CN102584882B - Method for preparing methyl phenyl dichlorosilane - Google Patents

Method for preparing methyl phenyl dichlorosilane Download PDF

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CN102584882B
CN102584882B CN201210035404.5A CN201210035404A CN102584882B CN 102584882 B CN102584882 B CN 102584882B CN 201210035404 A CN201210035404 A CN 201210035404A CN 102584882 B CN102584882 B CN 102584882B
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谭军
陈洁
刘辉
皮永蕊
韦晓燕
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Tangshan coupling Silicon Industry Co.,Ltd.
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Jiaxing University
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Abstract

The invention discloses a method for preparing methyl phenyl dichlorosilane. The method comprises the following steps of: performing reflux reaction on 1,1,2,2-tetrachloro-1,2-dimethyldisilane and bromobenzene serving as main raw materials at the temperature of between 90 and 200 DEG C for 8 to 24 hours in the presence of a zerovalent palladium metal complex/ionic liquid serving as a catalyst, condensing a product, and performing solid-liquid separation to obtain the methyl phenyl dichlorosilane (MePhSiCl2). By the preparation method, the conversion rate of the raw materials is high, a volatile solvent is not used, and the yield of the target product, namely the MePhSiCl2 is high. The method for preparing the MePhSiCl2 is simple and practicable, easy to industrialize, low in equipment investment cost, safely and stably operated and good in industrial application prospect, and has the characteristics that the reaction is simple, the method is easy to operate, the product is easily separated from a byproduct, and the like.

Description

The preparation method of dichloromethyl phenylsilane
Technical field
The invention belongs to catalyst preparation research field, relate in particular to a kind of dichloromethyl phenylsilane (MePhSiCl 2) preparation method.
Background technology
Organosilicon material be mainly a class take Si-O key as main chain, on Si atom, introduce again the macromolecular compound of organic group as side chain, its excellent performance, function uniqueness, be widely used in the fields such as military project, space flight, medical treatment, chemical industry.Organochlorosilane is the main raw material that is prepared with organosilicon polymer material and other functional silane.Therefore, the production status of organochlorosilane has determined the height of a national Silicone Industry level to a great extent.In more than the 20 kind of organosilane monomer using at current production polysiloxane, with the consumption maximum of methyl chlorosilane, more than it accounts for the 90wt% of whole organosilane monomer total amount.But, though the polysiloxane product that methyl chlorosilane is made has a series of advantage, also come with some shortcomings, for example high temperature resistant poor performance at low temperatures, radioprotective is poor, poor etc. to the consistency of organic compound, mineral filler.Therefore, use other extraordinary silane or organic monomer and even corresponding polymkeric substance to carry out modification, become one of main direction of studying current and organosilicon material from now on, and had development prospect.And dichloromethyl phenylsilane (MePhSiCl 2, wherein Me is-CH 3, Ph is-C 6h 5) be a kind of important monomer of preparing methyl phenyl silicone, it is to improving the performance of organopolysiloxane, and the thermotolerance to raising organosilicon product, chemical stability, radioresistance etc. have obvious effect especially.
About MePhSiCl 2preparation method, patent documentation is in the past summed up four large classes such as mainly comprising condensation method, Grignard, discrimination method or cracking process.Condensation method is mainly to adopt MeSiHCl 2with C 6h 6or PhCl is raw material, at BCl 3, Ni, H 3bO 3, AlCl 3or under the catalyst action such as alkyl imidazole hydrochloride ionic liquid, under the conditions such as heat or ultraviolet lighting radiation, carry out liquid phase or gas-phase reaction is prepared MePhSiCl 2, the technique that the method is comparatively ripe is rhythmic reaction.Although object product MePhSiCl 2yield is higher, but has by product PhSiCl in product always 3(under 101.35KPa, boiling point is 201 ℃) and MePhSiCl 2the problems such as (under 101.35KPa, boiling point is 205 ℃) separating-purifying difficulty, this process also exists catalyzer to be difficult to the difficult problems such as recycling with product separation difficulty and catalyzer simultaneously, the MePhSiCl that causes the method to prepare 2monomer quality is lower.In addition, in such reaction, also can produce the strong carcinogenic by products such as biphenyl, make product postprocessing technique trouble.English Patent GB646629, GB635645, GB672180, GB782333; U.S. Pat 2546330, US2598436; Russian patent USSR362841, USSR530883; French Patent FR1415110; Disclosed these class methods that all belong to such as Chinese patent CN1807238A, CN101628917A, CN1807432A.
