JPH0242088A - (phenyldimethylcarbinyl)silane compound - Google Patents
(phenyldimethylcarbinyl)silane compoundInfo
- Publication number
- JPH0242088A JPH0242088A JP1135103A JP13510389A JPH0242088A JP H0242088 A JPH0242088 A JP H0242088A JP 1135103 A JP1135103 A JP 1135103A JP 13510389 A JP13510389 A JP 13510389A JP H0242088 A JPH0242088 A JP H0242088A
- Authority
- JP
- Japan
- Prior art keywords
- group
- phenyldimethylcarbinyl
- compound
- silane compound
- formula
- 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
- -1 silane compound Chemical class 0.000 title claims description 14
- 229910000077 silane Inorganic materials 0.000 title claims description 11
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 3
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 125000003944 tolyl group Chemical group 0.000 claims abstract description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 4
- 150000003377 silicon compounds Chemical class 0.000 abstract description 7
- 239000003960 organic solvent Substances 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 abstract description 3
- 239000011777 magnesium Substances 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 229910052786 argon Inorganic materials 0.000 abstract description 2
- 239000012298 atmosphere Substances 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract description 2
- 239000002685 polymerization catalyst Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 238000006884 silylation reaction Methods 0.000 abstract 1
- 229920002554 vinyl polymer Polymers 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 238000001819 mass spectrum Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 150000004795 grignard reagents Chemical class 0.000 description 6
- 239000007818 Grignard reagent Substances 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 3
- 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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000005055 methyl trichlorosilane Substances 0.000 description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- IPAIXTZQWAGRPZ-UHFFFAOYSA-N chloro-methyl-phenylsilicon Chemical compound C[Si](Cl)C1=CC=CC=C1 IPAIXTZQWAGRPZ-UHFFFAOYSA-N 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 1
- JAYBZWYBCUJLNQ-UHFFFAOYSA-N dichloro-(chloromethyl)-methylsilane Chemical compound C[Si](Cl)(Cl)CCl JAYBZWYBCUJLNQ-UHFFFAOYSA-N 0.000 description 1
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 description 1
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000005048 methyldichlorosilane Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229940094443 oxytocics prostaglandins Drugs 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003180 prostaglandins Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は立体障害の大きい、かさ高い置換基をもつ新規
化合物、（フエニルジメチルカルビニル）シラン化合物
に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a (phenyldimethylcarvinyl)silane compound, which is a novel compound having a bulky substituent that is highly sterically hindered.
（従来の技術と問題点）
従来、立体障害の大きい、かさ高い置換基をもったケイ
素化合物としてｔ−ブチルジメチルクロロシランが知ら
れており、これはプロスタグランジン（性ホルモン）、
チェナマイシン（抗生物質）などの医薬品合成に選択的
特殊シリル化剤として使用される有用な化合物である。(Prior art and problems) T-butyldimethylchlorosilane has been known as a silicon compound with a bulky substituent that is highly sterically hindered.
It is a useful compound used as a selective special silylating agent in the synthesis of pharmaceuticals such as chenamycin (an antibiotic).
このｔ−ブチルジメチルクロロシランの合成法としては
、■ｔ−ブチルリチウムを利用する方法［Ｊ、Ｏｒｇ、
Ｃｈｅｍ、、４３゜３６４９ （１９７８）、Ｊ、Ａｍ
、 Ｃｈｅｍ、 Ｓｏｃ、 、 ７６、１０３０ ｆ１
９５４１ ］、■グリニヤール反応を利用する方法があ
るが、■は金属リチウム、有機リチウムの取扱が危険な
ため工業的方法とは言えず、また ■は中間体として水
素シラン化合物を経由するため工程が長くなる欠点があ
りいずれも満足できるものではなかった。As a method for synthesizing this t-butyldimethylchlorosilane, ■method using t-butyllithium [J, Org.
Chem, 43°3649 (1978), J.Am.
