JPS6222790A - Production of tertiary hydrocarbonsilyl compound - Google Patents
Production of tertiary hydrocarbonsilyl compoundInfo
- Publication number
- JPS6222790A JPS6222790A JP60163548A JP16354885A JPS6222790A JP S6222790 A JPS6222790 A JP S6222790A JP 60163548 A JP60163548 A JP 60163548A JP 16354885 A JP16354885 A JP 16354885A JP S6222790 A JPS6222790 A JP S6222790A
- Authority
- JP
- Japan
- Prior art keywords
- tertiary
- grignard reagent
- compound
- tertiary hydrocarbon
- group
- 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 12
- 150000001875 compounds Chemical class 0.000 title abstract description 5
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 16
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 16
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 15
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 15
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- -1 silyl compound Chemical class 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- MDLRQEHNDJOFQN-UHFFFAOYSA-N methoxy(dimethyl)silicon Chemical compound CO[Si](C)C MDLRQEHNDJOFQN-UHFFFAOYSA-N 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- CQRPUKWAZPZXTO-UHFFFAOYSA-M magnesium;2-methylpropane;chloride Chemical compound [Mg+2].[Cl-].C[C-](C)C CQRPUKWAZPZXTO-UHFFFAOYSA-M 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- GBIVWHCGIPAPPG-UHFFFAOYSA-N tert-butyl(ethoxy)silane Chemical compound CCO[SiH2]C(C)(C)C GBIVWHCGIPAPPG-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SWGWDYZQRUQDBU-UHFFFAOYSA-N tert-butyl-ethoxy-methylsilane Chemical compound CCO[SiH](C)C(C)(C)C SWGWDYZQRUQDBU-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OLIBVNMJDNNSKI-UHFFFAOYSA-N CC(C)(C)[Mg] Chemical compound CC(C)(C)[Mg] OLIBVNMJDNNSKI-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- REWAIEPNWASBIQ-UHFFFAOYSA-M Cl[Mg]C(C)(C)C1=CC=CC=C1 Chemical compound Cl[Mg]C(C)(C)C1=CC=CC=C1 REWAIEPNWASBIQ-UHFFFAOYSA-M 0.000 description 1
- 235000011511 Diospyros Nutrition 0.000 description 1
- 244000236655 Diospyros kaki Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000007664 blowing 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
- 230000005587 bubbling Effects 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
- HXLVDKGPVGFXTH-UHFFFAOYSA-N butyl(dimethyl)silane Chemical compound CCCC[SiH](C)C HXLVDKGPVGFXTH-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl 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
- LGGVVBJZJDTYBE-UHFFFAOYSA-N dimethyl(2-methylbutan-2-yl)silane Chemical compound CCC(C)(C)[SiH](C)C LGGVVBJZJDTYBE-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 229940094443 oxytocics prostaglandins Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- CRNIHJHMEQZAAS-UHFFFAOYSA-N tert-amyl chloride Chemical compound CCC(C)(C)Cl CRNIHJHMEQZAAS-UHFFFAOYSA-N 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
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- OZWKZRFXJPGDFM-UHFFFAOYSA-N tripropoxysilane Chemical compound CCCO[SiH](OCCC)OCCC OZWKZRFXJPGDFM-UHFFFAOYSA-N 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
- 238000010792 warming Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（監業上の利用分野）
本発明は第３級炭化水素シリル化合物の製造方法、特に
は工業的に危険なリチウム化合物を使用しないで安全に
かつ容ＭＥ、医薬品などの合成に有効な特殊シリル化剤
として有用な第３級炭化水素シリル化合物を製造する方
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of use in supervision) The present invention provides a method for producing tertiary hydrocarbon silyl compounds, in particular, a method for producing silyl compounds of tertiary hydrocarbons, which can be produced safely without using lithium compounds, which are industrially dangerous. The present invention relates to a method for producing a tertiary hydrocarbon silyl compound useful as a special silylating agent effective in the synthesis of.
