JPS6039080B2 - Method for producing organosilicon compounds - Google Patents
Method for producing organosilicon compoundsInfo
- Publication number
- JPS6039080B2 JPS6039080B2 JP51126944A JP12694476A JPS6039080B2 JP S6039080 B2 JPS6039080 B2 JP S6039080B2 JP 51126944 A JP51126944 A JP 51126944A JP 12694476 A JP12694476 A JP 12694476A JP S6039080 B2 JPS6039080 B2 JP S6039080B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- sodium
- reaction
- producing
- 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.)
- Expired
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 150000003961 organosilicon compounds Chemical class 0.000 title claims description 12
- 150000002430 hydrocarbons Chemical group 0.000 claims description 10
- 150000003388 sodium compounds Chemical class 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 16
- 150000004820 halides Chemical class 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 235000015424 sodium Nutrition 0.000 description 10
- 239000011734 sodium Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- -1 sodium alkoxide Chemical class 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 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 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical class [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000238558 Eucarida Species 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- NEXSMEBSBIABKL-UHFFFAOYSA-N hexamethyldisilane Chemical compound C[Si](C)(C)[Si](C)(C)C NEXSMEBSBIABKL-UHFFFAOYSA-N 0.000 description 2
- 229920000548 poly(silane) polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- MGAXYKDBRBNWKT-UHFFFAOYSA-N (5-oxooxolan-2-yl)methyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1OC(=O)CC1 MGAXYKDBRBNWKT-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical class C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- KQHIGRPLCKIXNJ-UHFFFAOYSA-N chloro-methyl-silylsilane Chemical class C[SiH]([SiH3])Cl KQHIGRPLCKIXNJ-UHFFFAOYSA-N 0.000 description 1
- AFQQIZUQLQKSIR-UHFFFAOYSA-N chloromethyl(silyl)silane Chemical class [SiH3][SiH2]CCl AFQQIZUQLQKSIR-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
【発明の詳細な説明】
本発明は有機ケイ素化合物の改良された製造方法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved method for producing organosilicon compounds.
特に本発明はメチルアルコキシシリルナトリウム類と有
機ハロゲン化物との反応により、新しくケイ素−炭素結
合を形成することによる有機ケイ素化合物の製造方法に
関し、さらに、アルコキシジシラン類をナトリウム化合
物と反応させて上記〆チルアルコキシシリルナトリウム
類を合成することを経て、上記の反応を行わしめること
による、有機ケイ素化合物の製造方法に関する。シリコ
ーン工業において有機ケイ素化合物を製造するために、
一般に、ケイ素と有機ハロゲン化物とを銅触媒下に反応
させるいわゆる直接法が行われる。In particular, the present invention relates to a method for producing an organosilicon compound by forming a new silicon-carbon bond through the reaction of sodium methylalkoxysilyl and an organic halide, and further relates to a method for producing an organosilicon compound by reacting an alkoxydisilane with a sodium compound. The present invention relates to a method for producing an organosilicon compound by synthesizing sodium tylalkoxysilyl and then carrying out the above reaction. To produce organosilicon compounds in the silicone industry,
Generally, a so-called direct method is carried out in which silicon and an organic halide are reacted in the presence of a copper catalyst.
この直接法においては、工業的に有用なモノシラン類の
ほかに望ましからぬ副生成物として、ポリシラン類を主
成分とするいわゆる蒸留残櫨が生ずる。In this direct method, in addition to industrially useful monosilanes, so-called distillation residues containing polysilanes as a main component are produced as undesirable by-products.
これとは別に、ケイ素原子上に種々の置換基を有するア
ルコキシシラン類はシリコーン弾性体やシリコーン樹脂
などを製造するための原料として非常に有用であり、年
々その需要が増加しつつある。本発明は、工業上あまり
有用性をもたないポリシラン類、ここでは特にメチルァ
ルコキシジシラン類をナトリウム化合物と反応させ、こ
れをさらに有機ハロゲン化物と反応させて、工業的に有
用なアルコキシシラン類を得る方法を提供する。Apart from this, alkoxysilanes having various substituents on silicon atoms are very useful as raw materials for producing silicone elastomers, silicone resins, etc., and the demand for them is increasing year by year. In the present invention, industrially useful alkoxysilanes are produced by reacting polysilanes that are not very useful industrially, in particular methylalkoxydisilanes, with a sodium compound, and further reacting this with an organic halide. Provides a method to obtain types.
