JP3895053B2 - Production method of dihalomethylsilanes - Google Patents
Production method of dihalomethylsilanes Download PDFInfo
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- JP3895053B2 JP3895053B2 JP21585998A JP21585998A JP3895053B2 JP 3895053 B2 JP3895053 B2 JP 3895053B2 JP 21585998 A JP21585998 A JP 21585998A JP 21585998 A JP21585998 A JP 21585998A JP 3895053 B2 JP3895053 B2 JP 3895053B2
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- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000000034 method Methods 0.000 claims description 21
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical group C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- OKJPEAGHQZHRQV-UHFFFAOYSA-N iodoform Chemical compound IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 14
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical group [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 12
- 150000004756 silanes Chemical class 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 125000004953 trihalomethyl group Chemical group 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 4
- 150000008045 alkali metal halides Chemical class 0.000 claims description 4
- 125000006371 dihalo methyl group Chemical group 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 235000009518 sodium iodide Nutrition 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- RXBPBTHLRBDCFU-UHFFFAOYSA-N diiodomethyl(trimethyl)silane Chemical compound C[Si](C)(C)C(I)I RXBPBTHLRBDCFU-UHFFFAOYSA-N 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- -1 alkenyl silanes Chemical class 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 3
- 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 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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 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
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012267 brine Substances 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
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000002994 raw material 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
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 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
- 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 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
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 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
- 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
- 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
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 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
- 150000004820 halides Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 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
- 238000000926 separation method Methods 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
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 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
Description
【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。
【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。
【０００３】
【化１】
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. Organomet. Chem., 1970, 24, 647）。
また、次式で示される方法も知られている。
【０００５】
【化２】
この方法もクロロトリメチルシランを−９０℃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. Fr., 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。
【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（Ｍｅ３ＳｉＣＨＩ２）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。
【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。
【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（Ｍｅ３ＳｉＣｌ）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（Ｍｅ３ＳｉＣＨＩ２）の製造方法に関する。
【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。
【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。）
【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。
【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。
【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。
【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。
【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。
【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。
【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（ＴＨＦ）、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（ＤＭＦ）、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。
【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。
【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。
【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。）
【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。）
【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。
【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。
【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，６．０ｍｍｏｌ）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（Diiodomethyltrimethylsilane）：
ｂｐ．４９−５０℃（０．７Ｔｏｒｒ）；
ＩＲ（ｎｅａｔ）：２９５３，２８９５，１２６０，１２５０，１０６１，８４０，７５８，７０９，６９６ｃｍ−１；
１Ｈ−ＮＭＲ（ＣＤＣｌ３）：δ ０．２５（ｓ，９Ｈ），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，６．０ｍｍｏｌ）、ヨウ化ナトリウム（８９ｍｇ，０．６ｍｍｏｌ）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（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０．４０ｇ（収率５９％）得た。
【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。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel method for producing dihalomethylsilanes.
[0002]
[Prior art]
Conventionally, it has been known that diiodomethyltrimethylsilane (Me 3 SiCHI 2 ) can be obtained from diiodomethane or iodoform, but both require extremely low temperatures (−90 ° C.) and are industrially problematic. .
For example, a method represented by the following reaction formula is known.
[0003]
[Chemical 1]
In this method, a Grignard reagent is reacted with iodoform at −85 ° C. to form diiodomethylmagnesium chloride, and this is reacted with chlorotrimethylsilane at −85 ° C. to obtain the desired diiodomethyltrimethylsilane (Me 3 SiCHI 2). ) In a yield of about 77% (Seyferth, D., et al., J. Organomet. Chem., 1970, 24, 647).
A method represented by the following equation is also known.
[0005]
[Chemical 2]
This method is the same as the above method in that chlorotrimethylsilane is reacted at -90 ° C, but differs in that diiodomethane is used as a starting material. That is, sodium hexamethyldisilazide is allowed to act on diiodomethane at −90 ° C. to form diiodomethyl sodium, which is reacted with chlorotrimethylsilane at −90 ° C. to obtain the desired diiodomethyltrimethylsilane (Me 3 SiCHI 2). ) In a yield of about 67% (Charreau, P., Bull. Chem. Soc. Fr., 1990, 127, 275).