（従来の技術）
第３級炭化水素基をけいＸＩｉ！子と結合させる方法と
しては、従来、第３級アルキルリチウムを利用する方法
が知られているが、この方法は金属リチウム、有機リチ
ウムの取扱いが危険なことから工業的方法とはいえず、
他の方法の出現が望まれている。(Prior art) Determining the tertiary hydrocarbon group XIi! Conventionally, a method using tertiary alkyl lithium is known as a method for bonding with a molecule, but this method cannot be called an industrial method because handling of metal lithium and organic lithium is dangerous.
It is hoped that other methods will emerge.
（発明の構成）
本発明はこのような要望に応えることのできる第３級炭
化水素シリル化合物の製造方法に関するものであｊｌ、
これは一般式 Ｒ’ ＭｇＸ（こ＼にＲ１は第３級炭化
水素基、Ｘはハロゲン原子〕で示されるグリニヤール試
薬と、一般式人Ｒ８１）Ｉ （こ−にＲは非
置換まｍｎ ４−ｍ−ｎ
たは置換１価炭化水系基、Ａはアルコキシ基、ｍは１，
２または３．ｎは０，１または２．ｍ＋ｎ≦３）で示さ
れる有機けい素化合物とを有機溶媒中で反応させること
を特徴とするものである。(Structure of the Invention) The present invention relates to a method for producing a tertiary hydrocarbon silyl compound that can meet such demands.
This is a Grignard reagent represented by the general formula R' MgX (wherein R1 is a tertiary hydrocarbon group and m-n or a substituted monovalent hydrocarbon group, A is an alkoxy group, m is 1,
2 or 3. n is 0, 1 or 2. m+n≦3) is reacted with an organosilicon compound represented by m+n≦3) in an organic solvent.
すなわち１本発明者らは第３級炭化水素シリル化合物の
工業的な製造方法について種々検討した結果、第３級炭
化水素基を含有するグリニヤール試薬と上記した一般式
で示される有機けい素化合物を反応させるとグリニヤー
ル試薬中の第３級炭化水素基と有機けい素化合物中のア
ルコキシ基とが置換されて第３級炭化水素シリル化合物
が容具に得られること、またこ＼にｆｌられた第３級炭
化水素シリル化合物はけい素に結合した水素原子をもっ
ているので四塩化炭素などと反応させれげ容島にクロロ
シランとすることができるで各柿シリル化剤を有利に製
造し得ることを確認して本発明を完成させた。Namely, 1. As a result of various studies on industrial methods for producing tertiary hydrocarbon silyl compounds, the present inventors found that a Grignard reagent containing a tertiary hydrocarbon group and an organosilicon compound represented by the above general formula were used. When reacted, the tertiary hydrocarbon group in the Grignard reagent and the alkoxy group in the organosilicon compound are substituted, and a tertiary hydrocarbon silyl compound is obtained in the container. Since tertiary hydrocarbon silyl compounds have silicon-bonded hydrogen atoms, they can be reacted with carbon tetrachloride to form chlorosilanes, and it has been confirmed that various persimmon silylation agents can be advantageously produced. The present invention was completed.
本発明の方法で使用させるグリニヤール試薬は一般式
ＲｌＭｇＸ で示され、このＲ１はｔ−ブチル基、１
．１−ジメチルプロピル基、１，１−ジエチルプロピル
基などの第３級アルキル基−１、ｌ−ジメチルベンジル
基などの了り−ル基を含んだ第３級アルキル基で例示さ
れる第３級炭化水素基。The Grignard reagent used in the method of the present invention has the general formula
It is represented by RlMgX, where R1 is a t-butyl group, 1
．． Tertiary alkyl groups such as 1-dimethylpropyl group and 1,1-diethylpropyl group - Tertiary alkyl groups including tertiary alkyl groups such as 1,1-dimethylbenzyl group Hydrocarbon group.
