JP2000044580A - Production of dihalomethylsilane - Google Patents
Production of dihalomethylsilaneInfo
- Publication number
- JP2000044580A JP2000044580A JP10215859A JP21585998A JP2000044580A JP 2000044580 A JP2000044580 A JP 2000044580A JP 10215859 A JP10215859 A JP 10215859A JP 21585998 A JP21585998 A JP 21585998A JP 2000044580 A JP2000044580 A JP 2000044580A
- Authority
- JP
- Japan
- Prior art keywords
- group
- halogenated
- compound
- reaction
- present
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- OKJPEAGHQZHRQV-UHFFFAOYSA-N iodoform Chemical compound IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims abstract description 16
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims abstract description 15
- 150000004756 silanes Chemical class 0.000 claims abstract description 12
- 125000004953 trihalomethyl group Chemical group 0.000 claims abstract description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 239000011572 manganese Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 125000006371 dihalo methyl group Chemical group 0.000 claims abstract description 6
- 229910001508 alkali metal halide Inorganic materials 0.000 claims abstract description 5
- 150000008045 alkali metal halides Chemical class 0.000 claims abstract description 5
- 235000009518 sodium iodide Nutrition 0.000 claims abstract description 5
- 150000001408 amides Chemical class 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 23
- 229910000077 silane Inorganic materials 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- 239000004210 ether based solvent Substances 0.000 claims 1
- -1 metallic manganese) Chemical compound 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000000543 intermediate Substances 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- RXBPBTHLRBDCFU-UHFFFAOYSA-N diiodomethyl(trimethyl)silane Chemical compound C[Si](C)(C)C(I)I RXBPBTHLRBDCFU-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 125000005843 halogen group Chemical group 0.000 description 6
- 125000000623 heterocyclic group Chemical group 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- 125000003367 polycyclic group Chemical group 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 2
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- GTCXKDHNYFKMNB-UHFFFAOYSA-M IC(I)[Mg]Cl Chemical compound IC(I)[Mg]Cl GTCXKDHNYFKMNB-UHFFFAOYSA-M 0.000 description 1
- ZQONYYYBFUQOBI-UHFFFAOYSA-N IC(I)[Na] Chemical compound IC(I)[Na] ZQONYYYBFUQOBI-UHFFFAOYSA-N 0.000 description 1
- 238000006932 Simmons-Smith cyclopropanation reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- KWYZNESIGBQHJK-UHFFFAOYSA-N chloro-dimethyl-phenylsilane Chemical compound C[Si](C)(Cl)C1=CC=CC=C1 KWYZNESIGBQHJK-UHFFFAOYSA-N 0.000 description 1
- OJZNZOXALZKPEA-UHFFFAOYSA-N chloro-methyl-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](Cl)(C)C1=CC=CC=C1 OJZNZOXALZKPEA-UHFFFAOYSA-N 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- NZZFYRREKKOMAT-OUBTZVSYSA-N diiodomethane Chemical class I[13CH2]I NZZFYRREKKOMAT-OUBTZVSYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ジハロメチルシラ
ン類の、新規な製造方法に関する。TECHNICAL FIELD The present invention relates to a novel method for producing dihalomethylsilanes.
【０００２】[0002]
【従来の技術】従来、ジヨードメチルトリメチルシラン
（Ｍｅ３ＳｉＣＨＩ２）は、ジヨードメタンあるいはヨ
ードホルムから得られることは知られているが、いずれ
も極低温（−９０℃）を必要とし、工業的には問題であ
った。例えば、次式の反応式で示される方法が知られて
いる。 2. Description of the Related Art Hitherto, it has been known that diiodomethyltrimethylsilane (Me 3 SiCHI 2 ) can be obtained from diiodomethane or iodoform, but all require extremely low temperatures (−90 ° C.) and are industrially required. Was a problem. For example, a method represented by the following reaction formula is known.
