JPS63238089A - Production of 1,2-dichloro-1,2,2-trimethyl-1-phenyldisilane - Google Patents
Production of 1,2-dichloro-1,2,2-trimethyl-1-phenyldisilaneInfo
- Publication number
- JPS63238089A JPS63238089A JP7138087A JP7138087A JPS63238089A JP S63238089 A JPS63238089 A JP S63238089A JP 7138087 A JP7138087 A JP 7138087A JP 7138087 A JP7138087 A JP 7138087A JP S63238089 A JPS63238089 A JP S63238089A
- Authority
- JP
- Japan
- Prior art keywords
- disilane
- trimethyl
- phenyldisilane
- dichloro
- chloro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- WTTXLOLKUGXKAO-UHFFFAOYSA-N chloro-[chloro(dimethyl)silyl]-methyl-phenylsilane Chemical compound C[Si](C)(Cl)[Si](C)(Cl)C1=CC=CC=C1 WTTXLOLKUGXKAO-UHFFFAOYSA-N 0.000 title claims 3
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 12
- 125000001424 substituent group Chemical group 0.000 claims abstract description 6
- KTPJDYNQZVAFBU-UHFFFAOYSA-N dichloro-[chloro(dimethyl)silyl]-methylsilane Chemical compound C[Si](C)(Cl)[Si](C)(Cl)Cl KTPJDYNQZVAFBU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011968 lewis acid catalyst Substances 0.000 claims abstract description 5
- RAPWOOJFCRALDY-UHFFFAOYSA-N chloro-[dimethyl(phenyl)silyl]-methyl-phenylsilane Chemical compound C=1C=CC=CC=1[Si](C)(Cl)[Si](C)(C)C1=CC=CC=C1 RAPWOOJFCRALDY-UHFFFAOYSA-N 0.000 claims abstract description 4
- ITMGADTXSQKXOL-UHFFFAOYSA-N chloro-dimethyl-[methyl(diphenyl)silyl]silane Chemical compound C=1C=CC=CC=1[Si](C)([Si](C)(Cl)C)C1=CC=CC=C1 ITMGADTXSQKXOL-UHFFFAOYSA-N 0.000 claims abstract 2
- XIDWVHKAQRJJQM-UHFFFAOYSA-N dimethyl-[methyl(diphenyl)silyl]-phenylsilane Chemical compound C=1C=CC=CC=1[Si](C)(C=1C=CC=CC=1)[Si](C)(C)C1=CC=CC=C1 XIDWVHKAQRJJQM-UHFFFAOYSA-N 0.000 claims abstract 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 16
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 2
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 2
- 229920000548 poly(silane) polymer Polymers 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- TXEDGTTUEVJNPE-UHFFFAOYSA-N trichloro(trimethylsilyl)silane Chemical compound C[Si](C)(C)[Si](Cl)(Cl)Cl TXEDGTTUEVJNPE-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000002841 Lewis acid Substances 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- -1 phenylmagnesium halide Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- RQJRLVCBMAKXFG-UHFFFAOYSA-N phenyl(silyl)silane Chemical compound [SiH3][SiH2]C1=CC=CC=C1 RQJRLVCBMAKXFG-UHFFFAOYSA-N 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HMGXAYAWDCHLQR-UHFFFAOYSA-N [SiH3][Si](c1ccccc1)(c1ccccc1)c1ccccc1 Chemical compound [SiH3][Si](c1ccccc1)(c1ccccc1)c1ccccc1 HMGXAYAWDCHLQR-UHFFFAOYSA-N 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- LBVDSENPNYQTJL-UHFFFAOYSA-N diphenyl(phenylsilyl)silane Chemical group C=1C=CC=CC=1[SiH2][SiH](C=1C=CC=CC=1)C1=CC=CC=C1 LBVDSENPNYQTJL-UHFFFAOYSA-N 0.000 description 1
