lengths.
次に、本発明の実施例を挙げる。Next, examples of the present invention will be given.
実施例1
1−ブロモ−3−クロロプロパン17.2g (0,1
モル)のテトラヒドロフラン50m2の溶液中に、塩化
リチウム38.7mg及び塩化第二銅61.3mgをよ
く撹拌して溶解する。これを55から60°Cに加熱し
、撹拌しながら、金属マグネシウム2.43g (0,
1モル)と(4−クロロフェニル)クロロメチルジメチ
ルシラン21.9 g (0,1モル)から合成される
グリニヤール試薬(テトラヒドロフラン50mβ中溶液
)を30分間で滴下した。これをさらに2時間同温度に
保った後、冷却し、10%塩化アンモニウム水50mβ
を加え、酢酸エチル50mj2で2回抽出した。抽出液
を無水硫酸マグネシウムで乾燥し、減圧下に溶媒をスト
リップして得られた残査を減圧蒸留した。140℃(3
mmHg)で留出する留分として(4−クロロブチル)
(4−クロロフェニル)ジメチルシラン
H3
H3
を得た。収量19.7g (収率72%)であった。得
られた留分が上記のシランであることは下記の分析結果
から確かめられた。Example 1 1-bromo-3-chloropropane 17.2 g (0,1
38.7 mg of lithium chloride and 61.3 mg of cupric chloride are dissolved in a solution of 50 m2 of tetrahydrofuran with stirring thoroughly. This was heated to 55 to 60°C, and while stirring, 2.43 g of metallic magnesium (0,
A Grignard reagent (solution in 50 mβ of tetrahydrofuran) synthesized from 21.9 g (0.1 mol) of (4-chlorophenyl)chloromethyldimethylsilane) was added dropwise over 30 minutes. After keeping this at the same temperature for another 2 hours, it was cooled and 50 mβ of 10% ammonium chloride water was added.
was added and extracted twice with 50 mj2 of ethyl acetate. The extract was dried over anhydrous magnesium sulfate, the solvent was stripped off under reduced pressure, and the resulting residue was distilled under reduced pressure. 140℃ (3
mmHg) as a distillate (4-chlorobutyl)
(4-chlorophenyl)dimethylsilane H3 H3 was obtained. The yield was 19.7 g (yield 72%). It was confirmed from the analysis results below that the obtained fraction was the above-mentioned silane.
質量スペクトル m/e
259、204.189.169 (base)核磁気
共鳴スペクトル TCDCfl、、δ、 ppm1O1
25(6H,Sl ;0.82 (2H,ml 、 1
.33 (6H,ml 、 1.75 f2H,m)3
、51 (2H,t、 、I’6.5Hzl 、 7.
34 (2H,d、 J=8.3Hzl 、 7.43
(2H,d、 J=8.3Hzl
実施例2
実施例1と同様にして、■−ブロモー5−クロロベンク
ンとクロロメチルジメチルフェニルシランを用いて3m
m1gにおける沸点が130℃のシランを得た。このも
のは下記の分析結果から6−クロロへキシルジメチルフ
ェニルシラン
CI。Mass spectrum m/e 259, 204.189.169 (base) Nuclear magnetic resonance spectrum TCDCfl,, δ, ppm1O1
25 (6H, Sl; 0.82 (2H, ml, 1
.. 33 (6H, ml, 1.75 f2H, m)3
,51 (2H,t, ,I'6.5Hzl, 7.
34 (2H, d, J=8.3Hzl, 7.43
(2H, d, J = 8.3Hzl Example 2 In the same manner as in Example 1, 3m
A silane having a boiling point of 130° C. per ml was obtained. This product is 6-chlorohexyldimethylphenylsilane CI based on the analysis results below.
であることが確かめられた。It was confirmed that.
