JP6044361B2 - Method for producing dichloromonohydrosilane compound - Google Patents

Description

  The present invention relates to a process for producing a dichloromonohydrosilane compound, and more specifically, a dichloromonohydrosilane compound obtained by reacting a trichloroorganosilane compound with a monohydrosilane compound in the presence of a catalyst, particularly in the presence of an ammonium salt or a phosphonium salt. It relates to a method of manufacturing.

  Since dichloromonohydrosilane compounds have Si-H bonds and can be reacted with various olefins and alkynes having functional groups, synthesis of various silane compounds such as various silane coupling agents and functional silicone oils. It is a compound useful as a raw material. In particular, a dichloromonohydrosilane compound having a reactive group as an organo group can synthesize a silane compound having two identical or different reactive groups by performing a hydrosilylation reaction with an olefin compound having a reactive group. It is particularly useful because it can.

  Dichloromethylsilane, which is the head of the dichloromonohydrosilane compound, is produced by a direct method in which metal silicon is reacted with methyl chloride (Non-patent Document 1: J. Am. Chem. Soc, 1945, Vol. 67, page 1772). Has been.

  As a method for producing a dichloromonohydrosilane compound having an organo substituent having a reactive group, a method in which an organotrichlorosilane compound and an alkyltrihydrosilane compound are reacted using a tertiary amine as a catalyst is known (Patent Document 1: U.S. Pat. No. 3,465,019).

  Further, as a method for producing an α-position hetero-substituted alkyldichlorosilane compound, an α-hetero-substituted alkyldichlorohydrosilane compound is produced by reacting an α-position heterosubstituted alkyltrichlorosilane compound with a monohydrosilane compound in the presence of a catalyst. The method is known. It is described that the reactivity of the group on silicon is high in the silane compound having an α-position hetero-substituted alkyl group (Patent Document 2: International Publication No. 2010/4948). For example, chloromethyltrichlorosilane having high reactivity on silicon easily reacts with a hydrosilane compound to obtain dichloromonohydrosilane.

US Pat. No. 3,465,019 International Publication No. 2010/4948

J. et al. Am. Chem. Soc, 1945, 67, 1772

  However, in the method of Patent Document 1, the alkyltrihydrosilane compound used as the hydrosilane compound needs to be produced by reducing the alkyltrichlorosilane compound with a metal hydride or the like, is expensive, and is industrially available. It is difficult to carry out this method on an industrial scale because it is difficult.

  In addition, the chloromethyltrichlorosilane of Patent Document 2 is difficult to obtain, but the α-position substituent is highly reactive, so there are many side reactions in which the chloro group of the chloromethyl group is reduced to a methyl group. There was a problem that happened. Furthermore, when an expensive triorganosilane compound such as triethylsilane or phenyldimethylsilane is used as the hydrosilane compound, the reaction rate of chloromethyltrichlorosilane is high and the production ratio of the desired chloromethyldichlorosilane is increased. be able to. However, when the reaction is carried out using dichloromethylsilane, which is inexpensive and readily available, it can be removed under pressure using an autoclave or using a glass tube reactor in order to increase the production ratio of chloromethyldichlorosilane. It is necessary to carry out the reaction under pressure in an air-sealed tube, and the reaction at normal pressure has a problem that the production ratio of chloromethyldichlorosilane is lowered. In addition, when chlorodimethylsilane is used as the hydrosilane compound, there is a problem that the production ratio of chloromethyldichlorosilane is low even if the reaction is carried out under pressure by degassing and sealing using a glass tube reactor. was there. Furthermore, when it implements under pressure on an industrial scale, there exists a problem that a special reaction apparatus is required.

  On the other hand, in the method of Non-Patent Document 1, since the reaction temperature is high, it is difficult to produce a hydrosilane compound having a functional group.

  From the above, it has been desired to develop a method for producing a dichloromonohydrosilane compound, particularly a dichloromonohydrosilane compound having a reactive group other than the α-position, using an inexpensive and readily available monohydrosilane compound.

  The present invention is in response to the above-mentioned demand, and uses a trichlorosilane compound having an organo group having no substituent at the α-position and a monohydrosilane compound, particularly inexpensive and readily available chlorodimethylsilane or dichloromethylsilane. It is an object of the present invention to provide a method for producing a dichloromonohydrosilane compound.

  As a result of intensive studies to achieve the above object, the present inventors have reacted dichloromonohydrosilane by reacting a trichloroorganosilane compound unsubstituted at the α-position with a monohydrosilane compound in the presence of a catalyst. It has been found that a compound can be produced, and has led to the present invention.