Ｘは塩累、臭素などのハロゲン原子とされるものであ：
）、これにはｔ−ブチルマグネシウムクロライド−１，
１−ジメチルプロピルマグネシウムブロミ）”、１．１
−ジエチルプロピルマグネシウムクロライド、１．１−
ジメチルベンジルマグネシウムクロライドなどが例示さ
れる。なお、このグリニヤール試薬は解法でｍ表するこ
とができ、これは例えはフラスコ中に金属マグネシウム
と不活性溶剤とｌ−てのテトラハイドロフランを仕込み
、こ＼にハロゲン化第３級炭化水素化合物を滴下し加温
化に反応させることによって得ることがで炒る。X is a salt or a halogen atom such as bromine:
), which includes t-butylmagnesium chloride-1,
1-dimethylpropylmagnesium bromide)”, 1.1
-diethylpropylmagnesium chloride, 1.1-
Examples include dimethylbenzylmagnesium chloride. In addition, this Grignard reagent can be expressed as m in the solution method, which means, for example, that metal magnesium, an inert solvent, and 1-tetrahydrofuran are placed in a flask, and a halogenated tertiary hydrocarbon compound is added to this. Roasting can be obtained by dropping and reacting with warming.
また、こ〜に使用される有機けい素化合物は一般式 〜
ＲＨ８１Ｈ，−、−、で示され、このＲ３はメチル基、
エチル基、プロピル基、ブチル基などのアルキル基、ビ
ニル基、アリル基などのアルケニル基−フェニル基−ト
リル基などのアリール基、シクロヘキシル基などのシク
ロアルキル基マたはこれらの基の炭素原子に結合した水
系原子の一部または全部をハロゲン原子−シアノ基２シ
リルエーテル基、ピラニエルエーテル基などで置換した
基かＩ−）ｉ１！択される非置換または置換１価炭化水
素基、Ａはメトキシ基−エトキシ基などのアルコキシ基
、ｍは１〜３の整数、ｎは０〜２の整数でｍ ＋ ｎが
３以下の整数とされるものであ＋３．これには
メチルジメトキシシラｙ ０Ｈ３（ＯＨａＯ）２Ｓｉ
Ｈ。In addition, the organosilicon compound used for this has the general formula ~
RH81H, -, -, this R3 is a methyl group,
Alkyl groups such as ethyl, propyl, and butyl groups, alkenyl groups such as vinyl and allyl groups, phenyl groups, aryl groups such as tolyl groups, cycloalkyl groups such as cyclohexyl groups, or carbon atoms of these groups. A group in which part or all of the bonded aqueous atoms are substituted with a halogen atom, a cyano group, a silyl ether group, a pyraniel ether group, etc. I-)i1! A is an alkoxy group such as a methoxy group or an ethoxy group, m is an integer of 1 to 3, n is an integer of 0 to 2, and m + n is an integer of 3 or less; +3. This includes methyldimethoxysilay0H3(OHaO)2Si
H.
トリメトキシシラｙ （ＯＨ，Ｏ）３，７３１Ｈ。Trimethoxysilay (OH, O) 3,731H.
ジメチルメトキシシラ／ （ＯＨ，）２（ＯＨ３０）
ＳＩＨ。Dimethylmethoxysila/ (OH,)2(OH30)
S.I.H.
メチルジェトキシシラ７０Ｈ３ＣらＨ，０）２ＳｉＨ。Methyljethoxysila70H3C et al H,0)2SiH.
トリプロポキシシラン （ＯＨＯ） Ｓ’ｉ”Ｈ＋エ
チルジェトキシシラｙ Ｏ，Ｈ，（０２Ｈ，０）２８
ｉＨなどが例示される。Tripropoxysilane (OHO) S'i”H+ethyljetoxysilane O,H, (02H,0)28
iH etc. are exemplified.
本発明の方洪は上記したグリニヤール試薬と有機けい素
化合物とを反応させて第３級炭化水素シリル化合物る得
るものであ１３．この反応は次式％式％
によって進行するが、この反応は１０〜１５０℃。13. The method of the present invention is to react the Grignard reagent described above with an organosilicon compound to obtain a tertiary hydrocarbon silyl compound.13. This reaction proceeds according to the following formula % formula %, and this reaction is carried out at 10 to 150°C.