本発明に類似する方法としては（ＣＨ３）３ＳｉＳｉ（
ＣＨ３）３で示されるへキサメチルジシランをナトリウ
ムァルコキシドと反応させて、さらに有機ハロゲン化物
と反応させる、すなわち（Ｃは）３ＳｉＳｉ（ＣＨ３）
３十ＣＨ８０Ｎａ→（ＣＨ３）３ＳＩＮａ＋（ＣＨ３）
３Ｓｉ（ＯＣ瓜）によって示される桜井らの方法（ｒｅ
ｔｒａｈｅｄｒｏｎにｔｔｅ鼠１５１１、（１９７１）
）があるが、出発物であるへキサメチルジシランは、直
接法によるモノシラン類を合成する際ジシラン蟹分に含
まれるクロロメチルジシラン類や、そのアルコキシ化物
と異なって工業的に得にくく、さらにへキサメチルホス
ホリックトリアミド（ＨＭ円Ａ）という非常に高価な溶
媒を用いなければ、目的とするモノシラン類が充分な収
率で得られないという致命的な欠点がある。As a method similar to the present invention, (CH3)3SiSi(
Hexamethyldisilane represented by CH3)3 is reacted with sodium alkoxide and further reacted with an organic halide, i.e. (C is)3SiSi(CH3)
30CH80Na→(CH3)3SINa+(CH3)
The method of Sakurai et al. (re
trahedron tte mouse 1511, (1971)
), but hexamethyldisilane, which is a starting material, is difficult to obtain industrially, unlike chloromethyldisilanes contained in the disilane fraction when synthesizing monosilanes by the direct method, and its alkoxylated products, and furthermore, A fatal drawback is that the desired monosilanes cannot be obtained in sufficient yield unless a very expensive solvent called hexamethylphosphoric triamide (HM circle A) is used.
本発明は、かかる欠点を除去し、工業的に比較的入手し
やすい、ケイ素原子上にアルコキシ基を有するメチルア
ルコキシジシラン類を出発物に用い、テトラヒドロフラ
ンのような安価な溶媒中で容易にかつ収率良くメチルア
ルコキシシラン類を製造する方法を提供するものである
。The present invention eliminates such drawbacks and uses methylalkoxydisilanes having an alkoxy group on a silicon atom, which are relatively easily available industrially, as a starting material, and which can be easily and easily collected in an inexpensive solvent such as tetrahydrofuran. The present invention provides a method for efficiently producing methylalkoxysilanes.
本発明は、各種の方法により得られた一般式（ＲＯ）ｎ
（ＣＨ３）３‐ｎＳｉＮａで表わされるメチルアルコキ
シシリルナトリウム類と、一般式ＲＩＸで表わされる有
機ハロゲン化物とを反応させることを特徴とする、（Ｒ
Ｏ）ｎ（ＣＨ３）３心ＳＩＲＩで表わされる有機ケイ素
化合物の製造方法に関するものである。The present invention provides general formula (RO)n obtained by various methods.
(R
The present invention relates to a method for producing an organosilicon compound represented by O)n(CH3) three-core SIRI.