, Chem, Soc, , 76, 1030 f1
9541], ■There is a method using the Grignard reaction, but (■) cannot be called an industrial method because handling of metallic lithium and organic lithium is dangerous, and (2) requires a process through a hydrogen silane compound as an intermediate. None of them were satisfactory, as they had the disadvantage of being long.
（問題点を解決するための手段）
本発明者らはこれら従来の問題点を解決し、公知のｔ−
ブチルジメチルクロロシラン化合物と同程度もしくはそ
れ以上の機能をもつシリル化合物を得る目的のもとに種
々検討した結果、工業的汎用原料であるメチルスチレン
とハロゲン化水素から容易にフェニルジメチル力ルビニ
ルハロゲナイドが得られ、これとミＳｉＸ結合を有する
ケイ素化合物とをＭｇ−有機溶媒系に同時に添加して反
応させることにより、文献未載の新規な（フエニルジメ
チルカルビニル）シラン化合物が得られることを見出し
、本発明を完成するに至ったものである。(Means for solving the problems) The present inventors have solved these conventional problems and
As a result of various studies aimed at obtaining a silyl compound with the same or higher functionality than butyldimethylchlorosilane compound, we found that phenyldimethylruvinylhalogen can be easily obtained from methylstyrene and hydrogen halide, which are industrial general-purpose raw materials. By simultaneously adding this and a silicon compound having a Mi-SiX bond to an Mg-organic solvent system and reacting, a novel (phenyldimethylcarvinyl)silane compound, which has not been described in any literature, can be obtained. This discovery led to the completion of the present invention.
本発明は、一般式
（式中β＝１〜２ 、 ｍ 、ｎ＝ｏ〜２．ｍ＋ｎ≦２
、Ｒ’ Ｒ２はメチル基、エ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、またはフェニ
ル基、トリル基などのアリール基、Ｘはハロゲン原子を
表わす）
で示される（フエニルジメチルカルビニル）シラン化合
物を要旨とするものである。The present invention is based on the general formula (where β=1-2, m, n=o-2.m+n≦2
, R' R2 is an alkyl group such as a methyl group or an ethyl group,
The gist is a (phenyldimethylcarvinyl)silane compound represented by an alkenyl group such as a vinyl group or an allyl group, or an aryl group such as a phenyl group or a tolyl group, where X represents a halogen atom.
以下これを詳しく説明すると、本発明の新規化合物であ
る（フエニルジメチルカルビニル）シランは、下記の方
法により工業的に得ることができる。To explain this in detail below, (phenyldimethylcarvinyl)silane, which is a new compound of the present invention, can be obtained industrially by the following method.
この方法においては、まず不活性有機溶媒中に金属マグ
ネシウムを添加し、これにメチルスチレンとハロゲン化
水素水溶液との加熱反応によって得られたフェニルジメ
チルカルビニルハロゲナイドと一般式Ｒ１□Ｒ”ｎＳｉ
Ｘ４−ｍ−１で示されるケイ素化合物との混合物を添加
し、反応させる。この場合の反応は、上記のハロゲン原
子と金属マグネシウムとからまずグリニヤール試薬が生
成し、さらに次式によって進行する。In this method, metal magnesium is first added to an inert organic solvent, and phenyldimethylcarvinyl halide obtained by a heating reaction between methylstyrene and an aqueous hydrogen halide solution is added to the mixture with the general formula R1□R"nSi.
A mixture with a silicon compound represented by X4-m-1 is added and reacted. In this case, the reaction first generates a Grignard reagent from the above-mentioned halogen atom and magnesium metal, and then proceeds according to the following formula.
℃
この反応に用いられるフェニルジメチルカルビニルハロ
ゲナイドは熱的に不安定で、蒸留するとかなりの割合で
脱ハロゲン化してメチルスチレンにもとってしまうため
、メチルスチレンとノ飄ロゲン化水素水溶液とを加熱反
応させて得られたフェニルジメチル力ルビニルハロゲナ
イドは直ち（こ水層から分離する必要がある。°C The phenyldimethylcarbinyl halide used in this reaction is thermally unstable and dehalogenates to a large extent when distilled, resulting in methylstyrene being removed. The phenyldimethylruvinylhalogenide obtained by heating and reacting must be immediately separated from the aqueous layer.