【０００３】[0003]
【化１】 Embedded image
【０００４】この方法は、ヨードホルムに−８５℃でグ
リニャール試薬を反応させて、ジヨードメチルマグネシ
ウムクロリドとし、これに−８５℃でクロロトリメチル
シランを反応させて、目的のジヨードメチルトリメチル
シラン（Ｍｅ３ＳｉＣＨＩ２）を約７７％の収率で得る
というものである（Seyferth, D., et al., J. Organom
et. Chem., 1970, 24, 647）。また、次式で示される方
法も知られている。According to this method, iodoform is reacted with a Grignard reagent at -85 ° C. to give diiodomethylmagnesium chloride, which is then reacted with chlorotrimethylsilane at -85 ° C. to give the desired diiodomethyltrimethylsilane (Me 3 SiCHI 2 ) in a yield of about 77% (Seyferth, D., et al., J. Organom).
et. Chem., 1970, 24, 647). A method represented by the following equation is also known.
【０００５】[0005]
【化２】 Embedded image
【０００６】この方法もクロロトリメチルシランを−９
０℃で反応させるという点においては前記の方法と同じ
であるが、出発原料としてジヨードメタンを用いる点で
異なっている。即ち、ジヨードメタンに−９０℃でナト
リウムヘキサメチルジシラジドを作用させて、ジヨード
メチルナトリウムとし、これに−９０℃でクロロトリメ
チルシランを反応させて目的のジヨードメチルトリメチ
ルシラン（Ｍｅ３ＳｉＣＨＩ２）を収率約６７％で得る
という方法である（Charreau, P., Bull. Chem. Soc. F
r., 1990, 127, 275）。In this method, chlorotrimethylsilane is added to -9.
This is the same as the above-mentioned method in that the reaction is carried out at 0 ° C., except that diiodomethane is used as a starting material. In other words, sodium hexamethyldisilazide is allowed to act on diiodomethane at -90 ° C to form diiodomethylsodium, which is reacted with chlorotrimethylsilane at -90 ° C to obtain the target diiodomethyltrimethylsilane (Me 3 SiCHI 2). ) In a yield of about 67% (Charreau, P., Bull. Chem. Soc. F
r., 1990, 127, 275).
【０００７】ジヨードメタン誘導体はシクロプロパン環
を合成するシモンズ−スミス（Simmons-Smith） 反応の
原料として有用であるばかりでなく、本発明のジヨード
メチルトリメチルシランはさらにシリル基を有してお
り、アルデヒド類と反応してビニル位にシリル基が置換
した、アルケニルシランの合成原料としても有用な化合
物である。これらのシクロプロパン誘導体やアルケニル
シランは、各種の医薬、農薬などの生理活性物質や、各
種の工業材料の合成中間体として有用なものである。[0007] The diiodomethane derivative is not only useful as a starting material for Simmons-Smith reaction for synthesizing a cyclopropane ring, but also the diiodomethyltrimethylsilane of the present invention further has a silyl group. It is a compound useful as a raw material for the synthesis of alkenylsilanes, in which a silyl group is substituted at the vinyl position by reacting with a compound. These cyclopropane derivatives and alkenylsilanes are useful as physiologically active substances such as various medicines and agricultural chemicals and synthetic intermediates of various industrial materials.
【０００８】[0008]
【発明が解決しようとする課題】本発明のジヨードメチ
ルトリメチルシラン（Ｍｅ３ＳｉＣＨＩ２）は、−８５
℃から−９０℃という極めて低温で、かつ、反応性の高
い強塩基を用いて金属化し、それをクロロトリメチルシ
ランで捕捉して製造されていたが、工業的な方法は知ら
れておらず、わずかに実験的に製造されていたに過ぎな
い。本発明は、ジヨードメチルトリメチルシラン（Ｍｅ
３ＳｉＣＨＩ２）などのシリル化ジハロメチル基を有す
る化合物を簡便且つ工業的に製造することができる方法
を提供するものである。The diiodomethyltrimethylsilane (Me 3 SiCHI 2 ) of the present invention is -85.
Extremely low temperature from ℃ to -90 ℃, and metallized using a highly reactive strong base, was produced by capturing it with chlorotrimethylsilane, but no industrial method is known, It was manufactured only experimentally. The present invention relates to diiodomethyltrimethylsilane (Me
It is intended to provide a method for easily and industrially producing a compound having a silylated dihalomethyl group such as 3 SiCHI 2 ).