Grignard mainly refers to and utilizes RCl (R is Me or Ph), first under organic solvent or catalyst action, generates organic Grignard reagent with Na, Mg or Al etc., then further with R nsiCl 4-n(R is Me or Ph, and n is 1～3) reaction preparation MePhSiCl 2.World patent WO 083665A1, WO068476A1; U.S. Pat 6541651, US0233005A1; Disclosed these class methods that all belong to such as Chinese patent CN1656103A, CN102225949A.Although Grignard route object product yield is higher, easily generates PhSiCl 3with the by product such as polychlorobiphenyl, need to use a large amount of organic solvents, and easily blast, production security is not good enough.In addition, the processing of a large amount of by product metal halogens is also a shortcoming of the method.
Discrimination method is that one is comparatively simply prepared MePhSiCl 2approach, it is mainly with Me 3siCl and PhSiCl 3for raw material or Me 2siCl 2with Ph 2siCl 2for raw material generates the product of different initial reactants by the exchange between group.Disclosed these class methods that all belong to such as English Patent GB663690, U.S. Pat 2636895, US2786861.The catalyzer that the method adopts is mainly AlCl 3deng Lewis hydrochlorate, as the PhSiCl of raw material 3, Ph 2siCl 2, Me 2siCl 2, Me 3the prices such as SiCl are higher, and catalyst A lCl 3there is again the effect that causes consumingly Si-Ph bond rupture, thereby make product composition complicated.Therefore the industrializing implementation prospect of the method is not also expected.
Cracking process refers to 1,1,2-tri-chloro-1,2,2-trimethylammonium disilane (MeCl 2siSiClMe 2) and 1,1,2,2-tetrachloro-2,2-dimethyl disilane (MeCl 2siSiCl 2me) two kinds of disilane are raw material, by preparing MePhSiCl with reacting of PhCl or PhBr 2.U.S. Pat 2598434, US3772347 etc. are disclosed is all this method, as reacted within the scope of 100～200 ℃ with the disilane composition in high boiling material with PhCl, with Pd/C or Pd (PPhMe 2) 2cl 2deng being catalyzer, at 200 ℃, react 24h, can obtain yield and be 46% MePhSiCl 2.Chinese patent CN101195633A is mainly with Me 2clSiSiCl 2me and MeCl 2siSiCl 2the mixture of Me is main raw material, under the organic complex catalyst action of the 8th subgroup metal or the 8th subgroup metal, in 90～160 ℃ of temperature ranges by preparing MePhSiCl with reacting of PhCl or PhBr 2.For disilane cracking process, even if applicant's result of study finds that PhCl is almost difficult to and MeCl under the tertiary amines such as Pd (0), Ru, tertiary phosphine, quaternary ammonium halide, season phosphine halogenide organometallic complex catalyst action 2siSiClMe 2and MeCl 2siSiCl 2two kinds of disilane generation scission reactions of Me, MePhSiCl in product 2yield is extremely low.
Summary of the invention
The object of this invention is to provide a kind of title complex/ionic liquid-catalyzed bromobenzene cracking 1,1,2 of zeroth order metallic palladium, 2-tetrachloro-1,2-dimethyl disilane (MeCl of adopting 2siSiCl 2me) dichloromethyl phenylsilane (MePhSiCl is prepared in reaction 2) preparation method.Disilane (MeCl in described the method 2siSiCl 2me) scission reaction is carried out very selectively, thereby can obtain the target product MePhSiCl of higher yields 2.
A kind of dichloromethyl phenylsilane (MePhSiCl 2) preparation method, with 1,1,2,2-tetrachloro-1,2-dimethyl disilane (MeCl 2siSiCl 2me), bromobenzene is raw material, take zeroth order metallic palladium title complex/ionic liquid as catalyzer, at 90～200 ℃ of temperature range internal reflux reaction 8～24h, obtains dichloromethyl phenylsilane.