質量スペクトル 川/e
239 (M”CHi) 、 177、171.155
.135 (basel核磁気共鳴スペクトル (CD
CJ2.、δ+ ppm10.271(6H,s)、0
.76(2H,n+1,1.36(6H,ml、1.7
4(2H。Mass spectrum Kawa/e 239 (M”CHi), 177, 171.155
.. 135 (Basel nuclear magnetic resonance spectrum (CD)
CJ2. , δ+ ppm10.271 (6H,s), 0
.. 76 (2H, n+1, 1.36 (6H, ml, 1.7
4 (2H.
ml 、 3.517 f2H,t、 J=8Hz)
、 7.36 (2H,m) 、 7.52 (2H,
ml実施例3
実施例1と同様にして、1−ブロモ−6−クロロヘキサ
ンとクロロメチルジメチル−p−フルオロフェニルシラ
ンを用いて3 mmHgにおける沸点が142℃のシラ
ンを得た。このものは下記の分析結果から7−クロロへ
ブチルジメチル−p−フルオロフェニルシラン
H2
であることが確かめられた。ml, 3.517 f2H,t, J=8Hz)
, 7.36 (2H, m) , 7.52 (2H,
ml Example 3 In the same manner as in Example 1, silane having a boiling point of 142° C. at 3 mmHg was obtained using 1-bromo-6-chlorohexane and chloromethyldimethyl-p-fluorophenylsilane. This product was confirmed to be 7-chlorohebutyldimethyl-p-fluorophenylsilane H2 from the following analysis results.
質量スペクトル m/e
188、173.153 (base) 、 139.
123.91核磁気共鳴スペクトル (CDCj2.、
δ+ ppm10、25 (6H,s] 、 1.31
(8H,ml 、 1.40 f2t(、ml 、
1.77 (211,m)3.52(2H,d、J=6
.81,7.05(2H,+n)、7.47f2t(、
ml実施例4
実施例1と同様にして、1−ブロモ−4−クロロブタン
とクロロメチルジメチル−3,5−ジクロロフェニルシ
ランを用いて合成を行い、ついでシリカゲルカラムクロ
マトグラフィーで分離することによってシラン化合物を
得た。このものは下記の分析結果から5−り四ロベンチ
ルジメチル−3,5−ジクロロフェニルシラン
であることが確かめられた。Mass spectrum m/e 188, 173.153 (base), 139.
123.91 nuclear magnetic resonance spectrum (CDCj2.,
δ+ ppm10,25 (6H,s], 1.31
(8H, ml, 1.40 f2t(, ml,
1.77 (211, m) 3.52 (2H, d, J=6
.. 81,7.05(2H,+n),7.47f2t(,
ml Example 4 Synthesis was carried out in the same manner as in Example 1 using 1-bromo-4-chlorobutane and chloromethyldimethyl-3,5-dichlorophenylsilane, and the silane compound was then separated by silica gel column chromatography. Obtained. This product was confirmed to be 5-tetrabentyldimethyl-3,5-dichlorophenylsilane from the following analysis results.
質量スペクトル m/e
308 (M”) 、 293 (M”−15) 、
238.223.203 (base)実施例5
実施例1と同様にして、1−ブロモ−4−クロロブタン
とエチルクロロメチルメチル−4−クロロフェニルシラ
ンを用いて合成を行い、ついでシリカゲルカラムクロマ
トグラフィーで分離することによってシラン化合物を得
た。このものは下記の分析結果からエチル−5−クロロ
ペンチルメチル−4−クロロフェニルシラン
C)13
であることが確かめられた。Mass spectrum m/e 308 (M”), 293 (M”-15),
238.223.203 (base) Example 5 Synthesis was performed in the same manner as in Example 1 using 1-bromo-4-chlorobutane and ethylchloromethylmethyl-4-chlorophenylsilane, and then separated by silica gel column chromatography. A silane compound was obtained by doing this. This product was confirmed to be ethyl-5-chloropentylmethyl-4-chlorophenylsilane C)13 from the following analysis results.