[0007]
The diiodomethane derivative is not only useful as a raw material for the Simmons-Smith reaction for synthesizing a cyclopropane ring, but the diiodomethyltrimethylsilane of the present invention further has a silyl group and reacts with aldehydes. Thus, it is a compound useful as a raw material for synthesizing alkenyl silanes in which a silyl group is substituted at the vinyl position. These cyclopropane derivatives and alkenylsilanes are useful as synthetic intermediates for physiologically active substances such as various drugs and agricultural chemicals and various industrial materials.
[0008]
[Problems to be solved by the invention]
The diiodomethyltrimethylsilane (Me 3 SiCHI 2 ) of the present invention is metallized with a strong base having a very low temperature of −85 ° C. to −90 ° C. and is captured by chlorotrimethylsilane. However, industrial methods are not known, and they were only slightly experimentally produced.
The present invention provides a method by which a compound having a silylated dihalomethyl group such as diiodomethyltrimethylsilane (Me 3 SiCHI 2 ) can be easily and industrially produced.
[0009]
[Means for Solving the Problems]
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 halogenated silane in the presence of manganese. The compound having a trihalomethyl group of the present invention is preferably haloform, more preferably iodoform. In addition, the halogenated silane of the present invention is preferably a halogenated trialkylsilane, more preferably chlorotrimethylsilane.
[0010]
Therefore, in more detail, the present invention relates to production of diiodomethyltrimethylsilane (Me 3 SiCHI 2 ) obtained by reacting iodoform (CHI 3 ) and chlorotrimethylsilane (Me 3 SiCl) in the presence of manganese metal. Regarding the method.
[0011]
The compound having a trihalomethyl group of the present invention has one halogen atom involved in the reaction in the trihalomethyl group and does not have a functional group that may inhibit the reaction of the present invention in the molecule. There is no restriction | limiting in particular, As a compound which has a preferable trihalomethyl group, the compound shown with the following general formula (I) can be mentioned.
[0012]
R-CX 3 (I)
(In the formula, R represents a hydrogen atom or an organic residue, and X represents the same or different halogen atoms.)
[0013]
As the organic residue R in the general formula (I), a linear or branched alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, 4 to 30 carbon atoms, Preferably it is 5-20, more preferably 6-10, a monocyclic, polycyclic or condensed cycloalkyl group, 6-30 carbons, preferably 6-20, more preferably 6-10 monocyclic, polycyclic. A ring or condensed cyclic aryl group, having at least one nitrogen atom, oxygen atom or sulfur atom in the ring, and the size of one ring is 5 to 20 members, preferably 5 to 10 members, more preferably 5 to 7-membered, saturated or unsaturated monocyclic, polycyclic or condensed heterocyclic group which may be condensed with the cycloalkyl group or aryl group, and the alkyl group described above. Substituted by aryl, cycloalkyl or heterocyclic groups Aralkyl groups, such as cycloalkylalkyl group or heterocyclic group-substituted alkyl group.
[0014]
These alkyl group, cycloalkyl group, aryl group, heterocyclic group, aralkyl group, cycloalkylalkyl group or heterocyclic group-substituted alkyl group is one or more substituents that do not inhibit the reaction of the present invention. These substituents include a keto group, a lower acyl group, a lower alkoxy group, a halogen and the like in addition to the alkyl group described above.
[0015]
Examples of the organic residue of R in the general formula (I) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, and n-octyl group. Alkyl groups such as n-nonyl group and n-decyl group, cycloalkyl groups such as cyclohexyl group and cyclopentyl group, aryl groups such as phenyl group and naphthyl group, heterocyclic groups such as thienyl group and furanyl group, benzyl group, Examples include aralkyl groups such as a phenethyl group.
[0016]
R in the general formula (I) may be the organic residue, but is preferably a hydrogen atom.
[0017]
X in the general formula (I) is a halogen atom such as fluorine, chlorine, bromine or iodine, and the three halogen atoms may be the same or different, but preferably the same A halogen atom, more preferably three iodine atoms.