またフェニルジメチルカルビニルノ＼ロゲナイドのグリ
ニヤール試薬は有機溶媒中で次式で示すような
ＣＨ３ＣＨ３
副反応を生じて溶媒中で濃度が高くなるので、これを防
ぎ、また生成されたグリニヤール試薬がリアクタントで
あるシラン化合物と直ちに反応できるようにしなければ
ならない。In addition, the Grignard reagent of phenyldimethylcarbinylno\rogenide causes a CH3CH3 side reaction as shown in the following formula in an organic solvent, and the concentration increases in the solvent. It must be able to react readily with certain silane compounds.
この方法における最も重要なポイントは、ｌ＋１ｇ−有
機溶媒系にフェニルジメチル力ルビニルハロゲナイドと
ケイ素化合物とを同時に添加反応させることであり、こ
れによってはじめて収率よく工業的生産が可能となる。The most important point in this method is to simultaneously add and react phenyldimethylruvinylhalogenide and a silicon compound to the 1+1g-organic solvent system, and only by this can industrial production be possible with a high yield.
また、一般に第三級炭化水素基のケイ素原子への導入は
アルキルリチウム試薬でのみ反応が容易に進行し、グリ
ニヤール試薬では進行しないのが普通である。一方、グ
リニヤール試薬の場合はりアクタントであるケイ素原子
上の置換基としてＨ基をもったケイ素化合物のみ反応が
容易に進行すると言われているが、本発明に係るシラン
のフエニルジメチルカルビニル基は第三級炭化水素基で
あるにも係らずグリニヤール試薬で容易にケイ素原子に
導入することが判明した。このことは誰もが予想しなか
った画期的な効果である。Furthermore, in general, the reaction for introducing a tertiary hydrocarbon group into a silicon atom proceeds easily only with an alkyllithium reagent, and generally does not proceed with a Grignard reagent. On the other hand, in the case of Grignard reagents, it is said that the reaction proceeds easily only with silicon compounds having an H group as a substituent on the actant silicon atom, but the phenyldimethylcarbinyl group of the silane according to the present invention It was found that although it is a tertiary hydrocarbon group, it can be easily introduced into a silicon atom using a Grignard reagent. This is an epoch-making effect that no one expected.
この方法で使用される前記一般式
Ｒ’ｍＲ”ｎ５ｔＸ＜ −ｍ−ｎのケイ素化合物として
はジメチルジクロロシラン、メチルトリクロロシラン、
ビニルメチルジクロロシラン、フェニルトリクロロシラ
ン、ジフェニルジクロロシラン、クロロメチルメチルジ
クロロシランなどが例示される。The silicon compounds of the general formula R'mR"n5tX<-m-n used in this method include dimethyldichlorosilane, methyltrichlorosilane,
Examples include vinylmethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, and chloromethylmethyldichlorosilane.
有機溶媒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、ベンゼン、トルエンなどの
炭化水素溶剤が例示されるが、これらは２種以上の混合
溶剤として使用してもよい。Examples of organic solvents include ether solvents such as diethyl ether and tetrahydrofuran, and hydrocarbon solvents such as benzene and toluene, but two or more of these may be used as a mixed solvent.
前記反応は１０〜１５０℃、好ましくは３０〜１００℃
の温度範囲で行なうのがよい。またこの反応系に酸素が
存在すると、反応段階でグリニヤール試薬が酸素と反応
し、収率低下の原因となるので、窒素、アルゴンなどの
不活性ガス雰囲気下で反応させるのがよい。The reaction is carried out at 10-150°C, preferably 30-100°C.
It is best to carry out the test within a temperature range of . Furthermore, if oxygen is present in this reaction system, the Grignard reagent will react with oxygen during the reaction stage, causing a decrease in yield, so it is preferable to carry out the reaction under an inert gas atmosphere such as nitrogen or argon.