- VVEAQOPVJBGVFY-UHFFFAOYSA-N disodium chloro(dioxido)borane Chemical compound B([O-])([O-])Cl.[Na+].[Na+] VVEAQOPVJBGVFY-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- GJMKAUACALCZOM-UHFFFAOYSA-L magnesium;oxolane;dichloride Chemical compound [Mg+2].[Cl-].[Cl-].C1CCOC1 GJMKAUACALCZOM-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 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
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- QFXXGTZVYQQGFZ-UHFFFAOYSA-N phenyl(phenylsilyl)silane Chemical compound C=1C=CC=CC=1[SiH2][SiH2]C1=CC=CC=C1 QFXXGTZVYQQGFZ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は、式(1)
で示される1、2−ジクロロ−1,2,2−トリメチル
−1−□ フェニルジシラン(以下、ジシラン(1)
と称する)を製造する方法に関するものであり、更に詳
しくは、式(II)
区
で示される1、1.2−トリクロロ−1,2,2−トリ
メチルジシラン(以下、ジシラン(II)と称する)と
、置換基として2個以上のフェニル基を有するジシラン
(以下ジシラン(m)と称する)とを、ルイス酸触媒の
存在下に反応させることからなるジシラン(1)を製造
する方法に関する。Detailed Description of the Invention (Industrial Application Field) The present invention provides 1,2-dichloro-1,2,2-trimethyl-1-□ phenyldisilane (hereinafter referred to as disilane (1)) represented by formula (1). )
It relates to a method for producing 1,1,2-trichloro-1,2,2-trimethyldisilane (hereinafter referred to as disilane (II)) represented by formula (II). and a disilane having two or more phenyl groups as substituents (hereinafter referred to as disilane (m)) in the presence of a Lewis acid catalyst.
(従来技術)
ジシラン(1)を製造する方法としては、本出願人が先
に出願した、ジシラン(II)とフェニルリチウムとを
反応さる方法(特願昭61−32808号)、ジシラン
(II)とフェニルマグネシウムハライドとをコバルト
触媒の存在下に反応させる方法(特願昭61−3280
9号)のように、ジシラン(n)の1−位のクロロ基1
個のみにフェニル基を選択的に導入する方法、および1
,1−ジクロロ−1゜2.2−トリメチル−2−フェニ
ルジシランをルイス酸の存在下に不均化反応させる方法
が存する。(Prior art) As a method for producing disilane (1), there is a method of reacting disilane (II) with phenyllithium (Japanese Patent Application No. 61-32808), which was previously filed by the applicant, and disilane (II). and phenylmagnesium halide in the presence of a cobalt catalyst (Patent application No. 61-3280)
No. 9), the chloro group 1 at the 1-position of disilane (n)
A method for selectively introducing phenyl groups only into
, 1-dichloro-1°2.2-trimethyl-2-phenyldisilane is subjected to a disproportionation reaction in the presence of a Lewis acid.
(発明が解決すべき問題点)
ジシラン(I[)へ1個のフェニル基を選択的に導入す
る方法は、本出願人が先に出願した特願昭61−328
08号および特願昭61−32809号に示すように、
ジシラン(II)にフェニルリチウムまたはフェニルマ
グネシウムハライドを反応させるが、これらフェニル化
試薬がジシラン〔■〕に対して過剰になると2個以上の
フェニル基が導入され、逐次反応生成物が副生する、あ
るいはジシラン(1)の異性体である1、1−ジクロロ
−1゜2.2−トリメチル−2−フェニルジシランが副
生ずるため、厳しい反応条件の制御が要求される。(Problems to be Solved by the Invention) A method for selectively introducing one phenyl group into disilane (I
As shown in No. 08 and Japanese Patent Application No. 61-32809,
Disilane (II) is reacted with phenyllithium or phenylmagnesium halide, but if these phenylating reagents are in excess with respect to disilane [■], two or more phenyl groups are introduced, and sequential reaction products are produced as by-products. Alternatively, since 1,1-dichloro-1.2-trimethyl-2-phenyldisilane, which is an isomer of disilane (1), is produced as a by-product, strict control of reaction conditions is required.