Accordingly, the present invention provides the following method for producing a dichloromonohydrosilane compound.
[1]
The following general formula (1)
R ¹ SiCl ₃ (1)
(In the formula, R ¹ is a C1-C20 unsubstituted or substituted monovalent hydrocarbon group having a substituent other than the α-position of the silicon atom.)
And a trichloroorganosilane compound represented by the following general formula (2)
HSiR ² _m Cl _3-m (2)
(In the formula, R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and m is 1, 2 or 3.)
And a monohydrosilane compound represented by the following general formula (3):
HSiR ¹ Cl ₂ (3)
(Wherein R ¹ is as described above.)
After producing a dichloromonohydrosilane compound represented by the formula, an unreacted monohydrosilane compound, the following general formula (4) produced by the above reaction
R ² _m SiCl _4-m (4)
(Wherein R ² and m are as described above.)
The dichloromonohydrosilane compound represented by the above general formula (3) is separated from the reaction solution by separating and removing the chlorosilane compound represented by formula (2) and the by- produced chlorodihydrosilane compound from the reaction solution . method for producing dichloromonofluoromethane hydrosilane compound characterized obtain Rukoto as a mixture.
[2]
The method for producing a dichloromonohydrosilane compound according to [1], wherein the catalyst is a quaternary ammonium salt or a quaternary phosphonium salt.
[3]
The method for producing a dichloromonohydrosilane compound according to [1] or [2], wherein the reaction is carried out under normal pressure.
[4]
The method for producing a dichloromonohydrosilane compound according to any one of [1] to [3], wherein the trichloroorganosilane compound is 3-chloropropyltrichlorosilane.
[5]
The method for producing a dichloromonohydrosilane compound according to any one of [1] to [4], wherein the monohydrosilane compound is chlorodimethylsilane or dichloromethylsilane.
[6]
The following general formula (4) produced by the reaction of the compounds of the above general formulas (1) and (2)
R ² _m SiCl _4-m (4)
(Wherein R ² and m are as described above.)
The dichloromonohydrosilane according to any one of [1] to [5], wherein the chlorosilane compound represented by general formula (3) is lower in boiling point than the dichloromonohydrosilane compound represented by the general formula (3). Compound production method.
[7]
The combination of the unreacted trichloroorganosilane compound and the dichloromonohydrosilane compound in the above mixture is
3-chloropropyltrichlorosilane and 3-chloropropyldichlorosilane,
2-cyanoethyltrichlorosilane and 2-cyanoethyldichlorosilane,
The method for producing a dichloromonohydrosilane compound according to any one of [1] to [6], which is 3-methacryloxypropyltrichlorosilane and 3-methacryloxypropyldichlorosilane, or phenyltrichlorosilane and phenyldichlorosilane.
[8]
The hydrosilylation reaction is carried out using the mixture obtained by the production method according to any one of [ 1] to [7], and then the unreacted trichloroorganosilane compound is distilled off. Production method.
[9]
The manufacturing method of the diorganoxy monohydrosilane compound which distills a triorganooxysilane compound off after performing organooxylation using the mixture obtained by the manufacturing method in any one of [1]-[7].

  According to the present invention, a dichloromonohydrosilane compound useful as a raw material for synthesizing various silane compounds such as a silane coupling agent and a functional silicone oil can be produced using a monohydrosilane compound that is inexpensive and easily available, and reacted under pressure. Therefore, it can be manufactured at a low cost.

（式中、Ｒ¹は炭素数２〜２０の非置換又はケイ素原子のα位以外に置換基を有する置換一価炭化水素基であり、Ｒ²は炭素数１〜２０の非置換又は置換一価炭化水素基であり、ｍは１、２又は３である。） The manufacturing method of the dichloromonohydrosilane compound represented by the following general formula (3) of the present invention includes a trichloroorganosilane compound represented by the following general formula (1) and a monohydrosilane represented by the following general formula (2). It is characterized by reacting a compound with a catalyst. Moreover, in the manufacturing method of this invention, the chlorosilane compound represented by following General formula (4) is byproduced with the dichloromonohydrosilane compound represented by General formula (3).

(In the formula, R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having 2 to 20 carbon atoms or a substituent other than the α-position of the silicon atom, and R ² is an unsubstituted or substituted one having 1 to 20 carbon atoms. A m-valent hydrocarbon group, and m is 1, 2 or 3.)