（発明の効果）
本発明の（フエニルジメチルカルビニル）シラン化合物
は ■分子内に立体障害の大きい、かさ高い置換基を有
しているため、立体選択性が高く、■アルコールとの反
応により得られたシリルエーテル結合が化学的に安定で
あることからステロイド、プロスタグランジンなどの医
薬品合成に有用な特殊シリル化剤として、また、立体規
則性をもったポリオレフィンの重合触媒、添加剤などの
用途に有用性をもつものである。(Effects of the invention) The (phenyldimethylcarvinyl)silane compound of the present invention has high stereoselectivity because it has a bulky substituent with large steric hindrance in the molecule, and ■ Because the resulting silyl ether bond is chemically stable, it can be used as a special silylating agent useful in the synthesis of pharmaceuticals such as steroids and prostaglandins, and as a polymerization catalyst and additive for stereoregular polyolefins. It has usefulness for its purpose.
実施例１
テトラハイドロフラン６００ｍ Ｉ２および金属マグネ
シウム１２ｇ（０，５モル）からなる混合物中に、ジメ
チルジクロロシラン６４．５ｇ（０，５モル）およびフ
エニルジメチルカルビニルクロライド７７、３ｇ （０
，５モル）の混合液をＮ２気流下、内温を４０〜５０℃
に維持しながら撹拌下に滴下した。滴下終了後内温を５
０℃に昇温してその温度で１時間撹拌を続けた。こうし
て得た反応液をろ過し、ろ液を濃縮し、減圧蒸留し、減
圧度２ｍｍＨｇで留出温度７４℃の留分をとったところ
、９０．３ｇの油状物が得られた。これは５Ｅ−３０の
１５％ｃｏａｔ ２ｍ・バツクドカラムによるガスクロ
マトグラフィーで調べたところ単一成分であった。こう
して得られた（フエニルジメチルカルビニル）ジメチル
クロロシランの質量スペクトル（ＭＳＩ、核磁気共鳴（
ＮＭＲ）および赤外吸収（ＩＲ）を測定したところ、次
の結果が得られた。Example 1 64.5 g (0.5 mol) of dimethyldichlorosilane and 77.3 g (0.5 mol) of phenyldimethylcarbinyl chloride are added in a mixture consisting of 600 m of tetrahydrofuran I2 and 12 g (0.5 mol) of metallic magnesium.
, 5 mol) under a N2 atmosphere, with an internal temperature of 40 to 50°C.
The solution was added dropwise while stirring while maintaining the temperature. After dropping, reduce the internal temperature to 5
The temperature was raised to 0°C and stirring was continued at that temperature for 1 hour. The reaction solution thus obtained was filtered, the filtrate was concentrated and distilled under reduced pressure, and a fraction with a distillation temperature of 74° C. was collected at a degree of vacuum of 2 mmHg to obtain 90.3 g of an oily substance. This was investigated by gas chromatography using a 5E-30 15% coat 2m backed column and was found to be a single component. Mass spectrum (MSI, nuclear magnetic resonance) of (phenyldimethylcarbinyl)dimethylchlorosilane thus obtained
NMR) and infrared absorption (IR) were measured, and the following results were obtained.
ＣＨｘ ｃｕｔ
ＭＳ：ｍ／ｅ （スペクトル強度比）
＊ ２１２（１６１＊ １９７（３） １７？（３１１
３５（３） １１９（１００１１１８（５６１＊ ９３
（３４１９Ｈ４３１７９（８１７８（８）７７（ｉｌｌ
６５ｆ８１４１（１８） ３９（８）＊印は塩素Ｃ２
３″の同位体元素ピークをともなう。CHx cut MS: m/e (spectral intensity ratio) * 212 (161 * 197 (3) 17? (311
35(3) 119(1001118(561*93
(3419H43179(8178(8)77(ill
65f8141(18) 39(8) *marked is chlorine C2
with a 3″ isotope peak.