好ましくは４０〜１００℃の温度範囲で行なわせること
がよい。この反応に使用される有機溶剤としてはジエチ
ルエーテル、テトラハイドロフランなどのエーテル系溶
剤、ヘキサメチルホスホリックアミドなどのリン酸アミ
ド溶剤、ベンゼン、トルエンなどの炭化水素系溶剤が例
示され、これらはその２揮または２種以上の混合溶剤と
し、て使用してもよいか、グリニヤール試薬の調製時に
使用したときに試薬の生成速度が遠くな番）、生成率も
高くするテトラハイドロフランを用いることが好ましい
。また、この反応系は酸素が存在するとその反応段階で
グリニヤール試薬が酸素と反応して収率低下の原因とな
るので、窒素、アルゴンなどの不活性雰囲気下で行なう
ことがよい。Preferably, the temperature range is 40 to 100°C. Examples of organic solvents used in this reaction include ether solvents such as diethyl ether and tetrahydrofuran, phosphoric acid amide solvents such as hexamethylphosphoric amide, and hydrocarbon solvents such as benzene and toluene. It may be used as a two-volatile solvent or a mixed solvent of two or more solvents, or it is possible to use tetrahydrofuran, which increases the production rate (as the reagent production rate is slow when used in the preparation of Grignard reagents). preferable. Furthermore, if oxygen is present in this reaction system, the Grignard reagent will react with oxygen during the reaction step, causing a decrease in yield, so it is preferable to carry out the reaction under an inert atmosphere such as nitrogen or argon.
なお１本発明の方法によれば特殊な設備を使用しなくて
も安全に目的とする第三級炭化氷菓シリル化合物を高い
収率で容易に得ることができるという有利性が与えられ
るが、この方法で得られた第３級炭化水素シリル化合物
は容易に第３級炭化水系ジアルキルハロシラｙなどとす
ることができ。Note that the method of the present invention has the advantage that the target tertiary carbonized frozen silyl compound can be easily obtained in high yield safely without using special equipment. The tertiary hydrocarbon silyl compound obtained by this method can be easily converted into a tertiary hydrocarbon dialkylhalosilyl compound and the like.
このものは分子内にかさ高第３級炭化水素基をもってい
るので■立体選択性が高い、■トリメチルシリルエーテ
ル型にくらべて化学的に安定である。Since this product has a bulky tertiary hydrocarbon group in its molecule, 1) it has high stereoselectivity, and 2) it is chemically stable compared to the trimethylsilyl ether type.
ということからステロイド−プロスタグランジンなどの
合成に有効なシリル化剤とされるという有用性をもつも
のであ６」、この方法を利用して合成される特殊シリル
化剤としてはｔ−ブチルジメチルクロロシラン、ｔ−７
’チルジフエニルクワロシランなどが例示される。Therefore, it has the usefulness of being an effective silylating agent for the synthesis of steroid prostaglandins, etc.6'', and t-butyldimethyl is a special silylating agent synthesized using this method. Chlorosilane, t-7
Examples include tyldiphenylqualosilane.
実施例１
５００ｔｎｌのフラスコ中に金属マグネシウム１２ｇ（
０，５モル）、テトラハイドロフラン３００１Ｒ１およ
び少量のヨウ素を仕込み、窒素ガス雰囲気下にこ＼Ｋｔ
−ブチルクロライド４６．３ ｇ（０，５モル）を内温
４０〜５０℃で１１）＝＆聞で滴下し、さらに５５℃で
１時間攪拌してグリニヤール試薬としてのｔ−プチルマ
グネシウ今りｐライ１ドを調製した。Example 1 12 g of metallic magnesium (
0.5 mol), tetrahydrofuran 3001R1 and a small amount of iodine, and place it under a nitrogen gas atmosphere.
46.3 g (0.5 mol) of butyl chloride was added dropwise at an internal temperature of 40 to 50°C, and the mixture was further stirred at 55°C for 1 hour to prepare t-butylmagnesium as a Grignard reagent. Ride 1 was prepared.