【０００９】[0009]
【課題を解決するための手段】本発明は、トリハロメチ
ル基を有する化合物とハロゲン化シランとをマンガンの
存在下に反応させてシリル化ジハロメチル基を有する化
合物を製造する方法に関する。本発明のトリハロメチル
基を有する化合物としては、好ましくはハロホルム、よ
り好ましくはヨードホルムが挙げられる。また、本発明
のハロゲン化シランとしては、好ましくはハロゲン化ト
リアルキルシラン、より好ましくはクロロトリメチルシ
ランが挙げられる。SUMMARY OF THE INVENTION The present invention relates to a method for producing a compound having a silylated dihalomethyl group by reacting a compound having a trihalomethyl group with a silane halide in the presence of manganese. As the compound having a trihalomethyl group of the present invention, preferably, haloform, more preferably, iodoform is used. Further, as the halogenated silane of the present invention, preferably, a halogenated trialkylsilane, more preferably, chlorotrimethylsilane is used.
【００１０】したがって、より詳細には本発明は、ヨー
ドホルム（ＣＨＩ３）とクロロトリメチルシラン（Ｍｅ
３ＳｉＣｌ）とを、マンガン金属の存在下に反応させて
なるジヨードメチルトリメチルシラン（Ｍｅ３ＳｉＣＨ
Ｉ２）の製造方法に関する。Therefore, more specifically, the present invention relates to iodoform (CHI 3 ) and chlorotrimethylsilane (Me
3 SiCl) in the presence of manganese metal in the presence of diiodomethyltrimethylsilane (Me 3 SiCH).
I 2 ).
【００１１】本発明のトリハロメチル基を有する化合物
は、トリハロメチル基に反応に関与するハロゲン原子を
１個有し、分子中に本発明の反応を阻害することのある
官能基を有さないものであれば特に制限はなく、好まし
いトリハロメチル基を有する化合物としては、次の一般
式（Ｉ）で示される化合物を挙げることができる。The compound having a trihalomethyl group according to the present invention has one halogen atom involved in the reaction in the trihalomethyl group and does not have a functional group in the molecule which may inhibit the reaction according to the present invention. There is no particular limitation as long as the compound has a preferred trihalomethyl group, and examples thereof include compounds represented by the following general formula (I).
【００１２】Ｒ−ＣＸ３ （Ｉ） （式中、Ｒは水素原子又は有機残基を示し、Ｘは同一又
はそれぞれ異なってもよいハロゲン原子を示す。）R-CX 3 (I) (wherein, R represents a hydrogen atom or an organic residue, and X represents the same or different halogen atoms.)
【００１３】前記一般式（Ｉ）における有機残基Ｒとし
ては、炭素数１〜３０、好ましくは１〜２０、より好ま
しくは１〜１５の直鎖状又は分枝状のアルキル基、炭素
数４〜３０、好ましくは５〜２０、より好ましくは６〜
１０の単環、多環又は縮合環式のシクロアルキル基、炭
素数６〜３０、好ましくは６〜２０、より好ましくは６
〜１０の単環、多環又は縮合環式のアリール基、環中に
少なくとも１個以上の窒素原子、酸素原子又は硫黄原子
を有し、１個の環の大きさが５〜２０員、好ましく５〜
１０員、より好ましく５〜７員であって、前記したシク
ロアルキル基又はアリール基と縮合していてもよい飽和
又は不飽和の単環、多環又は縮合環式の複素環式基、前
記したアルキル基に前記したアリール基、シクロアルキ
ル基又は複素環式基が置換したアラルキル基、シクロア
ルキルアルキル基又は複素環式基置換アルキル基などが
挙げられる。The organic residue R in the general formula (I) is a linear or branched alkyl group having 1 to 30, preferably 1 to 20, more preferably 1 to 15 carbon atoms, ~ 30, preferably 5-20, more preferably 6 ~
10 monocyclic, polycyclic or condensed cyclic alkyl groups having 6 to 30 carbon atoms, preferably 6 to 20, more preferably 6
10 to 10 monocyclic, polycyclic or condensed cyclic aryl groups, having at least one nitrogen atom, oxygen atom or sulfur atom in the ring, and one ring having a size of 5 to 20 members, preferably 5-
A saturated or unsaturated monocyclic, polycyclic or condensed heterocyclic group which is 10-membered, more preferably 5 to 7-membered and which may be condensed with the above-mentioned cycloalkyl group or aryl group, Examples of the alkyl group include an aralkyl group, a cycloalkylalkyl group, or a heterocyclic group-substituted alkyl group in which the above-described aryl group, cycloalkyl group, or heterocyclic group has been substituted.