（上記式中、ＲおよびＲＩは炭素数１から１０の炭化水
素基であり、Ｘはハロゲン原子である。またｎは１，２
および３から選ばれる数である。）さらに本発明は、一
般式（ＲＯ）ｍ（ＣＨ３）６‐ｍＳｉ２で表わされるメ
チルアルコキシジシラン類を、一般式Ｒ２０Ｎａで表わ
されるナトリウム化合物と反応させて、一般式（ＲＯ）
ｎ（ＣＨ３）３川ＳＩＮａで表わされるメチルアルコキ
シシリルナトリウム化合物を合成し、それと一般式ＲＩ
Ｘで表わされる有機ハロゲン化物とを反応させることを
特徴とする（ＲＯ）ｎ（ＣＨ３）３川ＳＩＲＩで表わさ
れる有機ケイ素化合物の製造方法に関するものである。
（上記式中、Ｒ，Ｒ１，Ｘおよびｎは前述のとおり。ｍ
は１，２，３，４，５および６から選ばれる数、Ｒ２は
水素および炭素数１から１０の１価の炭化水素基から選
ばれた１価の基である。）本発明における基礎反応は、
メチルァルコキシジシラン類とナトリウム化合物とを反
応させる、すなわち（ＲＯ）ｍ（Ｃ比）６‐ｍＳｊ２−
Ｒ２０Ｎａ→（ＲＯ）ｎ（ＣＨ３）３‐ｎＳｉｅＮａ由
十（ＲＯ）爪−ｎ（ＣＨ３）３−ｍ＋ｎＳｉ（ＯＲ２）
で示される反応式と、これから生ずるアルコキシシリル
ナトリウム類と有機ハロゲン化物との反応、すなわち、
（ＲＯ）ｎ（ＣＨ３）３ｎＳｉｅＮａ＄＋ＲＩＸ→（Ｒ
。(In the above formula, R and RI are hydrocarbon groups having 1 to 10 carbon atoms, X is a halogen atom, and n is 1,2
and 3. ) Further, the present invention provides a method for producing a compound of the general formula (RO) by reacting a methylalkoxydisilane represented by the general formula (RO)m(CH3)6-mSi2 with a sodium compound represented by the general formula R20Na.
A methylalkoxysilyl sodium compound represented by n(CH3)3kawaSINa was synthesized, and it was combined with the general formula RI
The present invention relates to a method for producing an organosilicon compound represented by (RO)n(CH3) SIRI, which is characterized by reacting an organohalide represented by X with an organic halide represented by X.
(In the above formula, R, R1, X and n are as described above. m
is a number selected from 1, 2, 3, 4, 5 and 6, and R2 is a monovalent group selected from hydrogen and a monovalent hydrocarbon group having 1 to 10 carbon atoms. ) The basic reaction in the present invention is
Reacting methylalkoxydisilanes with a sodium compound, i.e. (RO)m(C ratio)6-mSj2-
R20Na→(RO)n(CH3)3-nSieNaYuju(RO)claw-n(CH3)3-m+nSi(OR2)
The reaction between the reaction formula shown in and the resulting alkoxysilyl sodium and the organic halide, i.e.,
(RO)n(CH3)3nSieNa$+RIX→(R
.
）ｎ（ＣＨ３＞３−ｎＳｉＲＩ＋ＮａＸで表わされる式
から成るものである。本発明で用いられるメチルアルコ
キシジシラン類は、一般式（ＲＯ）ｍ（ＣＨ３）６‐ｍ
Ｓｊ２（ここでＲは炭素数１から１０の１価の炭化水素
基であり、ｍは１，２，３，４，５および６から選ばれ
る数である。)n(CH3>3-nSiRI+NaX. The methylalkoxydisilanes used in the present invention have the general formula (RO)m(CH3)6-m
Sj2 (here, R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and m is a number selected from 1, 2, 3, 4, 5, and 6).