質量スペクトル m/e
259 (M”−C2H5) 、 218.203.1
89 (basel 、 183.155核磁気共鳴ス
ペクトル FCDCI!、、、δ+ ppm)0、24
4 (3H,t) 、 0.76 (4H,ml 、
0.94 (3H,ml 、 1.31 f2H。Mass spectrum m/e 259 (M”-C2H5), 218.203.1
89 (basel, 183.155 nuclear magnetic resonance spectrum FCDCI!,,,δ+ ppm) 0, 24
4 (3H, t), 0.76 (4H, ml,
0.94 (3H, ml, 1.31 f2H.
m) 、 1 、45 f2H,m) 、 1 、75
(2H,ml 、 3.50 (2H,t、 J・6
.8) 。m) , 1 , 45 f2H, m) , 1 , 75
(2H, ml, 3.50 (2H, t, J・6
.. 8).
7、40 (4H,ml
実施例6
実施例1と同様にして、1−ブロモ−5−クロロペンタ
ンとクロロメチル−4−フルオロフェニルビニルメチル
シランを用いて合成を行い、ついでシリカゲルカラムク
ロマトグラフィーで分離することによってシラン化合物
を得た。このものは下記の分析結果から6−クロロへキ
シル−4−フルオロフェニルビニルメチルシラン
CH。7,40 (4H, ml Example 6 Synthesis was performed in the same manner as in Example 1 using 1-bromo-5-chloropentane and chloromethyl-4-fluorophenylvinylmethylsilane, and then silica gel column chromatography. A silane compound was obtained by separation, which was 6-chlorohexyl-4-fluorophenylvinylmethylsilane CH from the following analysis results.
であることが確かめられた。It was confirmed that.
質量スペクトル 川/e
269 (M”−C:R31、200,185,173
,165(basel核磁気共鳴スペクトル fc、D
CI23.δ、 ppm10、33 (3H,S) 、
0.84 f2H,ml 、 1.36 (6H,m
) 、 1.74 (2H,m13.51f2H,t、
J=6.4Hzl、5.75(IH,dodj、6.0
9(IH。Mass spectrum Kawa/e 269 (M”-C: R31, 200,185,173
, 165 (Basel nuclear magnetic resonance spectrum fc, D
CI23. δ, ppm10,33 (3H,S),
0.84 f2H,ml, 1.36 (6H,m
), 1.74 (2H, m13.51f2H,t,
J=6.4Hzl, 5.75(IH, dodj, 6.0
9 (IH.
dod) 、 6.27 (IH,dod) 、 7.
05 (2H,t、 J=8.8Hz、 7.48(2
H,dod、J=8.3,6.4Hz)実施例7
実施例1と同様にして、1−ブロモ−4−り四ロブタン
と4−クロロフェニルクロロメチルシク0ブロビルメヂ
ルシランを用いて合成を行い、ついでシリカゲルカラム
クロマトグラフィーで分離することによってシラン化合
物を得た。このものは下記の分析結果から4−クロロフ
ェニル−5−クロロペンチルシクロプロピルメチルシラ
ンH3
であることが確かめられた。dod), 6.27 (IH, dod), 7.
05 (2H,t, J=8.8Hz, 7.48(2
H, dod, J = 8.3, 6.4 Hz) Example 7 In the same manner as in Example 1, using 1-bromo-4-ditetrabutane and 4-chlorophenylchloromethylsilane, A silane compound was obtained by performing synthesis and then separating by silica gel column chromatography. This product was confirmed to be 4-chlorophenyl-5-chloropentylcyclopropylmethylsilane H3 from the following analysis results.
質量スペクトル m/e
285 (M”−CH,l 、 259.230.19
5 (base)核磁気共鳴スペクトル fcDcJ2
.、δ+ ppm)−0,24flH,m) 、 0.
12 f3H,Sl 、 0.23 (2H,m) 、
0.65 f2H。Mass spectrum m/e 285 (M”-CH,l, 259.230.19
5 (base) nuclear magnetic resonance spectrum fcDcJ2
.. , δ+ ppm)-0,24flH,m), 0.
12 f3H,Sl, 0.23 (2H,m),
0.65 f2H.
m) 、 0.76 f2H,ml 、 1.42 (
4H,ml 、 1.76 (2H,m) 、 3.5
1(2H,t、 J=6.81 、7.34 f2H,
d、 J・8.3) 、 7.47 (2H,d。m), 0.76 f2H,ml, 1.42 (
4H, ml, 1.76 (2H, m), 3.5
1 (2H, t, J=6.81, 7.34 f2H,
d, J・8.3), 7.47 (2H, d.