Here, as the unsubstituted or substituted monovalent hydrocarbon group having 2 to 20 carbon atoms, particularly 2 to 10 carbon atoms of R ^{1 in} the general formulas (1) and (3), a straight chain having 2 to 20 carbon atoms, Examples include branched or cyclic alkyl groups, alkenyl groups, aryl groups, aralkyl groups, and the like. Specifically, linear alkyl groups such as ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, tert -Branched alkyl groups such as butyl group, texyl group and 2-ethylhexyl group, cyclic alkyl groups such as cyclopentyl group and cyclohexyl group, alkenyl groups such as vinyl group, allyl group and propenyl group, phenyl group and tolyl group And aryl groups such as benzyl group and the like, and aralkyl groups such as benzyl group.

  In addition, some or all of the hydrogen atoms of these hydrocarbon groups may be substituted. Specific examples of the substituent include organo groups such as methoxy, ethoxy, and (iso) propoxy groups. Oxy group, fluorine atom, chlorine atom, bromine atom, halogen atom group such as iodine atom, cyano group, isocyanate group, organothio group, organosulfonyl group, organocarbonyloxy group, organooxycarbonyl group, diorganoamino group, Examples thereof include a bis (triorganosilyl) amino group and an alkylsilyl group, and these can be used in combination. In the case of having these substituents, those having a substituent other than the α-position of the silicon atom are preferred in order to suppress side reactions due to the substituent at the α-position of the silicon atom and from the viewpoint of the availability of the trichloroorganosilane compound. .

  Specific examples of the trichloroorganosilane compound represented by the general formula (1) include ethyltrichlorosilane, propyltrichlorosilane, butyltrichlorosilane, hexyltrichlorosilane, octyltrichlorosilane, decyltrichlorosilane, dodecyltrichlorosilane, Linear alkyltrichlorosilane such as octadecatrichlorosilane, branched alkyltrichlorosilane such as isopropyltrichlorosilane, isobutyltrichlorosilane, tert-butyltrichlorosilane, cyclic alkyltrichlorosilane such as cyclopentyltrichlorosilane, cyclohexyltrichlorosilane, vinyltri Alkenyltrichlorosilane such as chlorosilane and allyltrichlorosilane, phenyltrichlorosilane, o-tolyltrichlorosila M-tolyltrichlorosilane, p-tolyltrichlorosilane, phenyl-containing trichlorosilane such as benzyltrichlorosilane, 3-chloropropyltrichlorosilane, 4-chlorobutyltrichlorosilane, 6-chlorohexyltrichlorosilane, 3-bromopropyltri Haloalkyltrichlorosilanes such as chlorosilane, 3-iodopropyltrichlorosilane, 3,3,3-trifluoropropyltrichlorosilane, cyanoalkyltrichlorosilanes such as 2-cyanoethyltrichlorosilane and 3-cyanopropyltrichlorosilane, 3-isocyanatopropyl Organooxy such as trichlorosilane, 3-methylthiopropyltrichlorosilane, 3-acryloxypropyltrichlorosilane, 3-methacryloxypropyltrichlorosilane Alkyl trichlorosilane, 3-dimethylaminopropyl trichlorosilane, 3- bis (trimethylsilyl) propyl trichlorosilane, 3- trimethylsilylpropyl trichlorosilane and the like.

  Specific examples of the dichloromonohydrosilane compound represented by the general formula (3) of the present invention include ethyldichlorosilane, propyldichlorosilane, butyldichlorosilane, hexyldichlorosilane, octyldichlorosilane, decyldichlorosilane, Linear alkyl dichlorosilanes such as dodecyldichlorosilane, octadecadichlorosilane, etc., branched alkyl dichlorosilanes such as isopropyl dichlorosilane, isobutyl dichlorosilane, tert-butyl dichlorosilane, etc., cyclic alkyl dichlorosilanes such as cyclopentyl dichlorosilane, cyclohexyl dichlorosilane, etc. Alkenyldichlorosilane such as chlorosilane, vinyldichlorosilane, allyldichlorosilane, phenyldichlorosilane, o-tolyldichlorosilane, m-tolyldichlorosilane, p Phenyl group-containing dichlorosilane such as tolyldichlorosilane, benzyldichlorosilane, 3-chloropropyldichlorosilane, 4-chlorobutyldichlorosilane, 6-chlorohexyldichlorosilane, 3-bromopropyldichlorosilane, 3-iodopropyldichlorosilane, Haloalkyldichlorosilanes such as 3,3,3-trifluoropropyldichlorosilane, 2-cyanoethyldichlorosilane, cyanoalkyldichlorosilanes such as 3-cyanopropyldichlorosilane, 3-isocyanatopropyldichlorosilane, 3-methylthiopropyldichlorosilane Organooxyalkyl dichlorosilanes such as 3-acryloxypropyl dichlorosilane and 3-methacryloxypropyl dichlorosilane, 3-dimethylaminopropyl dichlorosilane, - bis (trimethylsilyl) propyl dichlorosilane, 3-trimethylsilyl propyl dichlorosilane, and the like.