【００１４】これらのアルキル基、シクロアルキル基、
アリール基、複素環式基、アラルキル基、シクロアルキ
ルアルキル基又は複素環式基置換アルキル基は、本発明
の反応を阻害しない１個又は２個以上の置換基を有して
もよく、これらの置換基としては前記したアルキル基な
どのほかに、ケト基、低級アシル基、低級アルコキシ
基、ハロゲンなどが挙げられる。These alkyl groups, cycloalkyl groups,
An aryl group, a heterocyclic group, an aralkyl group, a cycloalkylalkyl group or a heterocyclic group-substituted alkyl group may have one or more substituents which do not inhibit the reaction of the present invention. Examples of the substituent include a keto group, a lower acyl group, a lower alkoxy group, and a halogen in addition to the above-described alkyl group.
【００１５】前記一般式（Ｉ）のＲの有機残基の例とし
ては、メチル基、エチル基、ｎ−プロピル基、イソプロ
ピル基、ｎ−ブチル基、ｔ−ブチル基、ｎ−ヘキシル
基、ｎ−オクチル基、ｎ−ノニル基、ｎ−デシル基など
のアルキル基、シクロヘキシル基、シクロペンチル基な
どのシクロアルキル基、フェニル基、ナフチル基などの
アリール基、チエニル基、フラニル基などの複素環基、
ベンジル基、フェネチル基などのアラルキル基等が挙げ
られる。Examples of the organic residue of R in the general formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, -Octyl group, n-nonyl group, alkyl group such as n-decyl group, cyclohexyl group, cycloalkyl group such as cyclopentyl group, phenyl group, aryl group such as naphthyl group, thienyl group, heterocyclic group such as furanyl group,
And aralkyl groups such as benzyl group and phenethyl group.
【００１６】前記一般式（Ｉ）のＲは、前記の有機残基
であってもよいが、好ましくは水素原子である。R in the general formula (I) may be the aforementioned organic residue, but is preferably a hydrogen atom.
【００１７】また、前記一般式（Ｉ）のＸは、フッ素、
塩素、臭素、ヨウ素などのハロゲン原子であり、３個の
ハロゲン原子は同一であっても、それぞれ異なっていて
もよいが、好ましくは同一のハロゲン原子であり、より
好ましくは３個のヨウ素原子である。X in the general formula (I) is fluorine,
A halogen atom such as chlorine, bromine or iodine, and the three halogen atoms may be the same or different, but are preferably the same halogen atom, and more preferably three iodine atoms. is there.
【００１８】本発明のハロゲン化シランとしては、反応
性のハロゲン−ケイ素結合を有する化合物であれば反応
に供することもできるが、シランの残りの３個の基が前
記した有機残基を有するものが好ましく、より好ましく
は、アルキル基、アリール基などの炭化水素基である。
ハロゲン化シランの残りの３個の基は同一のものであっ
ても、異なるものであってもよい。好ましいハロゲン化
シランとしてはハロゲン化トリ炭化水素シランが挙げら
れ、より具体的には、例えば、クロロトリメチルシラ
ン、クロロトリエチルシランなどのハロゲン化トリアル
キルシラン、クロロフェニルジメチルシラン、クロロジ
フェニルメチルシランなどのハロゲン化アリールジアル
キシシラン、ハロゲン化アルキルジアリールシラン、ハ
ロゲン化トリアリールシランなどが挙げられる。また、
ハロゲン化シランのハロゲンとしては、前記したハロゲ
ンでよいが、塩素が好ましい。As the halogenated silane of the present invention, any compound having a reactive halogen-silicon bond can be used for the reaction, but the remaining three groups of the silane have the above-mentioned organic residues. And more preferably a hydrocarbon group such as an alkyl group and an aryl group.
The remaining three groups of the halogenated silane may be the same or different. Preferred halogenated silanes include halogenated trihydrocarbon silanes, and more specifically, for example, halogenated trialkylsilanes such as chlorotrimethylsilane and chlorotriethylsilane; halogens such as chlorophenyldimethylsilane and chlorodiphenylmethylsilane Aryldialkoxysilane, halogenated alkyldiarylsilane, halogenated triarylsilane and the like. Also,
The halogen of the halogenated silane may be the halogen described above, but is preferably chlorine.