(問題を解決するための手段)
本発明者らは、ジシラン(I)を選択的に製造する方法
について検討を重ねた結果、ジシラン(If)とジシラ
ン(In)とをルイス酸触媒の存在下に反応させること
とにより所期の目的を達成することを見い出し、本発明
を完成したものである。(Means for Solving the Problem) As a result of repeated studies on a method for selectively producing disilane (I), the present inventors discovered that disilane (If) and disilane (In) were prepared in the presence of a Lewis acid catalyst. The present invention was completed by discovering that the intended purpose could be achieved by reacting with
本発明の原料であるジシラン〔■〕は、メチルクロライ
ドと金属ケイ素とからジクロロジメチルシランを合成す
るさいに副生ずるジシラン留分より得られる。またジシ
ランCm)は。Disilane [■], which is a raw material of the present invention, is obtained from a disilane fraction produced as a by-product during the synthesis of dichlorodimethylsilane from methyl chloride and metal silicon. Also, disilane Cm).
フェニル基のほかメチル基および/またはクロロ基を有
するもので5代表的なものとしては。Five typical examples include those having a methyl group and/or a chloro group in addition to a phenyl group.
1−クロロ−1,2,2−トリメチル−1,2−ジフェ
ニルジシラン、1−クロロ−1eL2−トリメチル−2
,2−ジフェニルジシラン、1,2.2−トリメチル−
1,1,2−トリフェニルジシランが例示される。これ
らのジシラン(m)はそれぞれ単独で、または2種以上
の混合物で使用できる。本発明の代表的は反応式を示す
と
(以下余白)
CH3CH,CH,CH。1-chloro-1,2,2-trimethyl-1,2-diphenyldisilane, 1-chloro-1eL2-trimethyl-2
, 2-diphenyldisilane, 1,2.2-trimethyl-
An example is 1,1,2-triphenyldisilane. These disilanes (m) can be used alone or in a mixture of two or more. The typical reaction formula of the present invention is shown below (in the margin below): CH3CH, CH, CH.
CH,CH□
CH3CH3CH3CH3
CH,CH3
CQ CQ
(以下余白)
のようにジシラン(m)が2個のフェニル基を有すると
きは、1当量のジシラン[II]と1当量のジシラン(
m)より2当量のジシラン(1)を、3個のフェニル基
を有するときは、2当量のジシラン【■−〕と1当量の
ジシラン〔■〕より3当量のジシランCI)を生成する
。When disilane (m) has two phenyl groups, as in CH,CH
m) to produce 2 equivalents of disilane (1), and when it has three phenyl groups, 2 equivalents of disilane [■-] and 1 equivalent of disilane [■] to produce 3 equivalents of disilane CI).
本発明において触媒として用いるルイス酸としては、非
プロトン性ルイス酸である塩化アルミニウム(Alll
CL) 、リチウムクロロアルミネート(Li Am
CQ、)、 三塩化ホウ素(Bi、)、ナトリウムク
ロロボレート(Na B CI2.)、三塩化ガリウム
(GaCfia)、塩化第二鉄(FeCn3)、塩化亜
鉛(ZnCfA、)、塩化第二スズ(SnCQ4)、四
塩化チタン(Ti CQJ 、塩化コバルト(C。The Lewis acid used as a catalyst in the present invention includes aluminum chloride (All
CL), lithium chloroaluminate (Li Am
CQ,), boron trichloride (Bi,), sodium chloroborate (Na B CI2.), gallium trichloride (GaCfia), ferric chloride (FeCn3), zinc chloride (ZnCfA, ), tin chloride (SnCQ4) ), titanium tetrachloride (Ti CQJ ), cobalt chloride (C.
CQ2)、塩化ニッケル(NiCQ2)、塩化マグネシ
ウム(MgCQ2)などのほか、ビストリフェニルホス
フィンコバルトクロライド((PPh、) 、C。CQ2), nickel chloride (NiCQ2), magnesium chloride (MgCQ2), etc., as well as bistriphenylphosphine cobalt chloride ((PPh, ), C.