Furthermore, as the unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, particularly 1 to 8 carbon atoms of R ² in the above general formulas (2) and (4), a linear or branched chain having 1 to 20 carbon atoms. And a cyclic or cyclic alkyl group, alkenyl group, aryl group, aralkyl group and the like. Specifically, linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl Group, branched alkyl group such as tert-butyl group, texyl group and 2-ethylhexyl group, cyclic alkyl group such as cyclopentyl group and cyclohexyl group, alkenyl group such as vinyl group and propenyl group, phenyl group and tolyl group And aryl groups such as benzyl group and the like, and aralkyl groups such as benzyl group.

  In addition, some or all of the hydrogen atoms of these hydrocarbon groups may be substituted. Specific examples of the substituent include organo groups such as methoxy, ethoxy, and (iso) propoxy groups. Oxy group, fluorine atom, chlorine atom, bromine atom, halogen atom group such as iodine atom, cyano group, isocyanate group, organothio group, organosulfonyl group, organocarbonyloxy group, organooxycarbonyl group, diorganoamino group, Examples thereof include a bis (triorganosilyl) amino group and an alkylsilyl group, and these can be used in combination.

  Specific examples of the monohydrosilane compound represented by the general formula (2) include chlorosilanes such as dichloromethylsilane, chlorodimethylsilane, dichloroethylsilane, diethylchlorosilane, phenyldichlorosilane, diphenylchlorosilane, triethylsilane, And triorganosilanes such as tripropylsilane, tert-butyldimethylsilane, triisopropylsilane, phenyldimethylsilane, diphenylmethylsilane, and triphenylsilane. It is preferable to use dichloromethylsilane or chlorodimethylsilane because of its high reactivity and easy availability.

  Although the usage-amount of the monohydrosilane compound of this invention shown by General formula (2) is not specifically limited, Preferably it is 0.3-4.0 mol with respect to 1 mol of trichloroorganosilane compounds, More preferably, it is 0.4. It is -3.0 mol, Most preferably, it is 0.6-2.0 mol. If the amount of monohydrosilane compound used is too small, the reaction may not proceed sufficiently, and the amount of dichloromonohydrosilane compound produced may be reduced. If the amount of monohydrosilane compound used is too large, the dichloromonohydrosilane compound may further increase. The by-product amount of the chlorodihydrosilane compound produced by the reaction may increase and the yield may decrease. The amount of the monohydrosilane compound used can be determined by carrying out the reaction while confirming the amount of by-product of the chlorodihydrosilane compound by gas chromatography or NMR. In order to suppress the by-product amount of the chlorodihydrosilane compound, when the amount of the monohydrosilane compound used for the reaction is 1.0 mol or less, an unreacted trichlorosilane compound remains.

  Here, when a dichlorosilane compound is used as the monohydrosilane compound represented by the general formula (2), the chlorosilane compound represented by the general formula (4) generated by the reaction is a trichlorosilane compound. For this reason, as the reaction proceeds, the trichlorosilane compound represented by the general formula (4) and the trichloroorganosilane compound represented by the general formula (1) compete, and the unreacted monohydrosilane of the general formula (2) Even if the compound remains, the reaction with the trichloroorganosilane compound of the general formula (1) may not proceed.

  In this case, when the boiling point of the chlorosilane compound of the general formula (4) is lower than the boiling point of the dichloromonohydrosilane compound (3), the unreacted monohydrosilane compound (2) and the produced chlorosilane compound (4) are usually used. After distilling off by distillation under pressure or reduced pressure, the reaction rate of the trichloroorganosilane compound (1) can be increased by adding the monohydrosilane compound (2) and reacting again.

  Moreover, even when the chlorosilane compound (4) produced | generated by reaction is other than a trichlorosilane compound, the produced | generated chlorosilane compound (4) and the trichloroorganosilane compound (1) compete, and the reaction rate of a trichloroorganosilane compound (1) In some cases, it may be preferable to perform the same operation.