【００１９】本発明の方法においては、溶媒を使用する
のが好ましく、溶媒としてはテトラヒドロフラン（ＴＨ
Ｆ）、ジオキサン、ジメトキシエタン（ＤＭＥ）、エー
テルなどのエーテル系、ジメチルホルムアミド（ＤＭ
Ｆ）、ジメチルアセトアミド（ＤＭＡ）などのアミド系
の溶媒の１種又は２種以上を組み合わせて用いるのが好
ましい。本発明の方法におけるさらに好ましい溶媒とし
ては、テトラヒドロフラン（ＴＨＦ）、ジメトキシエタ
ン（ＤＭＥ）、ジメチルホルムアミド（ＤＭＦ）、ジメ
チルアセトアミド（ＤＭＡ）の１種以上を挙げることが
できる。In the method of the present invention, a solvent is preferably used, and the solvent may be tetrahydrofuran (TH
F), dioxane, dimethoxyethane (DME), ethers such as ethers, dimethylformamide (DM
It is preferable to use one or more of amide solvents such as F) and dimethylacetamide (DMA). More preferred solvents in the method of the present invention include one or more of tetrahydrofuran (THF), dimethoxyethane (DME), dimethylformamide (DMF), and dimethylacetamide (DMA).
【００２０】本発明の方法における反応温度は、特に制
限はないが、好ましくは−２０℃〜溶媒の沸点温度、よ
り好ましくは０℃〜室温である。The reaction temperature in the method of the present invention is not particularly limited, but is preferably from -20 ° C to the boiling point of the solvent, more preferably from 0 ° C to room temperature.
【００２１】本発明の方法は、マンガン、好ましくは金
属マンガンの存在下に、トリハロメチル基を有する化合
物とハロゲン化シランとを、好ましくは溶媒の存在下
に、これらを混合して反応させることができる。本発明
の方法は、マンガン誘導体、好ましくは金属マンガンの
存在下に反応させることにより行うことができるが、反
応系にさらにヨウ化ナトリウムなどのアルカリ金属ハロ
ゲン化物を存在させることもできる。本発明の方法にお
いて使用されるハロゲン化アルカリ金属としては、ナト
リウムのハロゲン化物が好ましく、具体的にはヨウ化ナ
トリウムなどが挙げられる。In the method of the present invention, a compound having a trihalomethyl group and a halogenated silane are mixed and reacted in the presence of manganese, preferably metallic manganese, preferably in the presence of a solvent. it can. The method of the present invention can be carried out by reacting in the presence of a manganese derivative, preferably metal manganese. However, an alkali metal halide such as sodium iodide can be further present in the reaction system. As the alkali metal halide used in the method of the present invention, a sodium halide is preferable, and specific examples include sodium iodide.
【００２２】本発明の好ましい態様を前記の一般式
（Ｉ）を用いて化学反応式で示すと次の反応式（１）の
ようになる。 Ｒ−ＣＸ３ ＋ Ｚ３−Ｓｉ−Ｘ’ → Ｒ−ＣＸ２−Ｓｉ−Ｚ３ （１） （式中、Ｒ及びＸは前記のものを示し、Ｘ’はハロゲン
原子を示し、Ｚはシランの置換基を示す。）A preferred embodiment of the present invention is represented by the following reaction formula (1) when represented by a chemical reaction formula using the above general formula (I). R—CX 3 + Z 3 —Si—X ′ → R—CX 2 —Si—Z 3 (1) (wherein, R and X are as described above, X ′ is a halogen atom, and Z is silane Represents a substituent.)
【００２３】さらに、本発明のより好ましい態様をより
具体的な化学反応式で示すと次の反応式（２）のように
なる。 ＣＨＩ３ ＋ Ｍｅ３ＳｉＣｌ → Ｍｅ３ＳｉＣＨＩ２ （２） （式中、Ｍｅはメチル基を示す。）Further, the more preferable embodiment of the present invention is represented by the following reaction formula (2) by a more specific chemical reaction formula. CHI 3 + Me 3 SiCl → Me 3 SiCHI 2 (2) (In the formula, Me represents a methyl group.)