つぎＫこ−に内温６０℃でメチルジェトキシシラン６７
ｇ（０，５モル）を１時間で滴下し一滴下終了後も内温
６６℃で３時間攪拌して熟成させたところ、熟成時間の
経過とともに白色結晶が析出してきたので、この反応混
合物を冷却し、城圧ｆ過してからＦ液を蒸留し９０〜１
１０℃の留分をとったところ、５４ｇのｔ−ブチルメチ
ルエトキシシランが得られた（収率７４％）。Next, at an internal temperature of 60°C, methyljethoxysilane 67
g (0.5 mol) was added dropwise over 1 hour, and the mixture was stirred and aged for 3 hours at an internal temperature of 66°C. As the aging time progressed, white crystals were precipitated. After cooling and passing through the pressure f, the F liquid is distilled to 90-1
When the 10° C. fraction was collected, 54 g of t-butylmethylethoxysilane was obtained (yield 74%).
実施例２
５００１ｎｌのフラスコ中に金属マグネシウム１２ｇ（
０，５モル）、テトラハイドロフラン１００ｍ（。Example 2 12 g of metallic magnesium (
0.5 mol), tetrahydrofuran 100 m (.
トルエン２５０ｄおよび少量のヨウ素を仕込み。Add 250d of toluene and a small amount of iodine.
窒素ガス雰囲気にこ−に１．１−ジメチルプロピルクロ
ライド５３．３ｇ（０，５モル）を内温４０〜５０℃で
１時間で滴下し、さらに６０℃で１時間攪拌してグリニ
ヤール試薬としての１．１− ジメチルプロピルマグネ
シウムクロライドを調製した。53.3 g (0.5 mol) of 1,1-dimethylpropyl chloride was added dropwise to the nitrogen gas atmosphere over 1 hour at an internal temperature of 40 to 50°C, and the mixture was further stirred at 60°C for 1 hour to form a Grignard reagent. 1.1-Dimethylpropylmagnesium chloride was prepared.
つぎにこ−に内温８０℃でジメチルメトキシシラン４５
ｇ（０，５モル）を１時間で滴下し１滴下終了後も内温
９０℃で４時間攪拌を続けて熟成させたのち１反応混合
物を冷却し、３００ｍ１の水中に注ぎ、有機層を蒸留し
たところ、１．１−ジメチルプロピルジメチルシラン２
３．４ｇ（収率３６％）が得られた。Next, dimethylmethoxysilane 45 was added at an internal temperature of 80°C.
g (0.5 mol) was added dropwise over 1 hour, and even after the addition of 1 drop, stirring was continued for 4 hours at an internal temperature of 90°C to age the reaction mixture. 1. The reaction mixture was cooled, poured into 300 ml of water, and the organic layer was distilled. As a result, 1,1-dimethylpropyldimethylsilane 2
3.4 g (yield 36%) was obtained.
応用例
５００＋ｌのフラスコ中に金属マグネシウム１２ｇ（０
，５モル）、テトラハイドロフラン１５０ｍＡ！および
少量のヨウ素を仕込み、音素ガス雰囲気下にこ−にメチ
ルクロライド３０．３ ｇ（０，６モル）を内温４０〜
５０℃で２時間で吹込み、さらに５５℃で１時間攪拌し
てグリニヤール試薬としてのメチルマグネシウムクロラ
イドを調製したのち。Application example 12 g of metallic magnesium (0
, 5 mol), tetrahydrofuran 150 mA! Then, add a small amount of iodine, and add 30.3 g (0.6 mol) of methyl chloride to the mixture at an internal temperature of 40 to 40 mol.
After blowing at 50°C for 2 hours and further stirring at 55°C for 1 hour to prepare methylmagnesium chloride as a Grignard reagent.
こ−に内温２０〜３０℃で実施例１で合成したｔ−ブチ
ルメチルエトキシシラン５１ｇを滴下し。To this, 51 g of t-butylmethylethoxysilane synthesized in Example 1 was added dropwise at an internal temperature of 20 to 30°C.