Accordingly, the boiling point of the chlorosilane compound (4) is preferably lower than the boiling point of the dichloromonohydrosilane compound (3). The difference in boiling point between the dichloromonohydrosilane compound (3) and the chlorosilane compound (4) is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, and particularly preferably 30 ° C. or higher. As an example of the combination of the synthesis raw material trichloroorganosilane compound (1) and the monohydrosilane compound (2) of the reaction produced by the dichloromonohydrosilane compound (3) and the chlorosilane compound (4) having such a boiling point difference,
3-chloropropyltrichlorosilane and dichloromethylsilane,
3-chloropropyltrichlorosilane and chlorodimethylsilane,
2-cyanoethyltrichlorosilane and dichloromethylsilane,
2-cyanoethyltrichlorosilane and chlorodimethylsilane,
3-methacryloxypropyltrichlorosilane and dichloromethylsilane,
3-methacryloxypropyltrichlorosilane and chlorodimethylsilane,
Phenyltrichlorosilane and dichloromethylsilane,
Phenyltrichlorosilane and chlorodimethylsilane,
Phenyltrichlorosilane and triethylsilane,
Examples include a combination of phenyltrichlorosilane and tert-butyldimethylsilane.

  Examples of the catalyst used in the present invention include quaternary ammonium salts or quaternary phosphonium salts. Specifically, methyltributylammonium chloride, methyltributylammonium bromide, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, triethylammonium chloride, tripropylammonium chloride, benzyltrimethylammonium chloride Quaternary ammonium salts such as benzyltributylammonium chloride, trioctylmethylammonium chloride, cetyltrimethylammonium chloride, tetraphenylammonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetraphenylphosphonium chloride, benzyltriphenylphosphonium chloride, etc. Quaternary phospho Umm salts. During the reaction, it is more preferable to use a quaternary phosphonium salt because it is difficult to cause a decomposition reaction during distillation purification.

  Although the usage-amount of the catalyst of this invention is not specifically limited, Preferably it is 0.00001-0.5 mol with respect to 1 mol of trichloroorganosilane compounds of Formula (1), More preferably, it is 0.001-0.2 mol, Most preferably, it is 0.005-0.05 mol. If the amount is less than 0.00001 mol, the reaction may not proceed sufficiently. On the other hand, if the amount is more than 0.5 mol, the reaction rate may not be improved and the economy may be poor.

  The reaction temperature of the present invention is not particularly limited, but is preferably 20 to 200 ° C, more preferably 50 to 150 ° C, and particularly preferably 90 to 130 ° C. If the temperature is lower than 20 ° C, the reaction may not proceed sufficiently. If the temperature is higher than 200 ° C, the catalyst may be decomposed and the reaction may not proceed. The reaction time is preferably 1 to 30 hours, particularly 2 to 15 hours.

  The reaction of the present invention proceeds even without solvent, but a solvent can also be used. Examples of the solvent used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, octane, isooctane, toluene, xylene, mesitylene, tetralin and decalin, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, acetonitrile and the like. Examples include aprotic polar solvents, chlorinated hydrocarbon solvents such as dichloromethane and chloroform. These solvents may be used alone or in combination of two or more. When the boiling point of the trichloroorganosilane compound and monohydrosilane compound used in the reaction of the present invention is low and the temperature necessary for the reaction to proceed at normal pressure cannot be achieved, the reaction is carried out in a high boiling point solvent, The reaction can proceed.

  Although this reaction can be carried out under normal pressure or under pressure, it is preferably carried out under normal pressure because a special reaction apparatus is not required.

  Although it does not specifically limit as reaction atmosphere of this invention, In order to avoid a hydrolysis of a chlorosilane compound and it is preferable from safety | security in inert gas atmosphere, such as nitrogen, argon, helium.

  The method for purifying the reaction solution obtained in the present invention to obtain the target dichloromonohydrosilane compound is not particularly limited, but it is preferably purified by distillation. When performing distillation purification, the catalyst component is in a dissolved state in the reaction solution. Therefore, if the temperature in the distillation kettle rises during distillation, the quaternary ammonium salt used in the catalyst decomposes and the tertiary amine compound is converted. When mixed in the fraction, the dichloromonohydrosilane compound may be disproportionated to produce a chlorodihydrosilane compound and a trichlorosilane compound. Therefore, distillation is performed at a low temperature under reduced pressure, preferably at a temperature not higher than the reaction temperature (for example, 30 to 90 ° C.), and the reaction mixture is separated from the catalyst to obtain a crude distillate, followed by rectification. The desired dichloromonohydrosilane compound can be separated.

  In distillation purification of the crude distillate, the dichloromonohydrosilane compound (3) can be separated from other unreacted components in the reaction solution to obtain a high-purity compound, or the unreacted monohydrosilane compound (2) and A chlorosilane compound (4) produced by the reaction of the monohydrosilane compound (2) and a by-produced chlorodihydrosilane compound are separated, and a distillate fraction is obtained without separation from the unreacted trichloroorganosilane compound (1). The trichloroorganosilane compound (1) can also be separated after use in the next step. For example, when the dichloromonohydrosilane compound (3) is used in the hydrosilylation reaction in the next step and the hydrosilylation product is a distillable substance, the trichloroorganosilane compound (1) and the hydrosilylation are used. The boiling point difference of the product may be larger than the boiling point difference between the trichloroorganosilane compound (1) and the dichloromonohydrosilane compound (3), and the trichloroorganosilane compound (1) may be easily separated.