ＮＭＲ：δ（ｐｐｍ）
ＣＨ，ＣＨａ
（ｃｌ （ｂ） （ａ）
（ａｌｏ、２２（ｓ）、 （ｂ）１．４０（ｓｌ、
（ｃｌ６．８０〜７．２０（ｍ）ＩＲ：（ｃｌ’１
３０５０、 ２９７０． ２８７５． １６００． １
５００． １４７５． １３７０゜１２６０、 １０４
０． ９２０． ８４０． ８１０． ７９０． ７０
０実施例２
（フエニルジメチルカルビニル）ジメチルクロロシラン
２１．２５ｇ（０，１モル）をシクロヘキサノール１０
ｇ （０，１モルｌ 、 Ｎ、Ｎ−ジメチルフォルムア
ミド１００＋ｎｊ２およびトリエチルアミン１０．１ｇ
の混合溶液中に室温で滴下して反応させたのち、反応混
合物をろ過、濃縮、減圧蒸留して、シリルエーテル化合
物（Ａｌ ： ＱＣｆｃＨａｌ ｚ−５ｉ （ＣＨｓｌ
ｇ−００２６ｇ ヲ得た。同様にして、ｔ−ブチルジ
メチルクロロシランでシクロヘキサノールをシリル化し
て、シリルエーテル化合物（Ｂｌ ： ｔ−Ｃ４Ｈｅ
（ＣＨｓ） ｚ−３ｉｏ Ｏヲ得た。NMR: δ (ppm) CH, CHa (cl (b) (a) (alo, 22 (s), (b) 1.40 (sl,
(cl6.80-7.20 (m) IR: (cl'1 3050, 2970. 2875. 1600. 1
500. 1475. 1370°1260, 104
0. 920. 840. 810. 790. 70
Example 2 21.25 g (0.1 mol) of (phenyldimethylcarvinyl)dimethylchlorosilane was mixed with 10 ml of cyclohexanol.
g (0.1 mol l, N,N-dimethylformamide 100+nj2 and triethylamine 10.1 g
The reaction mixture was filtered, concentrated, and distilled under reduced pressure to form a silyl ether compound (Al: QCfcHal z-5i (CHsl
g-0026g was obtained. Similarly, cyclohexanol was silylated with t-butyldimethylchlorosilane to form a silyl ether compound (Bl: t-C4He
(CHs) I got z-3io O.
得られたシリルエーテル化合物（Ａｌおよび（Ｂｌをそ
れぞれ１％ｃｏｎｃ ＨＣｌ２１１ｑを含有するエタノ
ール溶液に１０％濃度となるように加えて室温で放置し
た。添加後１０分経った時点で、溶液中で分解消失した
シリルエーテル化合物の割合をＧＣ分析により調べたと
ころ次の結果が得られた。The obtained silyl ether compounds (Al and (Bl) were each added to an ethanol solution containing 1% conc HCl211q to a concentration of 10% and allowed to stand at room temperature. 10 minutes after the addition, they decomposed in the solution. When the proportion of the silyl ether compound that disappeared was investigated by GC analysis, the following results were obtained.
実施例３
ジメチルジクロロシランの代りにメチルトリクロロシラ
ン７４．８ｇ （０，５モル）を使用した他は実施例１
と同様に行なったところ、沸点７８℃／２ｍｍＨｇの油
状物８６ｇが得られた。これは５Ｅ−３０の１５％ｃｏ
ａｔ ２ｍ・バツクドカラムによるガスクロマトグラフ
ィーで調べたところ単一成分であった。こうして得られ
た（フエニルジメチルカルビニル）メチルジクロロシラ
ンの質量スペクトル（ＭＳ）、核磁気共鳴（ＮＭＲ）お
よび赤外吸収スペクトル（ＩＲＩを測定したところ、次
の結果が得られた。Example 3 Example 1 except that 74.8 g (0.5 mol) of methyltrichlorosilane was used instead of dimethyldichlorosilane.