Principal reaction equation in the present invention is:
Figure BDA0000136292710000031
Wherein, MePhSiCl 2outward appearance is colourless transparent liquid, and boiling point is 205 ℃ (101.35KPa); MeSiHCl 2for colourless liquid, vapour pressure is 53.32kPa (23.7 ℃), and boiling point is 41.9 ℃ (101.35KPa); Dibromobenzene (C 6h 4br 2) boiling point is 218-224 ℃ (101.35KPa).
While carrying out back flow reaction in the inventive method in 90～200 ℃ of temperature ranges, due to by product MeSiHCl 2boiling point is lower, therefore refluxes and finishes rear major part and be removed, and after product condensation, can separate out part solid impurity, therefore removes solid impurity by solid-liquid separation, obtains containing target product MePhSiCl 2liquid phase mixture (this liquid phase mixture also has part material and by product C 6h 4br 2), as need further separate or purification target product MePhSiCl 2can adopt the means such as conventional rectifying.Also can directly adopt gas chromatography-mass spectrography to containing target product MePhSiCl 2liquid phase mixture carry out quantitatively and detect qualitatively.
In the present invention, described MePhSiCl 2in Me be-CH 3, Ph is-C 6h 5; Described MeCl 2siSiCl 2me in Me is-CH 3; Described Me 2cl 2siSiCl 2me in Me is-CH 3.
Zeroth order metallic palladium title complex described in the present invention is selected from tetrakis triphenylphosphine palladium (0) (Pd (PPh 3) 4), two (tri-butyl phosphine) palladium (0) (Pd[(t-Bu) 3p] 2), two (dibenzalacetone) palladium (0) (Pd (dba) 2), three (dibenzylidene indenes acetone) two palladiums (0) (Pd 2(dba) 3), two [1,2-two (diphenylphosphine) ethane] palladium (0) (Pd (DPPE) 2), two (tricyclohexyl phosphine) palladium (0) (Pd (PCy 3) 2) at least one.
As preferably, described zeroth order metallic palladium title complex is two (tricyclohexyl phosphine) palladium (0) (Pd (PCy 3) 2), two [1,2-two (diphenylphosphine) ethane] palladium (0) (Pd (DPPE) 2), three (dibenzylidene indenes acetone) two palladiums (0) (Pd 2(dba) 3) or two (dibenzalacetone) palladium (0) (Pd (dba) 2).Select these zeroth order metallic palladium title complexs can improve yield and the transformation efficiency of reaction.
Ionic liquid described in the present invention is selected from 1-butyl-3-methyl imidazolium tetrafluoroborate ([Bmim] BF 4), 1-ethyl-3-methylimidazole a tetrafluoro borate ([Emim] BF 4), 1-hexyl-3-methyl imidazolium tetrafluoroborate ([Hmim] BF 4), 1-octyl group-3-methyl imidazolium tetrafluoroborate ([Omim] BF 4), 1-butyl-3-Methylimidazole hexafluorophosphate ([Bmim] PF 6), 1-ethyl-3-methylimidazole hexafluorophosphate ([Emim] PF 6), chlorination-1-ethyl-3-methylimidazole-aluminum chloride ionic liquid ([Bmim] Cl+AlCl 3), bromination-1-ethyl-3-methylimidazole-aluminum chloride ionic liquid ([Emim] Br+AlCl 3) at least one.
As preferably, described ionic liquid is 1-hexyl-3-methyl imidazolium tetrafluoroborate ([Hmim] BF 4) or 1-octyl group-3-methyl imidazolium tetrafluoroborate ([Omim] BF 4).Select these ionic liquids can improve yield and the transformation efficiency of reaction.
Range of reaction temperature described in the present invention is 90～200 ℃, and preferred temperature of reaction span of control is 120～180 ℃.
Reacting reflux time described in the present invention is 8～24h, and preferred reacting reflux time is 12～24h.
In the present invention, MeCl 2siSiCl 2the volume ratio of Me and bromobenzene is 1: 2.