  Moreover, after changing the chloro group of the dichloromonohydrosilane compound obtained in the present invention to an organooxy group to obtain a diorganooxymonohydrosilane compound, it can be used as a raw material for hydrosilylation reaction and various silicone compounds. . Also in this case, when a mixture of a dichloromonohydrosilane compound and a trichlorosilane compound is used to form an organooxysilane mixture, the difference in boiling point of the triorganooxysilane compound as the diorganooxymonohydrosilane compound is It may be larger than the boiling point difference of the chlorosilane compound and may be easily purified. When the organooxy group has a molecular weight larger than that of the methoxy group, the difference in boiling point becomes larger after such an organooxysilane compound. Therefore, it can be separated as a mixture of a dichloromonohydrosilane compound and a trichlorosilane compound and used in the next step.

  By separating the dichloromonohydrosilane compound and the trichlorosilane compound from the components in the other reaction solution, distillation is facilitated, loss during distillation is reduced, and the distillation yield of the dichloromonohydrosilane compound is improved. preferable. In particular, when the chlorosilane compound of the above general formula (4) produced by the reaction is lower than the boiling point of the dichloromonohydrosilane compound, the unreacted monohydrosilane compound (2), the chlorosilane compound (4), and the by-produced chlorodi The mixture of the remaining dichloromonohydrosilane compound and trichlorosilane compound obtained by distilling the hydrosilane compound by distillation can also be used for the reaction in the next step as it is.

  Thus, it is preferable that the boiling point of the chlorosilane compound (4) is lower than the boiling point of the dichloromonohydrosilane compound (3) even in the step of performing distillation purification. The difference in boiling point between the dichloromonohydrosilane compound (3) and the chlorosilane compound (4) is preferably 10 ° C. or more, more preferably 20 ° C. or more, and particularly preferably 30 ° C. or more. As an example of a combination of a trichloroorganosilane compound (1) and a monohydrosilane compound (2), which is a synthetic raw material for a reaction in which a dichloromonohydrosilane compound (3) and a chlorosilane compound (4) having different boiling points are generated. Include those mentioned above.

  EXAMPLES Hereinafter, although an Example and a reference example demonstrate this invention concretely, this invention is not limited to the following Example.

[ Reference Example 1]
Preparation of phenyldichlorosilane A 500 mL four-necked glass flask was equipped with a reflux condenser, a thermometer and a stirrer, and the inside was purged with nitrogen. This flask was charged with 211.5 g (1.0 mol) of phenyltrichlorosilane and 5.9 g (0.02 mol) of tetrabutylphosphonium chloride. While adjusting the internal temperature to 100 to 120 ° C., 69.0 g (0.6 mol) of triethylsilane was dropped over 2 hours, and then aging was performed for 1 hour at the same temperature. While adjusting the obtained reaction liquid under reduced pressure so that the internal temperature does not exceed 90 ° C., the reaction liquid mixture was discharged and separated from the catalyst. By rectifying the obtained fraction, 90.3 g of phenyldichlorosilane (0.508 mol, yield 84.7% based on triethylsilane) and 88.2 g of triethylchlorosilane (0.585 mol, based on triethylsilane) were obtained. Yield 97.5%).

[ Reference Example 2]
Preparation of phenyldichlorosilane A 500 mL four-necked glass flask was equipped with a reflux condenser, a thermometer and a stirrer, and the inside was purged with nitrogen. This flask was charged with 211.5 g (1.0 mol) of phenyltrichlorosilane and 2.9 g (0.01 mol) of tetrabutylphosphonium chloride. While adjusting the internal temperature to 80 to 110 ° C., 207.0 g (1.8 mol) of dichloromethylsilane was added dropwise over 4 hours, followed by aging at the same temperature for 2 hours. The resulting reaction solution is distilled under reduced pressure, and after collecting low-boiling components such as unreacted dichloromethylsilane and trichloromethylsilane produced by the reaction with a dry ice trap, the internal temperature does not exceed 90 ° C. The mixture of phenylchlorosilane, phenyldichlorosilane, and phenyltrichlorosilane was allowed to flow out while being adjusted so as to be separated from the catalyst. The obtained fraction was rectified to obtain 79.7 g of phenyldichlorosilane (0.45 mol, yield 45% based on phenyltrichlorosilane).