【００２４】本発明の方法で製造されたシリル化ジハロ
メチル基を有する化合物、より具体的にはジヨードメチ
ルトリメチルシランは、これを反応系から単離して次の
反応に使用してもよいが、これを単離することなくその
まま次の反応に使用することもできる。The compound having a silylated dihalomethyl group produced by the method of the present invention, more specifically, diiodomethyltrimethylsilane may be isolated from the reaction system and used in the next reaction. This can be used for the next reaction without isolation.
【００２５】[0025]
【実施例】次に実施例を挙げて本発明の方法をより具体
的に説明するが、本発明の方法はこれらの実施例に限定
されるものではない。Next, the method of the present invention will be described more specifically with reference to examples. However, the method of the present invention is not limited to these examples.
【００２６】実施例１（ジヨードメチルトリメチルシラ
ンの合成） アルゴン雰囲気下、金属マンガン（０．３３ｇ，６．０
ｍｍｏｌ）のＴＨＦ（４ｍＬ）懸濁液に、クロロトリメ
チルシラン（０．７６ｍＬ，６．０ｍｍｏｌ）を加え、
２５℃で３０分間撹拌した。０℃にして、ヨードホルム
（０．８０ｇ，２．０ｍｍｏｌ）のＴＨＦ（６ｍＬ）溶
液を滴下した。１時間攪拌したのち、反応混合物を、セ
ライトでろ過し、水（２５ｍＬ）に注ぎ、ジエチルエー
テル（３ｘ２５ｍＬ）で抽出した。有機層を分離した
後、チオ硫酸ナトリウムと食塩水で洗い、無水硫酸マグ
ネシウムで乾燥した。濃縮ののち、ジヨードメチルトリ
メチルシランを０．１８ｇ（収率２６％）得た。 ジヨードメチルトリメチルシラン（Diiodomethyltrimet
hylsilane）： ｂｐ．４９−５０℃（０．７Ｔｏｒｒ）； ＩＲ（ｎｅａｔ）：２９５３，２８９５，１２６０，１
２５０，１０６１，８４０，７５８，７０９，６９６ｃ
ｍ−１；１ Ｈ−ＮＭＲ（ＣＤＣｌ３）：δ ０．２５（ｓ，９
Ｈ），４．４４（ｓ，１Ｈ）．Example 1 (Synthesis of diiodomethyltrimethylsilane) Metal manganese (0.33 g, 6.0) under an argon atmosphere
chlorotrimethylsilane (0.76 mL, 6.0 mmol) was added to a THF (4 mL) suspension of
Stirred at 25 ° C. for 30 minutes. The temperature was adjusted to 0 ° C., and a solution of iodoform (0.80 g, 2.0 mmol) in THF (6 mL) was added dropwise. After stirring for 1 hour, the reaction mixture was filtered over celite, poured into water (25 mL) and extracted with diethyl ether (3 × 25 mL). After separating the organic layer, it was washed with sodium thiosulfate and brine, and dried over anhydrous magnesium sulfate. After concentration, 0.18 g (yield 26%) of diiodomethyltrimethylsilane was obtained. Diiodomethyltrimethylsilane
hylsilane): bp. 49-50 ° C. (0.7 Torr); IR (neat): 2953, 2895, 1260, 1
250, 1061, 840, 758, 709, 696c
m -1 ; 1 H-NMR (CDCl 3 ): δ 0.25 (s, 9
H), 4.44 (s, 1H).
【００２７】実施例２（ジヨードメチルトリメチルシラ
ンの合成） アルゴン雰囲気下、金属マンガン（０．３３ｇ，６．０
ｍｍｏｌ）、ヨウ化ナトリウム（８９ｍｇ，０．６ｍｍ
ｏｌ）のジメトキシエタン（４ｍＬ）懸濁液に、クロロ
トリメチルシラン（０．７６ｍＬ，６．０ｍｍｏｌ）を
加え、２５℃で３０分間撹拌した。２５℃の水浴にし
て、ヨードホルム（０．８０ｇ，２．０ｍｍｏｌ）のジ
メトキシエタン（６ｍＬ）溶液を滴下した。１時間攪拌
したのち、反応混合物を、セライトでろ過し、水（２５
ｍＬ）に注ぎ、ジエチルエーテル（３ｘ２５ｍＬ）で抽
出した。有機層を分離した後、チオ硫酸ナトリウムと食
塩水で洗い、無水硫酸マグネシウムで乾燥した。濃縮の
のち、ジヨードメチルトリメチルシランを０．４０ｇ
（収率５９％）得た。Example 2 (Synthesis of diiodomethyltrimethylsilane) Metal manganese (0.33 g, 6.0) under an argon atmosphere
mmol), sodium iodide (89 mg, 0.6 mm
ol) in dimethoxyethane (4 mL) was added with chlorotrimethylsilane (0.76 mL, 6.0 mmol) and stirred at 25 ° C. for 30 minutes. In a water bath at 25 ° C., a solution of iodoform (0.80 g, 2.0 mmol) in dimethoxyethane (6 mL) was added dropwise. After stirring for 1 hour, the reaction mixture was filtered through celite, and water (25
mL) and extracted with diethyl ether (3 × 25 mL). After separating the organic layer, it was washed with sodium thiosulfate and brine, and dried over anhydrous magnesium sulfate. After concentration, 0.40 g of diiodomethyltrimethylsilane
(59% yield).