CQ□〕、ビステトラヒドロフランマグネシウムクロラ
イド((THF)2M、 CΩ2〕、テトラヒドロフラ
ンマグネシウムクロライド((THF)Mg CQ 2
)のように少なくとも1個以上の配位子をもつ金属錯体
化合物、あるいは酸化アルミニウム(AI2203)、
酸化第二鉄<Fet 03 )−酸化亜鉛(ZnO)
、酸化ニッケル(Nip)、酸化コバルト(Co O)
、塩化マグネシウム(Mg O) 、酸化鋼(Cu O
)、酸化ケイ素(Si Q2)などの金属酸化物が例示
されるが、これらに限るものではない。CQ□], bis-tetrahydrofuran magnesium chloride ((THF) 2M, CΩ2), tetrahydrofuran magnesium chloride ((THF)Mg CQ 2
) or aluminum oxide (AI2203),
Ferric oxide <Fet 03 )-zinc oxide (ZnO)
, nickel oxide (Nip), cobalt oxide (CoO)
, magnesium chloride (MgO), oxidized steel (CuO
), and metal oxides such as silicon oxide (Si Q2), but are not limited to these.
しかしながら、特に塩化アルミニウム、リチウムクロロ
アルミネート、又は酸化アルミニウムが好適である。However, aluminum chloride, lithium chloroaluminate or aluminum oxide are particularly suitable.
本発明のジシラン〔、口を製造する方法は、原料である
ジシラン[II]とジシラン[m]を。The method for producing disilane [2] of the present invention uses disilane [II] and disilane [m] as raw materials.
ルイス酸とともに非プロトン性溶媒、たとえば、ヘキサ
ン、シクロヘキサン、メチルシクロヘキサン、ベンゼン
、トルエン、キシレン、テトラヒドロフラン、エチルエ
ーテル、クロロホルム。Lewis acids together with aprotic solvents such as hexane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, tetrahydrofuran, ethyl ether, chloroform.
四塩化炭素、塩化メチレン、1,2−ジクロロエタンな
どの溶媒中、あるいは溶媒を用いることなく反応させる
。反応温度は0〜200℃、特に0〜120℃が好適で
あり、通常は0.1〜3時間で反応は完結する。反応終
了後は常法の精製法により精製して高純度のジシラン(
I)を得る。The reaction is carried out in a solvent such as carbon tetrachloride, methylene chloride, 1,2-dichloroethane, or without using a solvent. The reaction temperature is preferably 0 to 200°C, particularly 0 to 120°C, and the reaction is usually completed in 0.1 to 3 hours. After the reaction is complete, it is purified using a conventional purification method to obtain high-purity disilane (
I) is obtained.
(効 果)
本発明は、ジシラン(n)とジシランCm)とをルイス
酸の存在下に反応させることにより、電気伝導体、フォ
トレジスト、光情報記憶材料等としての機能を有するポ
リシランの中間体として有用な化合物であるジシラン(
Ilを得るものである。また原料であるジシラン〔■〕
およりジシラン(m)は、メチルクロライドと金属ケイ
素とからジクロロジメチルシランを合成するさいに10
〜20%副生ずるジシラン留分より得られるもので、現
在このジシラン留分は未利用のまま貯蔵または廃棄され
ており、本発明はかかる未利用資源の有効利用をもはか
るものである。(Effects) The present invention produces a polysilane intermediate having functions as an electrical conductor, a photoresist, an optical information storage material, etc. by reacting disilane (n) and disilane Cm) in the presence of a Lewis acid. Disilane, a compound useful as
Il is obtained. Also, the raw material disilane [■]
Oyori disilane (m) is obtained by using 10
It is obtained from a disilane fraction that is a by-product of ~20%, and currently this disilane fraction is stored or discarded unused, and the present invention aims to effectively utilize such unused resources.