[ Reference Example 3]
Production of 3-chloropropyldichlorosilane A 1,000 mL four-necked glass flask was equipped with a reflux condenser, a thermometer and a stirrer, and the interior was purged with nitrogen. This flask was charged with 742.0 g (3.5 mol) of 3-chloropropyltrichlorosilane and 20.6 g (0.07 mol) of tetrabutylphosphonium chloride. While adjusting the internal temperature to 95 to 120 ° C., 264.9 g (2.8 mol) of chlorodimethylsilane was added dropwise over 10 hours, and then aged for 3 hours at the same temperature. The resulting reaction solution is distilled under reduced pressure, and after collecting low boiling components such as unreacted chlorodimethylsilane and dichlorodimethylsilane produced by the reaction with a dry ice trap, the internal temperature does not exceed 90 ° C. While adjusting, the mixture of 3-chloropropylchlorosilane, 3-chloropropyldichlorosilane, and 3-chloropropyltrichlorosilane was allowed to flow out and separated from the catalyst. The obtained fraction was rectified to obtain 357.8 g of 3-chloropropyldichlorosilane (2.02 mol, yield 72.0% based on chlorodimethylsilane).

[ Reference Example 4]
Production of 3-chloropropyldichlorosilane A 1,000 mL four-necked glass flask was equipped with a reflux condenser, a thermometer and a stirrer, and the interior was purged with nitrogen. The flask was charged with 565.1 g (2.67 mol) of 3-chloropropyltrichlorosilane and 7.9 g (0.027 mol) of tetrabutylphosphonium chloride. Dichloromethylsilane (460.6 g, 4.0 mol) was added dropwise over 6 hours while adjusting the internal temperature to 80 to 120 ° C., and then aged at the same temperature for 2 hours. The obtained reaction solution is distilled under reduced pressure, and after collecting low boiling components such as unreacted dichloromethylsilane and dichlorodimethylsilane produced by the reaction with a dry ice trap, the internal temperature does not exceed 90 ° C. While adjusting, the mixture of 3-chloropropylchlorosilane, 3-chloropropyldichlorosilane, and 3-chloropropyltrichlorosilane was allowed to flow out and separated from the catalyst. The obtained fraction was rectified to obtain 227.5 g of 3-chloropropyldichlorosilane (1.28 mol, yield 48.0% based on chlorodimethylsilane).

[Example 1 ]
Production of 3-chloropropyldichlorosilane A 200 mL four-necked glass flask was equipped with a reflux condenser, a thermometer and a stirrer, and the interior was purged with nitrogen. This flask was charged with 106.0 g (0.5 mol) of 3-chloropropyltrichlorosilane and 2.9 g (0.01 mol) of tetrabutylphosphonium chloride. Chlorodimethylsilane (37.8 g, 0.4 mol) was added dropwise over 9 hours while adjusting the internal temperature to 95 to 120 ° C., and then aged at the same temperature for 3 hours. The resulting reaction solution is distilled under reduced pressure, and after collecting low boiling components such as unreacted chlorodimethylsilane and dichlorodimethylsilane produced by the reaction with a dry ice trap, the internal temperature does not exceed 90 ° C. While adjusting, the mixture of 3-chloropropylchlorosilane, 3-chloropropyldichlorosilane, and 3-chloropropyltrichlorosilane was allowed to flow out and separated from the catalyst. The obtained fraction was distilled to obtain 110.8 g of a mixture of 3-chloropropyldichlorosilane and 3-chloropropyltrichlorosilane (purity 51.9% of 3-chloropropyldichlorosilane, pure content 57.5 g, 0.005 g). 324 mol, yield 81.0% based on chlorodimethylsilane).

[Example 2]
Hydrosilylation reaction using a mixture of 3-chloropropyldichlorosilane and 3-chloropropyltrichlorosilane A reflux condenser, a thermometer and a stirrer were attached to a 100 mL four-necked glass flask, and the interior was purged with nitrogen. This flask was charged with 11.1 g (0.145 mol) of allyl chloride and 28.3 mg (2.9 × 10 ⁻⁶ mol) of a 2% by mass isopropanol solution of chloroplatinic acid. While controlling the internal temperature to 45 to 110 ° C., 49.8 g of a mixture of 3-chloropropyldichlorosilane and 3-chloropropyltrichlorosilane (purity 51.9% of 3-chloropropyldichlorosilane, pure content 25.8 g) 0.145 mol) was added dropwise over 4.5 hours, followed by aging at the same temperature for 1 hour. Byproducts associated with 3-chloropropyltrichlorosilane were not produced. The reaction solution was distilled under reduced pressure to obtain 22.8 g (0.09 mol, yield 61.9%) of bis (3-chloropropyl) dichlorosilane. By distillation, 3-chloropropyltrichlorosilane could be easily separated.
Thereby, hydrosilylation reaction was able to be performed using 3-chloropropyl dichlorosilane containing 3-chloropropyl trichlorosilane.