J=8.3)
実施例8〜76
実施例1と同様にして、前記一般式lにおいて第1表ま
たは第2表に示すR1,R2、X、nを有するハロ
0アル代ルシラン化合物を合成した。生成物の構造は質
量スペクトル及び核磁気共鳴スペクトルによって確認し
たが、質量スペクトルは第1表または第2表に併記した
とおりであった。J=8.3) Examples 8 to 76 In the same manner as in Example 1, halo-0-al silane compounds having R1, R2, X, and n shown in Table 1 or Table 2 in the general formula 1 were synthesized. did. The structure of the product was confirmed by mass spectrum and nuclear magnetic resonance spectrum, and the mass spectrum was as shown in Table 1 or Table 2.
Claims (1)
ニル基(ただし該置換基はハロゲン基、低級アルキル基
、低級アルコキシ基、低級ハロアルキル基および低級ハ
ロアルコキシ基から選ばれる基)を表し、R^2は炭素
数1〜3の炭化水素基を表し、Xは塩素原子または臭素
原子を表し、nは5〜20の整数を表す。] で示されるハロアルキルシラン化合物。 2、一般式2 ▲数式、化学式、表等があります▼ [式中、R^1はフェニル基または置換基を有するフェ
ニル基(ただし該置換基はハロゲン基、低級アルキル基
、低級アルコキシ基、低級ハロアルキル基および低級ハ
ロアルコキシ基から選ばれる基)を表し、R^2は炭素
数1〜3の炭化水素基を表す。]で示されるモノクロロ
メチルシランを相当するグリニヤール試薬に変換し、こ
れと 一般式3 ▲数式、化学式、表等があります▼ (式中、Xは塩素原子または臭素原子を表し、Yは塩素
原子、臭素原子またはヨウ素原子を表し、nは5〜20
の整数を表す。) で示されるジハロアルカンとを触媒の存在下に反応させ
ることを特徴とする 一般式1 ▲数式、化学式、表等があります▼ (式中、R^1、R^2、X、nは前記に同じ。)で示
されるハロアルキルシラン化合物の製造方法。[Claims] 1. General formula 1 ▲ Numerical formulas, chemical formulas, tables, etc. , lower alkoxy group, lower haloalkyl group, and lower haloalkoxy group), R^2 represents a hydrocarbon group having 1 to 3 carbon atoms, X represents a chlorine atom or a bromine atom, and n represents 5 Represents an integer between ~20. ] A haloalkylsilane compound represented by: 2. General formula 2 ▲ Numerical formulas, chemical formulas, tables, etc. (a group selected from a haloalkyl group and a lower haloalkoxy group), and R^2 represents a hydrocarbon group having 1 to 3 carbon atoms. ] Convert the monochloromethylsilane shown by the corresponding Grignard reagent, and use this and general formula 3 ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, X represents a chlorine atom or a bromine atom, Y represents a chlorine atom, Represents a bromine atom or an iodine atom, n is 5 to 20
represents an integer. ) General formula 1 characterized by reacting a dihaloalkane represented by The same applies to ).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9216389A JPH02270886A (en) | 1989-04-12 | 1989-04-12 | Organosilicon compound and production thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9216389A JPH02270886A (en) | 1989-04-12 | 1989-04-12 | Organosilicon compound and production thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02270886A true JPH02270886A (en) | 1990-11-05 |
Family
ID=14046759
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9216389A Pending JPH02270886A (en) | 1989-04-12 | 1989-04-12 | Organosilicon compound and production thereof |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH02270886A (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58177924A (en) * | 1982-04-12 | 1983-10-18 | Shin Etsu Chem Co Ltd | Preparation of cis-alkenyl chloride |
-
1989
- 1989-04-12 JP JP9216389A patent/JPH02270886A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58177924A (en) * | 1982-04-12 | 1983-10-18 | Shin Etsu Chem Co Ltd | Preparation of cis-alkenyl chloride |
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