(実施例) 以下、実施例により説明する。(Example) Examples will be explained below.
実施例1
冷却管、温度計および攪拌機を備えた100mi四つロ
フラスコにトルエン45m Qに溶解した1、1゜2−
トリクロロ−1,2,2トリメチルジシラン7.1g(
0,034モル)と1−クロロ−1,2,2−トリメチ
ル−1゜2−ジフェニルジシラン10.Og(0,03
4モル)を仕込み、無水塩化アルミニウム0.8g(0
,006モル)を加えて、50℃で2時間反応した0反
応終了後ヘキサン50m Qを加え、更にアセトン0.
6tdを滴下して無水塩化アルミニウムを失活させる。Example 1 1,1°2− dissolved in 45 mQ of toluene in a 100 m four-loaf flask equipped with a condenser, thermometer, and stirrer.
7.1 g of trichloro-1,2,2-trimethyldisilane (
0,034 mol) and 1-chloro-1,2,2-trimethyl-1°2-diphenyldisilane 10. Og(0,03
4 mol) and 0.8 g (0.4 mole) of anhydrous aluminum chloride.
,006 mol) was added and reacted for 2 hours at 50°C.After the reaction was completed, 50 mQ of hexane was added, and further 0.0 mQ of acetone was added.
6td was added dropwise to deactivate the anhydrous aluminum chloride.
次いで析出した塩を濾別し、溶媒を留去したのち、減圧
蒸留により89〜b
して、1,2−ジクロロ−1,2,2−トリメチル−1
−フェニルジシラン10.4 gを得た。収率61%。Next, the precipitated salt was filtered off, the solvent was distilled off, and 1,2-dichloro-1,2,2-trimethyl-1 was obtained by distillation under reduced pressure.
-10.4 g of phenyldisilane was obtained. Yield 61%.
沸点89〜90℃/3.OmHg
マススペクトル(GC−MS、EI 70eV)248
(M”、4%)、155(55%) 、 135(10
0%)、120(32%) 、 105(25%) 、
91(17%)、63(27%)
プロトンNMRスペクトル(60MHz、 CCQ 4
):δppma : 7.1〜7.7 (m、5 H
)b :0.8 (s、3H)
0.6 (s、3H)
0.5 (s、3H)
赤外吸収スペクトル(NaCQ ) :ロー1305
0、2950.1420.1400.1250.111
0なお、反応生成物の同定のため、反応生成物の少量を
リチウムアルミニウムハライドで還元し、還元生成物の
’H−NMRスペクトル(CSD、)を測定した結果、
下記のようにaの水素は確認されたが、bの水素は確認
されなかった。Boiling point 89-90℃/3. OmHg mass spectrum (GC-MS, EI 70eV) 248
(M”, 4%), 155 (55%), 135 (10
0%), 120 (32%), 105 (25%),
91 (17%), 63 (27%) Proton NMR spectrum (60 MHz, CCQ 4
): δppma: 7.1 to 7.7 (m, 5 H
)b: 0.8 (s, 3H) 0.6 (s, 3H) 0.5 (s, 3H) Infrared absorption spectrum (NaCQ): Rho 1305
0, 2950.1420.1400.1250.111
0 In order to identify the reaction product, a small amount of the reaction product was reduced with lithium aluminum halide, and the 'H-NMR spectrum (CSD) of the reduction product was measured.
As shown below, hydrogen in a was confirmed, but hydrogen in b was not confirmed.
a: δppm=3.6〜4.4(m)b:検出されず
従って、この反応生成物は1,2−ジクロロ−1,2,
2−トリメチル−1−フェニルジシランであることを確
認した。a: δppm=3.6-4.4 (m) b: Not detected Therefore, this reaction product is 1,2-dichloro-1,2,
It was confirmed that it was 2-trimethyl-1-phenyldisilane.