In the present invention, MeCl 2siSiCl 2the volume ratio of Me and ionic liquid is 1: 2, contains the zeroth order metallic palladium title complex of 0.1-0.25g/mL in ionic liquid.As preferably, MeCl 2siSiCl 2the volume ratio of Me and ionic liquid is 1: 2, contains the zeroth order metallic palladium title complex of 0.1g/mL in ionic liquid.When ionic liquid is [Hmim] BF 4or [Omim] BF 4, zeroth order metallic palladium title complex is two (tricyclohexyl phosphine) palladium (0) (Pd (PCy 3) 2), two [1,2-two (diphenylphosphine) ethane] palladium (0) (Pd (DPPE) 2), three (dibenzylidene indenes acetone) two palladiums (0) (Pd 2(dba) 3) or two (dibenzalacetone) palladium (0) (Pd (dba) 2) time, the yield of target product is higher.
Utilize method provided by the invention, in reaction, without using volatile solvent, simple to operate, side reaction is few, can obtain MePhSiCl by high yield 2.
The present invention adopts the composite catalyst system of zeroth order metallic palladium title complex/ionic liquid, and described zeroth order metallic palladium title complex disperses completely and exists with liquid form in ionic liquid, can effectively improve the yield of target product in reaction process.Equally, utilize preparation MePhSiCl provided by the invention 2method Production Flow Chart simple and easy to do, easily industrialization, equipment investment cost is low, operational safety performance is stable, product, with features such as by product are easily separated, has good prospects for commercial application.
Embodiment
By the following specific examples further illustrate the invention, should understand below only as exemplary, do not limit content of the present invention.
Embodiment 1
In 500 milliliters of there-necked flasks that reflux exchanger, thermometer be housed, under nitrogen protection, add successively 50mL Me 2clSiSiCl 2me, 100mL bromobenzene, 0.25g Pd (PPh 3) 4, 100mL[Emim] and Br+AlCl 3ionic liquid, is slowly warming up to 150 ℃, opens magnetic agitation reaction backflow 20h, removes MeSiHCl 2, reaction finishes rear product (to be mainly to MePhSiCl 2and dibromobenzene) carry out condensation, solid-liquid separation is removed solid impurity, obtains MePhSiCl 2liquid phase mixture.Then adopt gas chromatograph-mass spectrometer (GC-MS) to analyze to the liquid phase mixture of gained, calculate, raw material disilane transformation efficiency is 71%, product MePhSiCl 2yield is 54%.
Embodiment 2
In 500 milliliters of there-necked flasks that reflux exchanger, thermometer be housed, under nitrogen protection, add successively 50mL Me 2clSiSiCl 2me, 100mL bromobenzene, 0.25g Pd (PPh 3) 4, 100mL[Bmim] and Cl+AlCl 3ionic liquid, is slowly warming up to 150 ℃, opens magnetic agitation reaction backflow 20h, removes MeSiHCl 2, reaction finishes rear product (to be mainly to MePhSiCl 2and dibromobenzene) carry out condensation, solid-liquid separation is removed solid impurity, obtains MePhSiCl 2liquid phase mixture.Then adopt GC-MS to analyze to the liquid phase mixture of gained, calculate, raw material disilane transformation efficiency is 77%, product MePhSiCl 2yield is 60%.
Embodiment 3
In 500 milliliters of there-necked flasks that reflux exchanger, thermometer be housed, under nitrogen protection, add successively 50mL Me 2clSiSiCl 2me, 100mL bromobenzene, 0.25g Pd (PPh 3) 4, 100mL[Bmim] and PF 6ionic liquid, is slowly warming up to 120 ℃, opens magnetic agitation reaction backflow 20h, removes MeSiHCl 2, reaction finishes rear product (to be mainly to MePhSiCl 2and dibromobenzene) carry out condensation, solid-liquid separation is removed solid impurity, obtains MePhSiCl 2liquid phase mixture.Then adopt GC-MS to analyze to the liquid phase mixture of gained, calculate, raw material disilane transformation efficiency is 83%, product MePhSiCl 2yield is 73%.