[Example 3]
Production of 3-chloropropyldiethoxysilane A reflux condenser, a thermometer and a stirrer were attached to a 300 mL four-necked glass flask, and the interior was purged with nitrogen. The flask was charged with 95.5 g of a mixture of 3-chloropropyldichlorosilane and 3-chloropropyltrichlorosilane (purity 93.0%, purity 88.8 g, 0.5 mol of 3-chloropropyldichlorosilane). . While cooling the flask with ice water, 88.9 g (0.6 mol) of triethyl orthoformate was added dropwise over 3 hours, and then the internal temperature was raised to 50 ° C. and aged for 2 hours. The obtained reaction liquid was distilled to obtain 83.6 g (0.425 mol, yield 85.0%) of 3-chloropropyldiethoxysilane. The 3-chloropropyltriethoxysilane produced by the reaction of 3-chloropropyltrichlorosilane and triethyl orthoformate could be easily separated by distillation.
Thereby, even if it used the mixture of 3-chloropropyl dichlorosilane and 3-chloropropyl trichlorosilane, the synthesis | combination of organooxysilane was possible, and the impurity derived from 3-chloropropyl trichlorosilane was also easily separable. .

Claims (9)

The following general formula (1)
R ¹ SiCl ₃ (1)
(In the formula, R ¹ is a C1-C20 unsubstituted or substituted monovalent hydrocarbon group having a substituent other than the α-position of the silicon atom.)
And a trichloroorganosilane compound represented by the following general formula (2)
HSiR ² _m Cl _3-m (2)
(In the formula, R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and m is 1, 2 or 3.)
And a monohydrosilane compound represented by the following general formula (3):
HSiR ¹ Cl ₂ (3)
(Wherein R ¹ is as described above.)
After producing a dichloromonohydrosilane compound represented by the formula, an unreacted monohydrosilane compound, the following general formula (4) produced by the above reaction
R ² _m SiCl _4-m (4)
(Wherein R ² and m are as described above.)
The dichloromonohydrosilane compound represented by the above general formula (3) is separated from the reaction solution by separating and removing the chlorosilane compound represented by formula (2) and the by- produced chlorodihydrosilane compound from the reaction solution . method for producing dichloromonofluoromethane hydrosilane compound characterized obtain Rukoto as a mixture.   The method for producing a dichloromonohydrosilane compound according to claim 1, wherein the catalyst is a quaternary ammonium salt or a quaternary phosphonium salt.   The method for producing a dichloromonohydrosilane compound according to claim 1 or 2, wherein the reaction is carried out under normal pressure.   The method for producing a dichloromonohydrosilane compound according to any one of claims 1 to 3, wherein the trichloroorganosilane compound is 3-chloropropyltrichlorosilane.   The method for producing a dichloromonohydrosilane compound according to any one of claims 1 to 4, wherein the monohydrosilane compound is chlorodimethylsilane or dichloromethylsilane. The following general formula (4) produced by the reaction of the compounds of the above general formulas (1) and (2)
R ² _m SiCl _4-m (4)
(Wherein R ² and m are as described above.)
The dichloromonohydrosilane compound according to any one of claims 1 to 5, wherein the chlorosilane compound represented by general formula (3) has a boiling point lower than that of the dichloromonohydrosilane compound represented by the general formula (3). Manufacturing method. The combination of the unreacted trichloroorganosilane compound and the dichloromonohydrosilane compound in the above mixture is
3-chloropropyltrichlorosilane and 3-chloropropyldichlorosilane,
2-cyanoethyltrichlorosilane and 2-cyanoethyldichlorosilane,
The method for producing a dichloromonohydrosilane compound according to any one of claims 1 to 6, which is 3-methacryloxypropyltrichlorosilane and 3-methacryloxypropyldichlorosilane, or phenyltrichlorosilane and phenyldichlorosilane. Production of a hydrosilylation product of a dichloromonohydrosilane compound in which a hydrosilylation reaction is carried out using the mixture obtained by the production method according to any one of claims 1 to 7, and then an unreacted trichloroorganosilane compound is distilled off. Method. The manufacturing method of the diorganoxy monohydrosilane compound which distills a triorganooxysilane compound after performing organooxylation using the mixture obtained by the manufacturing method of any one of Claims 1-7.