滴下終了後４０℃で１時間熟成し、得られた反応混合物
を冷却してから３０ｏ＋ａ／の水中に注ぎ一有機層を分
液後蒸留したところ、ｔ−ブチルジメチルシラン４０．
ｌｉ’（収率９８．５％）が得られた。After the dropwise addition was completed, the reaction mixture was aged at 40°C for 1 hour, and the resulting reaction mixture was cooled and poured into water at 30°C, and the organic layer was separated and distilled.
li' (yield 98.5%) was obtained.
つぎに３００ｔｎｌのフラスコ中に上記で得られたｔ−
ブチルジメチルシラン４０ｇと四塩化炭素１００Ｎとを
仕込み、と−に内高２０〜３０℃で２５．７ｇの塩素を
３時間で吹込んだのちこの反応混合物中に音素ガスを２
時間吹込んで反応混合物中に残存する塩酸ガスと塩素ガ
スを追出し、ついでこの反応混合物を蒸留し、１２８〜
１３８℃の留分をとったところ、特殊シリル化剤として
有用とされるｔ−ブチルジメチルクロロシラン４４．１
ｇ（収率８５％）が得られた。Next, the t-
40 g of butyldimethylsilane and 100 N of carbon tetrachloride were charged, and 25.7 g of chlorine was blown into the reaction mixture at an internal height of 20 to 30°C for 3 hours.
Hydrochloric acid gas and chlorine gas remaining in the reaction mixture are expelled by bubbling for a period of time, and the reaction mixture is then distilled.
When the fraction at 138°C was taken, t-butyldimethylchlorosilane, which is said to be useful as a special silylating agent, was found to be 44.1%.
g (yield 85%) was obtained.
Claims (1)
素基、Ｘはハロゲン原子）で示されるグリニヤール試薬
と、一般式Ａ＿ｍＲ＾２＿ｎＳｉＨ＿４＿−＿ｍ＿−＿
ｎ（こゝにＲ＾２は非置換または置換１価炭化水素基、
Ａはアルコキシ基、ｍは１、２または３、ｎは０、１ま
たは２、ｍ＋ｎ≦３）で示される有機けい素化合物とを
有機溶剤中で反応させることを特徴とする第３級炭化水
素シリル化合物の製造方法。 ２、有機溶剤がテトラハイドロフランである特許請求の
範囲第１項記載の第３級炭化水素シリル化合物の製造方
法。 ３、グリニヤール試薬がｔ−ブチルマグネシウムハライ
ドである特許請求の範囲第１項記載の第３級炭化水素シ
リル化合物の製造方法。[Claims] 1. A Grignard reagent represented by the general formula R^1MgX (where R^1 is a tertiary hydrocarbon group and X is a halogen atom) and a Grignard reagent represented by the general formula A_mR^2_nSiH_4_-_m_-_
n (where R^2 is an unsubstituted or substituted monovalent hydrocarbon group,
A is an alkoxy group, m is 1, 2 or 3, n is 0, 1 or 2, m+n≦3) A tertiary hydrocarbon characterized by reacting with an organosilicon compound represented by the following formula in an organic solvent. A method for producing a silyl compound. 2. The method for producing a tertiary hydrocarbon silyl compound according to claim 1, wherein the organic solvent is tetrahydrofuran. 3. The method for producing a tertiary hydrocarbon silyl compound according to claim 1, wherein the Grignard reagent is t-butylmagnesium halide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60163548A JPS6222790A (en) | 1985-07-24 | 1985-07-24 | Production of tertiary hydrocarbonsilyl compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60163548A JPS6222790A (en) | 1985-07-24 | 1985-07-24 | Production of tertiary hydrocarbonsilyl compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6222790A true JPS6222790A (en) | 1987-01-30 |
| JPS6327351B2 JPS6327351B2 (en) | 1988-06-02 |
Family
ID=15775987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60163548A Granted JPS6222790A (en) | 1985-07-24 | 1985-07-24 | Production of tertiary hydrocarbonsilyl compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6222790A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01306259A (en) * | 1988-06-03 | 1989-12-11 | Seiko Epson Corp | Manufacture of ink jet head |
| JPH02170808A (en) * | 1988-12-23 | 1990-07-02 | Toagosei Chem Ind Co Ltd | Production of water-absorbing polymer |
| EP0405560A2 (en) * | 1989-06-28 | 1991-01-02 | Dow Corning Toray Silicone Company, Limited | Preparation of tertiary-hydrocarbylsilyl compounds |