【００２８】[0028]
【発明の効果】本発明の方法により合成中間体として工
業的にも重要なジハロメチルシリル基を有する化合物、
特にジヨードメチルトリメチルシランを、簡便かつ安全
な方法で製造することができる。本発明はこれらの化合
物の工業的な製造方法を提供するものである。According to the method of the present invention, a compound having a dihalomethylsilyl group which is industrially important as a synthetic intermediate,
In particular, diiodomethyltrimethylsilane can be produced by a simple and safe method. The present invention provides an industrial production method for these compounds.
Claims (7)
ゲン化シランとをマンガンの存在下に反応させてシリル
化ジハロメチル基を有する化合物を製造する方法。1. A method for producing a compound having a silylated dihalomethyl group by reacting a compound having a trihalomethyl group with a halogenated silane in the presence of manganese.
ホルムであり、ハロゲン化シランがハロゲン化トリ炭化
水素シランである請求項１に記載の方法。2. The method according to claim 1, wherein the compound having a trihalomethyl group is haloform, and the halogenated silane is a halogenated trihydrocarbon silane.
ドホルムであり、ハロゲン化シランがクロロトリメチル
シランである請求項１又は２に記載の方法。3. The method according to claim 1, wherein the compound having a trihalomethyl group is iodoform, and the halogenated silane is chlorotrimethylsilane.
３のいずれかに記載の方法。4. The reaction temperature according to claim 1, wherein the reaction temperature is 0 ° C. to room temperature.
3. The method according to any one of 3.
の存在下に行われる請求項１〜４のいずれかに記載の方
法。5. The method according to claim 1, wherein the reaction is further performed in the presence of an alkali metal halide.
トリウムである請求項５に記載の製造方法。6. The method according to claim 5, wherein the alkali metal halide is sodium iodide.
媒の１種以上である請求項１〜６のいずれかに記載の製
造方法。7. The production method according to claim 1, wherein the reaction solvent is at least one of an ether-based solvent and an amide-based solvent.
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| JP21585998A JP3895053B2 (en) | 1998-07-30 | 1998-07-30 | Production method of dihalomethylsilanes |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017201456A1 (en) * | 2016-05-19 | 2017-11-23 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Preparation of si-h containing iodosilanes via halide exchange reaction |
| US10384944B2 (en) | 2016-05-19 | 2019-08-20 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Preparation of Si—H containing iodosilanes via halide exchange reaction |
| KR20210003222A (en) * | 2018-05-01 | 2021-01-11 | 밀리켄 앤드 캄파니 | Method for producing halosilane compound |
-
1998
- 1998-07-30 JP JP21585998A patent/JP3895053B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017201456A1 (en) * | 2016-05-19 | 2017-11-23 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Preparation of si-h containing iodosilanes via halide exchange reaction |
| US10384944B2 (en) | 2016-05-19 | 2019-08-20 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Preparation of Si—H containing iodosilanes via halide exchange reaction |
| US10800661B2 (en) | 2016-05-19 | 2020-10-13 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Preparation of Si-H containing iodosilanes via halide exchange reaction |
| KR20210003222A (en) * | 2018-05-01 | 2021-01-11 | 밀리켄 앤드 캄파니 | Method for producing halosilane compound |
| KR102577557B1 (en) | 2018-05-01 | 2023-09-11 | 밀리켄 앤드 캄파니 | Method for producing halosilane compounds |
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