実施例2
トルエン600+a Qに溶解した1、1.2−トリク
ロロ−1,2,2−トルメチルジシラン83.1g(0
,40モル)と1−クロロ−1,2,2−トリメチル−
1,2−ジフェニルジシラン117g(0,40モル)
に、無水塩化アルミニウム10.7g (0,08モル
)を加えて、50℃で1時間反応した。反応終了後実施
例1と同様の後処理を行い、蒸留により単離することに
より1.2−ジクロロ−1,2,2−トリメチル−1−
フェニルジシラン141.8gを得た。収率71%。Example 2 83.1 g of 1,1,2-trichloro-1,2,2-tolumethyldisilane (0
, 40 mol) and 1-chloro-1,2,2-trimethyl-
117 g (0.40 mol) of 1,2-diphenyldisilane
10.7 g (0.08 mol) of anhydrous aluminum chloride was added to the mixture, and the mixture was reacted at 50° C. for 1 hour. After completion of the reaction, the same post-treatment as in Example 1 was carried out, and 1,2-dichloro-1,2,2-trimethyl-1-
141.8 g of phenyldisilane was obtained. Yield 71%.
沸点89〜90℃/3.0m1g
マススペクトル(GC−MS、EI 70eV)248
(M”、4%) 、 155(55%) 、135(1
00%)120(32%) 、105(25%) 、9
1(17%)、63(27%)
プロトンNMRスペクトル(60MHz−CON2):
δppma : 7.1〜7.7 (m 、 5 H
)b :0.8 (s、3H)
0.6 (s、3H)
0.5 (s、3H)
赤外吸収スペクトル(NaCQ ) : cs −13
050、2950,1420,1400,1250,1
110実施例3
トルエン250m 12に溶解した1、1.2−トリク
ロロ−1,2,2−トリメチルジシラン45.7g(0
,22モル)と1.2.2−トルメチル−1,1,2−
トリフェニルジシラン33.3g (0,10モル)に
、無水塩化アルミニウム4.3g(0,03モル)を加
えて、50℃で3時間反応した。反応終了後実施例1と
同様の後処理を行い、蒸留により単離することにより1
,2−ジクロロ−1゜2.2−トリメチル−1−フェニ
ルジシラン47.4gを得た。収率63%。Boiling point 89-90℃/3.0ml1g Mass spectrum (GC-MS, EI 70eV) 248
(M”, 4%), 155 (55%), 135 (1
00%) 120 (32%) , 105 (25%) , 9
1 (17%), 63 (27%) Proton NMR spectrum (60MHz-CON2):
δppma: 7.1-7.7 (m, 5H
)b: 0.8 (s, 3H) 0.6 (s, 3H) 0.5 (s, 3H) Infrared absorption spectrum (NaCQ): cs -13
050, 2950, 1420, 1400, 1250, 1
110 Example 3 45.7 g of 1,1,2-trichloro-1,2,2-trimethyldisilane (0
, 22 mol) and 1,2,2-tolumethyl-1,1,2-
4.3 g (0.03 mol) of anhydrous aluminum chloride was added to 33.3 g (0.10 mol) of triphenyldisilane, and the mixture was reacted at 50° C. for 3 hours. After the completion of the reaction, the same post-treatment as in Example 1 was carried out, and the product 1 was isolated by distillation.
, 47.4 g of 2-dichloro-1°2.2-trimethyl-1-phenyldisilane were obtained. Yield 63%.