| US5530465A (en) * | 1992-04-23 | 1996-06-25 | Seiko Epson Corporation | Liquid spray head and its production method |
| WO2003040156A1 (en) * | 2001-11-08 | 2003-05-15 | Hokko Chemical Industry Co., Ltd. | Production processes for triorganomonoalkoxysilanes and triorganomonochlorosilanes |
| WO2003084967A1 (en) * | 2002-04-04 | 2003-10-16 | Dow Corning Corporation | Process for chlorosilane intermediates manufacture |
| US7059711B2 (en) | 2003-02-07 | 2006-06-13 | Canon Kabushiki Kaisha | Dielectric film structure, piezoelectric actuator using dielectric element film structure and ink jet head |
| US7351847B2 (en) | 2004-01-06 | 2008-04-01 | Dow Corning Corporation | Grignard processes with increased content of diphenylchlorosilanes |
| US7456308B2 (en) | 2004-01-06 | 2008-11-25 | Dow Corning Corporation | Grignard processes with improved yields of diphenylchlorosilanes as products |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102629292B1 (en) * | 2019-02-15 | 2024-01-24 | 에이치디현대인프라코어 주식회사 | A construction machine with automatic transmission apparatus |
-
1985
- 1985-07-24 JP JP60163548A patent/JPS6222790A/en active Granted
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01306259A (en) * | 1988-06-03 | 1989-12-11 | Seiko Epson Corp | Manufacture of ink jet head |
| JPH02170808A (en) * | 1988-12-23 | 1990-07-02 | Toagosei Chem Ind Co Ltd | Production of water-absorbing polymer |
| EP0405560A2 (en) * | 1989-06-28 | 1991-01-02 | Dow Corning Toray Silicone Company, Limited | Preparation of tertiary-hydrocarbylsilyl compounds |
| US5530465A (en) * | 1992-04-23 | 1996-06-25 | Seiko Epson Corporation | Liquid spray head and its production method |
| US6345424B1 (en) | 1992-04-23 | 2002-02-12 | Seiko Epson Corporation | Production method for forming liquid spray head |
| CN1296374C (en) * | 2001-11-08 | 2007-01-24 | 北兴化学工业株式会社 | Production processes for triorganomonoalkoxysilanes and triorganomonochlorosilanes |
| WO2003040156A1 (en) * | 2001-11-08 | 2003-05-15 | Hokko Chemical Industry Co., Ltd. | Production processes for triorganomonoalkoxysilanes and triorganomonochlorosilanes |
| US8008521B2 (en) | 2001-11-08 | 2011-08-30 | Hokko Chemical Industry Co., Ltd. | Processes for the production of tri-organo-monoalkoxysilanes and process for the production of tri-organo-monochlorosilanes |
| WO2003084967A1 (en) * | 2002-04-04 | 2003-10-16 | Dow Corning Corporation | Process for chlorosilane intermediates manufacture |
| US7513608B2 (en) | 2003-02-07 | 2009-04-07 | Canon Kabushiki Kaisha | Dielectric film structure, piezoelectric actuator using dielectric element film structure and ink jet head |
| US7938515B2 (en) | 2003-02-07 | 2011-05-10 | Canon Kabushiki Kaisha | Dielectric film structure, piezoelectric actuator using dielectric element film structure and ink jet head |
| US7059711B2 (en) | 2003-02-07 | 2006-06-13 | Canon Kabushiki Kaisha | Dielectric film structure, piezoelectric actuator using dielectric element film structure and ink jet head |
| US7351847B2 (en) | 2004-01-06 | 2008-04-01 | Dow Corning Corporation | Grignard processes with increased content of diphenylchlorosilanes |
| US7456308B2 (en) | 2004-01-06 | 2008-11-25 | Dow Corning Corporation | Grignard processes with improved yields of diphenylchlorosilanes as products |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6327351B2 (en) | 1988-06-02 |
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