）で表わされるものであり、このようなメチルアルコキ
シジシラン類は、例えばメチルクロロシラン類の直接合
成法の高沸点残澄として得られるメチルクロロジシラン
類をアルコキシ化することにより得られるもので良く、
このようなメチルアルコキシジシラン類としては、例え
ば、（ＣＨ３０）（ＣＨ３）２ＳｉＳｉ（ＣＨ３）３，
（ＣＨ３０ ）（ＣＨ３）２ＳｉＳｉ（ＣＨ３）２（Ｏ
ＣＨ３），（ＣＨ３０）２（ＣＨ３）ＳｉＳｉ（ＣＨ３
）２（ＯＣＨ３），（ＣＨ３０）２（ＣＨ３）ＳｉＳｉ
（ＣＨ３）（ＯＣＨ３）２，（ＣＨ３０）３ＳｉＳｉ（
ＯＣＨ３）３，（Ｃ２比０）（ＣＨ３）２ＳｉＳｉ（Ｃ
Ｈ３）３，（Ｃ２日５０）（ＣＨ３）２ＳｉＳｉ（ＣＨ
３）２（ＯＣ２日５），（Ｃ２日３０）２（ＣＨ３）Ｓ
ｉＳｉ（ＣＨ３）２（ＯＣ２日５），（Ｃ２は○）２（
ＣＨ３）ＳｉＳｉ（ＣＨ３）（ＯＣ２日５）２，（Ｃ２
日３０）３ＳｉＳｉ（ＯＣ２日５）３，あるいはアルコ
キシ基としてフロポキシ基、イソプロポキシ基、ブート
キシ基、フェノキシ基などで置換されたメチルアルコキ
シジシランがある。), and such methylalkoxydisilanes may be obtained, for example, by alkoxylating methylchlorodisilanes obtained as a high-boiling point residue in a direct synthesis method of methylchlorosilanes,
Examples of such methylalkoxydisilanes include (CH30)(CH3)2SiSi(CH3)3,
(CH30)(CH3)2SiSi(CH3)2(O
CH3), (CH30)2(CH3)SiSi(CH3
)2(OCH3), (CH30)2(CH3)SiSi
(CH3)(OCH3)2,(CH30)3SiSi(
OCH3)3, (C2 ratio 0) (CH3)2SiSi(C
H3)3, (C2day50)(CH3)2SiSi(CH
3) 2 (OC 2 days 5), (C 2 days 30) 2 (CH 3) S
iSi(CH3)2(OC2day5), (C2 is ○)2(
CH3)SiSi(CH3)(OC2day5)2,(C2
Day 30) 3SiSi (OC2 Day 5) 3, or methylalkoxydisilane substituted with a fropoxy group, isopropoxy group, bootoxy group, phenoxy group, etc. as an alkoxy group.
そして本発明で用いられるメチルアルコキシシリルナト
リウム類は、上記のようなジシラン類にナトリウムメト
キシド、ナトリウムェトキシドおよびナトリウムフエノ
キシドのような一般式Ｒ２０Ｎａで示されるナトリウム
化合物を作用させることにより得られる。本発明で用い
られる一般式ＦＩＸで示される有機ハロゲン化物は、炭
素数１から１０の１価の炭化水素基を持つハロゲン化物
であり、炭化水素基としてはメチル基、エチル基、プロ
ピル基、ブチル基、ヘキシル基、ヂシル基およびこれら
の構造異性体で代表される飽和炭化水素基、ビニル基、
アリル基、スチリル基で代表される不飽和炭化水素基お
よびフェニル基などがあげられる。The methylalkoxysilyl sodiums used in the present invention can be obtained by reacting the above-mentioned disilanes with a sodium compound represented by the general formula R20Na such as sodium methoxide, sodium ethoxide, and sodium phenoxide. . The organic halide represented by the general formula FIX used in the present invention is a halide having a monovalent hydrocarbon group having 1 to 10 carbon atoms, and examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, and a butyl group. saturated hydrocarbon groups represented by hexyl groups, disyl groups, and structural isomers thereof, vinyl groups,
Examples include unsaturated hydrocarbon groups represented by allyl group and styryl group, and phenyl group.
またハロゲン原子としては塩素および臭素がある。これ
ら有機ハ。ゲン化物の使用量は、前記メチルアルコキシ
シリルナトリゥム類の総量に対して任意の量でよいが、
目的とするアルコキシシラン類の製造効率から考えて、
通常はメチルアルコキシシリルナトリウム類に対して享
倍モルから２倍モルの量で行われる。また用いられる溶
媒は生成物との分離が容易なもので、かつ目的物を収率
良く得るのに適した溶媒が選択され、それらの例として
はベンゼン、トルエン、キシレン、フロモベンゼン、エ
ーテル、テトラヒドロフラン、トリエチルアミンなどが
あげられる。反応は通常、常圧下、乾燥した窒素ガスの
ような不活性ガス雰囲気下で行われ、反応体を均一にす
るために適した損投手段を用いるのが有利である。Further, halogen atoms include chlorine and bromine. These organic ha. The amount of the genide used may be any amount based on the total amount of the methylalkoxysilyl sodium, but
Considering the production efficiency of the target alkoxysilanes,
Usually, it is carried out in an amount of 1 to 2 times the mole of sodium methylalkoxysilyl. The solvent to be used is one that is easy to separate from the product and is suitable for obtaining the desired product in good yield; examples thereof include benzene, toluene, xylene, furomobenzene, ether, tetrahydrofuran, Examples include triethylamine. The reaction is usually carried out under atmospheric pressure and an atmosphere of an inert gas such as dry nitrogen gas, and it is advantageous to use suitable drop-off means to homogenize the reactants.