沸点89〜90℃/3.0mHg
マススペクトル(GC−MS、E I 70eV)24
8(Mゝ、4%) 、 155(55%) 、 135
(100%)120(32%) 、 105(25%)
+ 91(17%)、63(27%)
プロトンNMRスペクトル(60MHz、 ccQ、)
:δppma : 7.1〜7.7 (m 、 5 H
)b :0.8 (s、 3H)
0.6 (s、3H)
0.5 (s、3H)
赤外吸収スペクトル(NaCQ ) :cs −130
50、2950,1420,1400,1250,11
10実施例4
メチルシクロヘキサン800履Ωに溶解した1、1゜2
−トリクロロ−1,2,2−トリメチルジシラン133
g(0,64モル)と1−クロロ−1,2,2−トリメ
チル−1,2−ジフェニルジシラン、1−クロロ−1,
1,2−トルメチル−2,2−ジフェニルジシランの混
合物(95:5)169g(0,58モル)に無水塩化
アルミニウム16.3g(0,12モル)を加えて、室
温で5時間反応した。Boiling point 89-90℃/3.0mHg Mass spectrum (GC-MS, E I 70eV) 24
8 (Mゝ, 4%), 155 (55%), 135
(100%) 120 (32%) , 105 (25%)
+ 91 (17%), 63 (27%) Proton NMR spectrum (60MHz, ccQ,)
: δppma: 7.1 to 7.7 (m, 5H
)b: 0.8 (s, 3H) 0.6 (s, 3H) 0.5 (s, 3H) Infrared absorption spectrum (NaCQ): cs -130
50, 2950, 1420, 1400, 1250, 11
10 Example 4 1,1°2 dissolved in methylcyclohexane 800Ω
-Trichloro-1,2,2-trimethyldisilane 133
g (0.64 mol) and 1-chloro-1,2,2-trimethyl-1,2-diphenyldisilane, 1-chloro-1,
16.3 g (0.12 mol) of anhydrous aluminum chloride was added to 169 g (0.58 mol) of a mixture (95:5) of 1,2-tolumethyl-2,2-diphenyldisilane, and the mixture was reacted at room temperature for 5 hours.
反応終了後実施例1と同様の後処理を行い、蒸留により
単離することにより1,2−ジクロロ−1,2゜2−ト
リメチル−1−フェニルジシラン208gを得た。After the reaction was completed, the same post-treatment as in Example 1 was carried out, and 208 g of 1,2-dichloro-1,2°2-trimethyl-1-phenyldisilane was obtained by isolation by distillation.
収率72%。Yield 72%.
沸点89〜90℃/3.Om)1g
マススペクトル(GC−MS、E I 70eV)24
8(M”、4%) 、155(55%) 、135(1
00%)120(32%) 、105(25%) 、
91(17%)、63(27%)
プロト:/ NMRスペクトル(60MHz、 C1,
Q、):δppma : 7.t〜7.7 (m 、
5 H)b :0.8 (s、 3H)0.6
(s、3H)
0.5 (s、3H)
赤外吸収スペクトル(NaC12) :■−13050
、2950,1420,1400,1250,1110
特許出願人 有機合成薬品工業株式会社手続補正書
昭和62年4月27日
昭和62年特許願第71380号
2、発明の名称
3、補正をする者
事件との関係 特許出願人
東京都中央区京橋二丁目17番4号
有機合成薬品工業株式会社
代表者玉重雅雄
4、代理人
6、補正の内容
(1)明細書第5頁第9行目「代表的は」を「代表的な
」に訂正する。Boiling point 89-90℃/3. Om) 1g Mass spectrum (GC-MS, E I 70eV) 24
8 (M”, 4%), 155 (55%), 135 (1
00%) 120 (32%), 105 (25%),
91 (17%), 63 (27%) Proto: / NMR spectrum (60MHz, C1,
Q, ): δppma: 7. t~7.7 (m,
5H)b:0.8 (s, 3H)0.6
(s, 3H) 0.5 (s, 3H) Infrared absorption spectrum (NaC12): ■-13050
, 2950, 1420, 1400, 1250, 1110
Patent Applicant: Organic Synthetic Pharmaceutical Industry Co., Ltd. Procedural Amendment April 27, 1988 Patent Application No. 71380 of 1988 2, Title of Invention 3, Relationship with the person making the amendment Case Patent Applicant: Kyobashi, Chuo-ku, Tokyo 2-17-4 Organic Synthetic Pharmaceutical Industry Co., Ltd. Representative Masao Tamashige 4, Agent 6 Contents of amendment (1) Changed “representative” to “representative” on page 5, line 9 of the specification correct.