Embodiment 4
In 500 milliliters of there-necked flasks that reflux exchanger, thermometer be housed, under nitrogen protection, add successively 50mL Me 2clSiSiCl 2me, 100mL bromobenzene, 0.25gPd (PPh 3) 4, 100mL[Emim] and PF 6ionic liquid, is slowly warming up to 140 ℃, opens magnetic agitation reaction backflow 20h, removes MeSiHCl 2, reaction finishes rear product (to be mainly to MePhSiCl 2and dibromobenzene) carry out condensation, solid-liquid separation is removed solid impurity, obtains MePhSiCl 2liquid phase mixture.Then adopt GC-MS to analyze to the liquid phase mixture of gained, calculate, raw material disilane transformation efficiency is 89%, product MePhSiCl 2yield is 77%.
Embodiment 5
In 500 milliliters of there-necked flasks that reflux exchanger, thermometer be housed, under nitrogen protection, add successively 50mL Me 2clSiSiCl 2me, 100mL bromobenzene, 0.2g Pd (PPh 3) 4, 100mL[Emim] and BF 4ionic liquid, is slowly warming up to 170 ℃, opens magnetic agitation reaction backflow 20h, removes MeSiHCl 2, reaction finishes rear product (to be mainly to MePhSiCl 2and dibromobenzene) carry out condensation, solid-liquid separation is removed solid impurity, obtains MePhSiCl 2liquid phase mixture.Then adopt GC-MS to analyze to the liquid phase mixture of gained, calculate, raw material disilane transformation efficiency is 92%, product MePhSiCl 2yield is 82%.
Embodiment 6
In 500 milliliters of there-necked flasks that reflux exchanger, thermometer be housed, under nitrogen protection, add successively 50mL Me 2clSiSiCl 2me, 100mL bromobenzene, 0.2g Pd (PPh 3) 4, 100mL[Bmim] and BF 4ionic liquid, is slowly warming up to 170 ℃, opens magnetic agitation reaction backflow 20h, removes MeSiHCl 2, reaction finishes rear product (to be mainly to MePhSiCl 2and dibromobenzene) carry out condensation, solid-liquid separation is removed solid impurity, obtains MePhSiCl 2liquid phase mixture.Then adopt GC-MS to analyze to the liquid phase mixture of gained, calculate, raw material disilane transformation efficiency is 96%, product MePhSiCl 2yield is 86%.
Embodiment 7
In 500 milliliters of there-necked flasks that reflux exchanger, thermometer be housed, under nitrogen protection, add successively 50mL Me 2clSiSiCl 2me, 100mL bromobenzene, 0.1g Pd (DPPE) 2, 100mL[Hmim] and BF 4ionic liquid, is slowly warming up to 140 ℃, opens magnetic agitation reaction backflow 15h, removes MeSiHCl 2, reaction finishes rear product (to be mainly to MePhSiCl 2and dibromobenzene) carry out condensation, solid-liquid separation is removed solid impurity, obtains MePhSiCl 2liquid phase mixture.Then adopt GC-MS to analyze to the liquid phase mixture of gained, calculate, raw material disilane transformation efficiency is 100%, product MePhSiCl 2yield is 90%.
Embodiment 8
In 500 milliliters of there-necked flasks that reflux exchanger, thermometer be housed, under nitrogen protection, add successively 50mL Me 2clSiSiCl 2me, 100mL bromobenzene, 0.1g Pd (PCy 3) 2, 100mL[Omim] and BF 4ionic liquid, is slowly warming up to 140 ℃, opens magnetic agitation reaction backflow 15h, removes MeSiHCl 2, reaction finishes rear product (to be mainly to MePhSiCl 2and dibromobenzene) carry out condensation, solid-liquid separation is removed solid impurity, obtains MePhSiCl 2liquid phase mixture.Then adopt GC-MS to analyze to the liquid phase mixture of gained, calculate, raw material disilane transformation efficiency is 100%, product MePhSiCl 2yield is 89%.