When the same procedure as above was carried out, 86 g of an oily substance with a boiling point of 78° C./2 mmHg was obtained. This is 15% co of 5E-30
Gas chromatography using an at 2m backed column revealed that it was a single component. When the mass spectrum (MS), nuclear magnetic resonance (NMR) and infrared absorption spectrum (IRI) of (phenyldimethylcarbinyl)methyldichlorosilane thus obtained were measured, the following results were obtained.
ＣＨ３ＣＨ３
ＭＳ：ｍ／ｅ （スペクトル強度比）
＊ ２３２（９） ＊ ２１７（０，５１＊ １９７（
１） １１９（１００１１０３（８１９１（４１１７９
ｆ８） ７８（８） ７７（９） ６５（４１＊ ６３
ｆ５）＊印は塩素（：９３７の同位体元素ピークをとも
なう。CH3CH3 MS: m/e (spectral intensity ratio) * 232 (9) * 217 (0,51 * 197 (
1) 119(1001103(8191(41179)
f8) 78(8) 77(9) 65(41*63
f5) * mark is accompanied by an isotope element peak of chlorine (:937).
ＮＭＲ：δｆｐｐｍ） ＣＨ３Ｃ＋（。NMR: δfppm) CH3C+(.
ｆｃ） （ｂ） （ａ）
（ａｌＯ，５４（ｓｌ、 （ｂｌｌ、５（ｓｌ、
（ｃ１６．９０〜７．２０（ｍ）ＩＲ： （ｃｍ−’）
３０５０、 ２９６０． ２８７０． １６００． １
５００． １４７０． １４５０゜１３７０、 １２６
０． １１３５． １０４０． ９２０． ９００．
７００実施例４
ジメチルジクロロシランの代りにフェニルメチルジクロ
ロシラン９５．５ｇ （０，５モル）を、またテトラハ
イドロフラン６００ｍβの代りにテトラハイドロフラン
３００＋ｎＪ２およびトルエン３００ｎ＋Ｊ２の混合溶
剤な使用した他は実施例１と同様に行なったところ、沸
点１３０℃／２ｍｍＨｇの油状物９６ｇが得られた。こ
れは５Ｅ−３０の１５％ｃｏａｔ ２ｍ・バツクドカラ
ムによるガスクロマトグラフィーで調べたところ単一成
分であった。こうして得られた（フエニルジメチルカル
ビニル）フェニルメチルクロルシランの質量スペクトル
（ＭＳ）、核６ｎ気共鳴（ＮＭＲ）および赤外吸収スペ
クトル（ＩＲ）を測定したところ、次の結果が得られた
。fc) (b) (a) (alO,54(sl, (bll,5(sl,
(c16.90-7.20 (m) IR: (cm-') 3050, 2960. 2870. 1600. 1
500. 1470. 1450°1370, 126
0. 1135. 1040. 920. 900.
700 Example 4 Example except that 95.5 g (0.5 mol) of phenylmethyldichlorosilane was used instead of dimethyldichlorosilane, and a mixed solvent of tetrahydrofuran 300+nJ2 and toluene 300n+J2 was used instead of tetrahydrofuran 600mβ. When the same procedure as in 1 was carried out, 96 g of an oily substance having a boiling point of 130° C./2 mmHg was obtained. This was investigated by gas chromatography using a 5E-30 15% coat 2m backed column and was found to be a single component. When the mass spectrum (MS), nuclear 6n gas resonance (NMR) and infrared absorption spectrum (IR) of the thus obtained (phenyldimethylcarbinyl)phenylmethylchlorosilane were measured, the following results were obtained.