(2)同第6頁反応式の第2行目
Ct(3CQ J CQCQ Jと
訂正する。(2) The second line of the reaction equation on page 6, Ct (corrected as 3CQ J CQCQ J.
(3)同第10頁第9〜10行目「おより」をrおよび
」と訂正する。(3) On page 10, lines 9 and 10, ``Oyori'' is corrected to ``r and''.
(4) 同第13頁下から第6行目r 141 、8
gJをr141.8g」と訂正する。(4) Page 13, line 6 from the bottom r 141, 8
Correct gJ to r141.8g.
(5) 同第14頁下から第7行目r45 、7gJ
をr45.7gJと訂正する。(5) Page 14, line 7 from the bottom r45, 7gJ
is corrected to r45.7gJ.
以上that's all
Claims (1)
ジシランと、置換基として2個以上のフェニル基を有す
るジシランとを、ルイス酸触媒の存在下に反応させるこ
とを特徴とする1,2−ジクロロ−1,2,2−トリメ
チル−1−フェニルジシランを製造する方法。 2、置換基として2個以上のフェニル基を有するジシラ
ンが1−クロロ−1,2,2−トリメチル−1,2−ジ
フェニルジシランである特許請求の範囲第1項記載の1
,2−ジクロロ−1,2,2−トリメチル−1−フェニ
ルジシランを製造する方法。 3、置換基として2個以上のフェニル基を有するジシラ
ンが1−クロロ−1,1,2−トリメチル−2,2−ジ
フェニルジシランである特許請求の範囲第1項記載の1
,2−ジクロロ−1,2,2−トリメチル−1−フェニ
ルジシランを製造する方法。 4、置換基として2個以上のフェニル基を有するジシラ
ンが1,2,2−トリメチル−1,1,2−トリフェニ
ルジシランである特許請求の範囲第1項記載の1,2−
ジクロロ−1,2,2−トリメチル−1−フェニルジシ
ランを製造する方法。[Claims] 1,1,1,2-trichloro-1,2,2-trimethyldisilane and a disilane having two or more phenyl groups as substituents are reacted in the presence of a Lewis acid catalyst. A method for producing 1,2-dichloro-1,2,2-trimethyl-1-phenyldisilane, characterized in that: 2. 1 according to claim 1, wherein the disilane having two or more phenyl groups as a substituent is 1-chloro-1,2,2-trimethyl-1,2-diphenyldisilane
, 2-dichloro-1,2,2-trimethyl-1-phenyldisilane. 3. 1 according to claim 1, wherein the disilane having two or more phenyl groups as a substituent is 1-chloro-1,1,2-trimethyl-2,2-diphenyldisilane
, 2-dichloro-1,2,2-trimethyl-1-phenyldisilane. 4. The 1,2-disilane according to claim 1, wherein the disilane having two or more phenyl groups as a substituent is 1,2,2-trimethyl-1,1,2-triphenyldisilane.
A method for producing dichloro-1,2,2-trimethyl-1-phenyldisilane.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7138087A JPH0725776B2 (en) | 1987-03-27 | 1987-03-27 | Method for producing 1,2-dichloro-1,2,2-trimethyl-1-phenyldisilane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7138087A JPH0725776B2 (en) | 1987-03-27 | 1987-03-27 | Method for producing 1,2-dichloro-1,2,2-trimethyl-1-phenyldisilane |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63238089A true JPS63238089A (en) | 1988-10-04 |
JPH0725776B2 JPH0725776B2 (en) | 1995-03-22 |
Family
ID=13458840
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP7138087A Expired - Fee Related JPH0725776B2 (en) | 1987-03-27 | 1987-03-27 | Method for producing 1,2-dichloro-1,2,2-trimethyl-1-phenyldisilane |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0725776B2 (en) |
-
1987
- 1987-03-27 JP JP7138087A patent/JPH0725776B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPH0725776B2 (en) | 1995-03-22 |
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