Embodiment 9
In 500 milliliters of there-necked flasks that reflux exchanger, thermometer be housed, under nitrogen protection, add successively 50mL Me 2clSiSiCl 2me, 100mL bromobenzene, 0.2g Pd[(t-Bu) 3p] 2, 100mL[Bmim] and BF 4ionic liquid, is slowly warming up to 130 ℃, opens magnetic agitation reaction backflow 17h, removes MeSiHCl 2, reaction finishes rear product (to be mainly to MePhSiCl 2and dibromobenzene) carry out condensation, solid-liquid separation is removed solid impurity, obtains MePhSiCl 2liquid phase mixture.Then adopt GC-MS to analyze to the liquid phase mixture of gained, calculate, raw material disilane transformation efficiency is 95%, product MePhSiCl 2yield is 85%.
Embodiment 10
In 500 milliliters of there-necked flasks that reflux exchanger, thermometer be housed, under nitrogen protection, add successively 50mL Me 2clSiSiCl 2me, 100mL bromobenzene, 0.25g Pd[(t-Bu) 3p] 2, 100mL[Bmim] and Cl+AlCl 3ionic liquid, is slowly warming up to 120 ℃, opens magnetic agitation reaction backflow 20h, removes MeSiHCl 2, reaction finishes rear product (to be mainly to MePhSiCl 2and dibromobenzene) carry out condensation, solid-liquid separation is removed solid impurity, obtains MePhSiCl 2liquid phase mixture.Then adopt GC-MS to analyze to the liquid phase mixture of gained, calculate, raw material disilane transformation efficiency is 79%, product MePhSiCl 2yield is 61%.
Embodiment 11
In 500 milliliters of there-necked flasks that reflux exchanger, thermometer be housed, under nitrogen protection, add successively 50mL Me 2clSiSiCl 2me, 100mL bromobenzene, 0.25g Pd[(t-Bu) 3p] 2, 100mL[Emim] and BF 4ionic liquid, is slowly warming up to 150 ℃, opens magnetic agitation reaction backflow 18h, removes MeSiHCl 2, reaction finishes rear product (to be mainly to MePhSiCl 2and dibromobenzene) carry out condensation, solid-liquid separation is removed solid impurity, obtains MePhSiCl 2liquid phase mixture.Then adopt GC-MS to analyze to the liquid phase mixture of gained, calculate, raw material disilane transformation efficiency is 93%, product MePhSiCl 2yield is 84%.
Embodiment 12
In 500 milliliters of there-necked flasks that reflux exchanger, thermometer be housed, under nitrogen protection, add successively 50mL Me 2clSiSiCl 2me, 100mL bromobenzene, 0.25g Pd[(t-Bu) 3p] 2, 100mL[Bmim] and BF 4ionic liquid, is slowly warming up to 150 ℃, opens magnetic agitation reaction backflow 20h, removes MeSiHCl 2, reaction finishes rear product (to be mainly to MePhSiCl 2and dibromobenzene) carry out condensation, solid-liquid separation is removed solid impurity, obtains MePhSiCl 2liquid phase mixture.Then adopt GC-MS to analyze to the liquid phase mixture of gained, calculate, raw material disilane transformation efficiency is 98%, product MePhSiCl 2yield is 86%.
Embodiment 13
In 500 milliliters of there-necked flasks that reflux exchanger, thermometer be housed, under nitrogen protection, add successively 50mL Me 2clSiSiCl 2me, 100mL bromobenzene, 0.1g Pd 2(dba) 3, 100mL[Hmim] and BF 4ionic liquid, is slowly warming up to 140 ℃, opens magnetic agitation reaction backflow 16h, removes MeSiHCl 2, reaction finishes rear product (to be mainly to MePhSiCl 2and dibromobenzene) carry out condensation, solid-liquid separation is removed solid impurity, obtains MePhSiCl 2liquid phase mixture.Then adopt GC-MS to analyze to the liquid phase mixture of gained, calculate, raw material disilane transformation efficiency is 100%, product MePhSiCl 2yield is 90%.