ＣＨ３ＣＨ３
ＭＳ：ｍ／ｅ （スペクトル強度比）
＊ ２７４（１８） ＊ １５５（１００） １１９（
３６１１１８（５１） １０３（６１９１（２９）、
７９（５１７８（５） ７７（６１６５（４） ＊
６３（１０）＊印は塩素Ｃｆ１３？の同位体元素ピー
クをともなう。CH3CH3 MS: m/e (spectral intensity ratio) * 274 (18) * 155 (100) 119 (
361118 (51) 103 (6191 (29),
79 (5178 (5) 77 (6165 (4) *
63(10) *mark is chlorine Cf13? with an isotope element peak of
ＮＭＲ：δ（ｐｐｍｌ
（ｃ）
（ｄｉ （ｂｌ （ａｔ
師）０．５（ｓ）、 （ｂＨ，４（ｗ）、 （ｃ１
６．８０〜７．０５（ｍｌ（ｄ）７．０４〜？、３０（
ｍｌ Ｊ＝６ｃｐｓＩＲ： （ｃｍ−’）
３０５０、２９６０．２８７０．１６００．１５００．
１４４０．１３７０゜１２６０、 １１２０． １０４
０． ９２０． ７００実施例５〜７
シラン化合物を種々代えた他は実施例４と同様に行なっ
た結果を以下に示す。NMR: δ (ppml (c) (di (bl (at master) 0.5 (s), (bH,4 (w), (c1
6.80~7.05 (ml(d)7.04~?, 30(
ml J=6cpsIR: (cm-') 3050, 2960.2870.1600.1500.
1440.1370°1260, 1120. 104
0. 920. 700 Examples 5 to 7 The same procedure as in Example 4 was performed except that the silane compound was changed. The results are shown below.
実施例 シラン化合物 生成物 ＭＳスペクトル
（ｍ／ｅ強度比）印は塩素
Ｃε３７の同位体元素ピークを
ともなう。Examples Silane Compound Product MS spectrum (m/e intensity ratio) mark with isotope peak of chlorine Cε37.
ＣＨ。CH.
ＣＨＣＨ２ 傘印は塩素 ０℃３７の同位体元素ピークを ともなう。CHCH2 The umbrella symbol is chlorine The isotopic element peak at 0℃37 Tomo.
中印は塩素 Ｃ２３７の同位体元素ピークを ともなう。The middle mark is chlorine The isotope element peak of C237 Tomo.
ＮＭＲ：δｆｐｐｍｌ （ｂｌ （ａ） （Ｃ） （ａｌ １．５０ ｆｓ） 。NMR: δfppml (bl (a) (C) (al 1.50 fs).
（ｂ） ６．９５〜６．７５ （ｍｌ 。(b) 6.95-6.75 (ml).
（ｃｌ ７．３５〜７．０５（ｍ）(cl 7.35~7.05(m)
Claims (1)
１、Ｒ＾２はメチル基、エ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、またはフェニル
基、トリル基などのアリール基、Ｘはハロゲン原子を表
わす） で示される（フェニルジメチルカルビニル）シラン化合
物。[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, l=1-2, m, n=0-2, m+n≦2, R^
1. R^2 is an alkyl group such as a methyl group or an ethyl group, an alkenyl group such as a vinyl group or an allyl group, or an aryl group such as a phenyl group or tolyl group, and X represents a halogen atom. carbinyl) silane compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1135103A JPH0242088A (en) | 1989-05-29 | 1989-05-29 | (phenyldimethylcarbinyl)silane compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1135103A JPH0242088A (en) | 1989-05-29 | 1989-05-29 | (phenyldimethylcarbinyl)silane compound |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61208337A Division JPS6363683A (en) | 1986-09-04 | 1986-09-04 | (phenyldimethylcarbinyl)silane compound and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0242088A true JPH0242088A (en) | 1990-02-13 |
| JPH0551595B2 JPH0551595B2 (en) | 1993-08-03 |
Family
ID=15143911
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1135103A Granted JPH0242088A (en) | 1989-05-29 | 1989-05-29 | (phenyldimethylcarbinyl)silane compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0242088A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5960867A (en) * | 1994-12-02 | 1999-10-05 | Hitachi, Ltd. | Condenser and power plant |
-
1989
- 1989-05-29 JP JP1135103A patent/JPH0242088A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5960867A (en) * | 1994-12-02 | 1999-10-05 | Hitachi, Ltd. | Condenser and power plant |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0551595B2 (en) | 1993-08-03 |
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