しかし、反応を密封された反応容器中で行ってもなんら
さしつかえない。反応を実際に行う場合には、反応の第
１段階において目的とするメチルアルコキシシリルナト
リウム類を得るためのメチルアルコキシジシラン類を、
適当な溶媒を含む有機ハロゲン化物およびナトリウム化
合物の混合物に滴下する方法がとられるが、これはほん
の一例であり反応操作を変えてもなんらさしつかえない
。反応は通常、例えば室温のような非常に温和な条件下
で数時間ないし数十時間で完結し、目的とするメチルア
ルコキシシラン類を収率良く得ることができる。However, there is nothing wrong with carrying out the reaction in a sealed reaction vessel. When the reaction is actually carried out, the methylalkoxydisilanes to obtain the target methylalkoxysilyl sodiums are used in the first step of the reaction.
A method is used in which the reaction mixture is added dropwise to a mixture of an organic halide and a sodium compound containing an appropriate solvent, but this is just one example, and the reaction procedure may be changed in any way. The reaction is usually completed in several hours to several tens of hours under very mild conditions such as room temperature, and the desired methylalkoxysilane can be obtained in good yield.
本発明によって得られる有機ケイ素化合物は、シリコー
ンゴム、シリコーンオイル、シリコーンワニスなど種々
の有機ケイ素化合物重合体の製造に幅広く利用される。The organosilicon compound obtained by the present invention is widely used in the production of various organosilicon compound polymers such as silicone rubber, silicone oil, and silicone varnish.
以下、実施例を記載するが、これらは本発明を限定する
ものではない。実施例 １，２
乾燥窒素雰囲下、それぞれ第１表に示される配合により
有機ハロゲン化物としてＣＨ３ＣＨ２ＣＨ２ＣＨ２ＣＩ
、ナトリウムアルコキシドとしてＣＨ３０Ｎａ、および
溶媒としてテトラヒドロフランの混合物に（ＣＨ３０）
４（ＣＨ３）２Ｓｉ２を滴下した。Examples will be described below, but these are not intended to limit the invention. Examples 1 and 2 Under a dry nitrogen atmosphere, CH3CH2CH2CH2CI was prepared as an organic halide according to the formulations shown in Table 1, respectively.
(CH30) in a mixture of , CH30Na as the sodium alkoxide, and tetrahydrofuran as the solvent.
4(CH3)2Si2 was added dropwise.
その後、２独特間室温で燭拝したところ、目的とする（
ＣＨ３）（ＣＨ３ＣＨ２ＣＨ２ＣＨ２）Ｓｊ（ＯＣＨ３
）２が第１表で示すような結果で得られた。さらにこの
反応混合物を２４時間室温で燭拝したところ、それぞれ
第１表に示されるように目的物がさらに高い収率で得ら
れた。第１表
実施例 ３
実施例１と同機に反応容器中に４．６夕（０．０５モル
）のＣＨ３ＣＨ２ＣＨ２ＣＱＣ１、５．４夕（０．１モ
ル）のＣＨ３０Ｎａ、１００ｍ‘のテトラヒドロフラン
を入れた。After that, I held a candlelight prayer at room temperature for 2 hours, and the desired result (
CH3)(CH3CH2CH2CH2)Sj(OCH3
) 2 was obtained with the results shown in Table 1. When this reaction mixture was further allowed to stand at room temperature for 24 hours, the desired products were obtained in higher yields as shown in Table 1. Table 1 Example 3 In the same reactor as in Example 1, 4.6 days (0.05 mol) of CH3CH2CH2CQC1, 5.4 days (0.1 mol) of CH30Na, and 100 m' of tetrahydrofuran were charged.