Embodiment 14
In 500 milliliters of there-necked flasks that reflux exchanger, thermometer be housed, under nitrogen protection, add successively 50mL Me 2clSiSiCl 2me, 100mL bromobenzene, 0.1g Pd (dba) 2, 100mL[Omim] and BF 4ionic liquid, is slowly warming up to 140 ℃, opens magnetic agitation reaction backflow 16h, removes MeSiHCl 2, reaction finishes rear product (to be mainly to MePhSiCl 2and dibromobenzene) carry out condensation, solid-liquid separation is removed solid impurity, obtains MePhSiCl 2liquid phase mixture.Then adopt GC-MS to analyze to the liquid phase mixture of gained, calculate, raw material disilane transformation efficiency is 100%, product MePhSiCl 2yield is 89%.
Embodiment 15
In 500 milliliters of there-necked flasks that reflux exchanger, thermometer be housed, under nitrogen protection, add successively 50mL Me 2clSiSiCl 2me, 100mL bromobenzene, 0.1g Pd (DPPE) 2, 100mL[Bmim] and BF 4ionic liquid, is slowly warming up to 160 ℃, opens magnetic agitation reaction backflow 16h, removes MeSiHCl 2, reaction finishes rear product (to be mainly to MePhSiCl 2and dibromobenzene) carry out condensation, solid-liquid separation is removed solid impurity, obtains MePhSiCl 2liquid phase mixture.Then adopt GC-MS to analyze to the liquid phase mixture of gained, calculate, raw material disilane transformation efficiency is 95%, product MePhSiCl 2yield is 85%.
Embodiment 16
In 500 milliliters of there-necked flasks that reflux exchanger, thermometer be housed, under nitrogen protection, add successively 50mL Me 2clSiSiCl 2me, 100mL bromobenzene, 0.1g Pd (PCy 3) 2, 100mL[Emim] and PF 6ionic liquid, is slowly warming up to 165 ℃, opens magnetic agitation reaction backflow 20h, removes MeSiHCl 2, reaction finishes rear product (to be mainly to MePhSiCl 2and dibromobenzene) carry out condensation, solid-liquid separation is removed solid impurity, obtains MePhSiCl 2liquid phase mixture.Then adopt GC-MS to analyze to the liquid phase mixture of gained, calculate, raw material disilane transformation efficiency is 98%, product MePhSiCl 2yield is 86%.

Claims (1)

1. a preparation method for dichloromethyl phenylsilane, is characterized in that, in 500 milliliters of there-necked flasks that reflux exchanger, thermometer be housed, adds successively 50mLMe under nitrogen protection 2clSiSiCl 2me, 100mL bromobenzene, 0.1g two [two (diphenylphosphine) ethane of 1,2-] palladium (0), 100mL1-hexyl-3-methyl imidazolium tetrafluoroborate ionic liquid, is slowly warming up to 140 ℃, opens magnetic agitation reaction backflow 15h, removes MeSiHCl 2, reaction finishes rear product to be carried out to condensation, and solid-liquid separation is removed solid impurity, obtains MePhSiCl 2liquid phase mixture.
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Preparation of methylphenyldichlorosilane through a catalytic cracking reaction of 1,2-dimethyl-1,1,2,2-tetrachlorodisilane with halobenzene;Yong-Rui Pi等,;《Journal of Chemical Research》;20111227;第35卷(第12期);第712-714页, 尤其是第712页右栏实验部分第2段、第713页表2条目4和第714页表3 *
Silicon-carbon bond formation by the reaction of disilanes with halobenzenes in the presence of tetrakis(triphenylphosphine)palladium(0);Hideyuki Matsumoto等,;《Journal of Organometallic Chemistry》;19750128;第85卷(第1期);第C1-C3页, 尤其是第C2页第2段和第C3页表1条目5 *
Yong-Rui Pi等,.Preparation of methylphenyldichlorosilane through a catalytic cracking reaction of 1,2-dimethyl-1,1,2,2-tetrachlorodisilane with halobenzene.《Journal of Chemical Research》.2011,第35卷(第12期),第712-714页, 尤其是第713页表3.
室温离子液体及其在催化和有机合成中的应用;顾彦龙等,;《化学进展》;20030531;第15卷(第3期);第222-241页, 尤其是第223页表1和图2、第224页表2以及第230页左栏最后一段至右栏第一段 *
顾彦龙等,.室温离子液体及其在催化和有机合成中的应用.《化学进展》.2003,第15卷(第3期),第222-241页, 尤其是第页.

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