[0018]
As the halogenated silane of the present invention, any compound having a reactive halogen-silicon bond can be used for the reaction, but preferably the remaining three groups of silane have the organic residues described above. More preferred are hydrocarbon groups such as alkyl groups and aryl groups. The remaining three groups of the halogenated silane may be the same or different. Preferred halogenated silanes include halogenated trihydrocarbon silanes, and more specifically, halogenated trialkylsilanes such as chlorotrimethylsilane and chlorotriethylsilane, halogens such as chlorophenyldimethylsilane and chlorodiphenylmethylsilane. And aryldialkoxysilanes, halogenated alkyldiarylsilanes, and halogenated triarylsilanes. Further, the halogen of the halogenated silane may be the aforementioned halogen, but chlorine is preferred.
[0019]
In the method of the present invention, it is preferable to use a solvent. Examples of the solvent include tetrahydrofuran (THF), dioxane, dimethoxyethane (DME), ethers such as ether, dimethylformamide (DMF), dimethylacetamide (DMA), and the like. It is preferable to use one or more amide solvents in combination. As a more preferable solvent in the method of the present invention, one or more of tetrahydrofuran (THF), dimethoxyethane (DME), dimethylformamide (DMF), and dimethylacetamide (DMA) can be mentioned.
[0020]
Although there is no restriction | limiting in particular in the reaction temperature in the method of this invention, Preferably it is -20 degreeC-boiling point temperature of a solvent, More preferably, it is 0 degreeC-room temperature.
[0021]
In the method of the present invention, a compound having a trihalomethyl group and a halogenated silane can be mixed and reacted in the presence of manganese, preferably metal manganese, preferably in the presence of a solvent.
The method of the present invention can be carried out by reacting in the presence of a manganese derivative, preferably metal manganese, but an alkali metal halide such as sodium iodide can also be present in the reaction system. As the alkali metal halide used in the method of the present invention, a halide of sodium is preferable, and specific examples thereof include sodium iodide.
[0022]
A preferred embodiment of the present invention is represented by the following chemical reaction formula (1) using the above general formula (I).
R—CX 3 + Z 3 —Si—X ′ → R—CX 2 —Si—Z 3 (1)
(In the formula, R and X are as defined above, X ′ is a halogen atom, and Z is a substituent of silane.)
[0023]
Furthermore, when a more preferable embodiment of the present invention is shown by a more specific chemical reaction formula, the following reaction formula (2) is obtained.
CHI 3 + Me 3 SiCl → Me 3 SiCHI 2 (2)
(In the formula, Me represents a methyl group.)
[0024]
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. It can also be used for the next reaction without separation.
[0025]
【Example】
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]
Example 1 (Synthesis of diiodomethyltrimethylsilane)
Under an argon atmosphere, chlorotrimethylsilane (0.76 mL, 6.0 mmol) was added to a suspension of metal manganese (0.33 g, 6.0 mmol) in THF (4 mL), and the mixture was stirred at 25 ° C. for 30 minutes. At 0 ° C., 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 through celite, poured into water (25 mL) and extracted with diethyl ether (3 × 25 mL). The organic layer was separated, washed with sodium thiosulfate and brine, and dried over anhydrous magnesium sulfate. After concentration, 0.18 g (yield 26%) of diiodomethyltrimethylsilane was obtained.
Diiodomethyltrimethylsilane:
bp. 49-50 ° C. (0.7 Torr);
IR (neat): 2953, 2895, 1260, 1250, 1061, 840, 758, 709, 696 cm −1 ;
1 H-NMR (CDCl 3 ): δ 0.25 (s, 9H), 4.44 (s, 1H).
[0027]
Example 2 (Synthesis of diiodomethyltrimethylsilane)
Chlorotrimethylsilane (0.76 mL, 6.0 mmol) was added to a suspension of metal manganese (0.33 g, 6.0 mmol) and sodium iodide (89 mg, 0.6 mmol) in dimethoxyethane (4 mL) under an argon atmosphere. In addition, the mixture was stirred at 25 ° C. for 30 minutes. In a 25 ° C. water bath, 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, poured into water (25 mL) and extracted with diethyl ether (3 × 25 mL). The organic layer was separated, washed with sodium thiosulfate and brine, and dried over anhydrous magnesium sulfate. After concentration, 0.40 g (59% yield) of diiodomethyltrimethylsilane was obtained.
[0028]
【The invention's effect】
By the method of the present invention, a compound having a dihalomethylsilyl group that is industrially important as a synthetic intermediate, particularly diiodomethyltrimethylsilane, can be produced in a simple and safe manner. The present invention provides an industrial process for producing these compounds.
Claims (7)
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