次に、２１．０夕（０．１モル）の（ＣＨ３０）４（Ｃ
Ｈ３）２Ｓｉ２を滴下し、２４時間室温で燈拝したとこ
ろ、目的とする（ＣＨ３）（ＣＨ３ＣＨ２ＣＨ２ＣＱ）
Ｓｉ（ＯＣＨ３）２が収率６０％で得られた。実施例
４〜６
乾燥窒素ガス雰囲気下、有機ハロゲン化物としてＣＨ３
ＣＨ２ＣＨ２ＣＨ２Ｂｒ、ナトリウムアルコキシドとし
てＣＨ３ＣＨ２０Ｎａ、ジシランとして（ＣＨ３０）２
（ＣＨ３）４Ｓｉ２を用いて種々の条件下で反応させた
ところ、いずれの場合にも生成物として（ＣＨ３ＣＨ２
ＣＨ２ＣＨ２）（ＣＨ３）２Ｓｉ（ＯＣＨ３）が高収率
で得られた。Next, 21.0 evenings (0.1 mol) of (CH30)4(C
H3) When 2Si2 was added dropwise and kept at room temperature for 24 hours, the desired (CH3) (CH3CH2CH2CQ) was obtained.
Si(OCH3)2 was obtained with a yield of 60%. Example
4-6 CH3 as organic halide under dry nitrogen gas atmosphere
CH2CH2CH2Br, CH3CH20Na as sodium alkoxide, (CH30)2 as disilane
When reacting with (CH3)4Si2 under various conditions, (CH3CH2
CH2CH2)(CH3)2Si(OCH3) was obtained in high yield.
配合量、反応条件および得られた結果を第２表に示す。Table 2 shows the blended amounts, reaction conditions, and results obtained.
第２表実施例 ７〜１２
有機ハロゲン化物としてＣ６比Ｂｒを用いたほかは実施
例１と同様の化合物を用いて種々の条件下で反応させた
ところ、生成物として（Ｃ６＆）（Ｃ＆）Ｓｉ（ＯＣＨ
３）２が高収率で得られた。Table 2 Examples 7 to 12 The same compounds as in Example 1 were used, except that C6 ratio Br was used as the organic halide, and the reaction was carried out under various conditions, resulting in (C6&)(C&)Si as the product. (OCH
3) 2 was obtained in high yield.
配合比、反応条件および得られた結果を第３表に示す。
第３表
実施例 １３〜１５
有機ハロゲン化物としてＣ６＆ＣＩを用いたほかは実施
例４と同様の化合物を用いて種々の条件下で反応させた
ところ、生成物として（Ｃ６４）（ＣＨ３）２Ｓｉ（Ｏ
ＣＨ３）が第４表に示すような結果で得られた。Table 3 shows the blending ratio, reaction conditions, and results obtained.
Table 3 Examples 13 to 15 The same compounds as in Example 4 were used, except that C6&CI was used as the organic halide, and the reaction was carried out under various conditions. As a result, (C64)(CH3)2Si(O
CH3) was obtained with the results shown in Table 4.
第４表
実施例 １６〜２０
第５表に示すような有機ハロゲン化物を用いて、２１夕
（０．１モル）の（ＣＨ３０）４（ＣＨ３）２Ｓｉ２、
５．４夕（０．１モル）のＣＨ３０Ｎａおよび溶媒とし
て１００私のテトラヒドロフラン存在下に反応させたと
ころ、それぞれ第５表に示すようなアルコキシシラン類
を得た。Table 4 Examples 16-20 Using organic halides as shown in Table 5, 21 (0.1 mol) of (CH30)4(CH3)2Si2,
When the mixture was reacted in the presence of 5.4 mol (0.1 mol) of CH30Na and 100 mol of tetrahydrofuran as a solvent, alkoxysilanes as shown in Table 5 were obtained.
第５表
実施例 ２１〜２４
第６表に示すようなアルコキシシランを用いて（０．０
５モル）、ＣＨ３０Ｎａ（０．０７モル）および溶媒と
して５０松【のテトラヒドロフラン存在下に反応させた
ところ、それぞれ第６表に示すようなアルコキシフェニ
ルシランを得た。Table 5 Examples 21 to 24 Using alkoxysilanes as shown in Table 6 (0.0
When the mixture was reacted in the presence of CH30Na (0.07 mole) and tetrahydrofuran (50 mole) as a solvent, alkoxyphenylsilanes as shown in Table 6 were obtained, respectively.
Claims (1)
Ｎａで表わされるメチルアルコキシシリルナトリウム類
と、一般式Ｒ＾１Ｘで表わされる有機ハロゲン化物とを
反応させることを特徴とする、（ＲＯ）＿ｎ（ＣＨ＿３
）＿３＿−＿ｎＳｉＲ＾１で表わされる有機ケイ素化合
物の製造方法。 （式中、ＲおよびＲ＾１は炭素数１から１０の１価の炭
化水素基であり、Ｘはハロゲン原子である。またｎは１
，２および３から選ばれる数である。）２ 一般式（Ｒ
Ｏ）＿ｍ（ＣＨ＿３）＿６＿−＿ｍＳｉ＿２で表わされ
るメチルアルコキシジシラン類と、一般式Ｒ＿２ＯＮａ
で表わされるナトリウム化合物とを反応させて、一般式
（ＲＯ）＿ｎ（ＣＨ＿３）＿３＿−＿ｎＳｉＮａを表わ
されるメチルアルコキシシリルナトリウム化合物を合成
し、それと一般式Ｒ＾１Ｘで表わされる有機ハロゲン化
物とを反応させることを特徴とする（ＲＯ）＿ｎ（ＣＨ
＿３）＿３＿−＿ｎＳｉＲ＾１で表わされる有機ケイ素
化合物の製造方法。（式中、ＲおよびＲ＾１は炭素数１
から１０の１価の炭化水素基であり、Ｘはハロゲン原子
である。またｎは１，２および３から選ばれる数である
。ｍは１，２，３，４，５および６から選ばれる数、Ｒ
＾２は水素および炭素数１から１０の１価の炭化水素基
から選ばれた１価の基である。）[Claims] 1 General formula (RO)_n(CH_3)_3_-_nSi
(RO)_n(CH_3
)_3_-_nSiR^1 A method for producing an organosilicon compound. (In the formula, R and R^1 are monovalent hydrocarbon groups having 1 to 10 carbon atoms, X is a halogen atom, and n is 1
, 2 and 3. )2 General formula (R
O)_m(CH_3)_6_-_mSi_2 and the general formula R_2ONa
A methylalkoxysilyl sodium compound represented by the general formula (RO)_n(CH_3)_3_-_nSiNa is synthesized by reacting with a sodium compound represented by (RO)_n(CH
_3) A method for producing an organosilicon compound represented by _3_-_nSiR^1. (In the formula, R and R^1 have 1 carbon number
to 10 monovalent hydrocarbon groups, and X is a halogen atom. Further, n is a number selected from 1, 2, and 3. m is a number selected from 1, 2, 3, 4, 5 and 6, R
^2 is a monovalent group selected from hydrogen and a monovalent hydrocarbon group having 1 to 10 carbon atoms. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51126944A JPS6039080B2 (en) | 1976-10-22 | 1976-10-22 | Method for producing organosilicon compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51126944A JPS6039080B2 (en) | 1976-10-22 | 1976-10-22 | Method for producing organosilicon compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5353620A JPS5353620A (en) | 1978-05-16 |
| JPS6039080B2 true JPS6039080B2 (en) | 1985-09-04 |
Family
ID=14947750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP51126944A Expired JPS6039080B2 (en) | 1976-10-22 | 1976-10-22 | Method for producing organosilicon compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6039080B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5068387A (en) * | 1989-12-01 | 1991-11-26 | Dow Corning Corporation | Production of organofunctional alkoxysilanes |
-
1976
- 1976-10-22 JP JP51126944A patent/JPS6039080B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5353620A (en) | 1978-05-16 |
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