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WO2018173993A1 - Production method for alkoxyhydrosilane and production method for alkoxyhalosilane - Google Patents

Production method for alkoxyhydrosilane and production method for alkoxyhalosilane Download PDF

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Publication number
WO2018173993A1
WO2018173993A1 PCT/JP2018/010720 JP2018010720W WO2018173993A1 WO 2018173993 A1 WO2018173993 A1 WO 2018173993A1 JP 2018010720 W JP2018010720 W JP 2018010720W WO 2018173993 A1 WO2018173993 A1 WO 2018173993A1
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Prior art keywords
alkoxyhalosilane
producing
group
alkoxyhydrosilane
formula
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PCT/JP2018/010720
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French (fr)
Japanese (ja)
Inventor
章徳 佐藤
誠 安田
能弘 西本
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株式会社カネカ
国立大学法人大阪大学
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Application filed by 株式会社カネカ, 国立大学法人大阪大学 filed Critical 株式会社カネカ
Priority to JP2019507654A priority Critical patent/JPWO2018173993A1/en
Priority to CN201880020434.4A priority patent/CN110461856B/en
Publication of WO2018173993A1 publication Critical patent/WO2018173993A1/en

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  • the present invention relates to a method for producing alkoxyhydrosilane, a method for producing alkoxyhalosilane suitably used as a raw material compound in the production method, and an alkoxyhalosilane having a specific structure.
  • alkoxyhydrosilane having a specific substituent on a carbon atom bonded to a silicon atom is also known, and it is known that a curable composition having a high curing rate can be obtained from a polymer produced therefrom.
  • Patent Document 1 alkoxyhydrosilane having a specific substituent on a carbon atom bonded to a silicon atom is also known, and it is known that a curable composition having a high curing rate can be obtained from a polymer produced therefrom.
  • a method for producing alkoxyhydrosilane a method of selectively hydrogenating a part of alkoxy groups of the corresponding trialkoxysilane in a plurality of steps can be considered.
  • methoxymethyltrimethoxysilane is reacted with acetyl chloride in the presence of a catalyst to obtain methoxymethyltrichlorosilane, then methoxymethyltrichlorosilane and methyldichlorosilane are reacted to obtain methoxymethyldichlorosilane
  • a method for producing methoxymethyldimethoxysilane (H—Si (CH 2 OCH 3 ) (OCH 3 ) 2 ) by reacting methoxymethyldichlorosilane with trimethyl orthoacetate or methanol and trimethyl orthoacetate has been proposed.
  • Patent Document 2 Synthesis Example 1
  • Patent Document 3 Example 6
  • Patent Document 4 Example 3
  • Patent Document 1 has a large number of steps and a low yield when selectively hydrogenating one or two of the three halogen atoms of organotrihalosilane. As a result, there is still room for improvement in the desired yield of alkoxyhydrosilane based on the amount of organotrimethoxysilane as a raw material.
  • the present invention has been made in view of the above problems, and a method for producing an alkoxyhydrosilane capable of producing a target product in a high yield and a method for producing an alkoxyhalosilane suitably used as a raw material in the method for producing an alkoxyhydrosilane.
  • the object is to provide a method and a novel alkoxyhalosilane of a specific structure.
  • the inventors of the present invention produce an alkoxyhalosilane having a predetermined structure by halogenating an alkoxysilane having a predetermined structure with a halogenating agent under specific conditions, and converting the alkoxyhalosilane having the predetermined structure into an ether.
  • the present inventors have found that the above problems can be solved by producing an alkoxyhydrosilane having a desired structure by hydrogenation using a hydrogenating agent in a solvent containing an aprotic organic solvent having a bond. It was.
  • H-SiR 1 a (OR 2 ) 3-a (1)
  • R 1 and R 2 are each independently a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a is 1 or 2.
  • R For each of 1 and OR 2 when there are a plurality of them, they may be the same or different.
  • a halogenating agent E
  • halogenating agent (E) when 1 mole equivalent of stoichiometric halogenating agent (E) is used to form 1 mol of alkoxyhalosilane (B) from 1 mol of alkoxysilane (C) The manufacturing method whose quantity is 1.5 molar equivalent or less.
  • X is a chlorine atom
  • the halogenating agent (E) is acetyl chloride.
  • R 3 is an alkyl group having 1 to 20 carbon atoms, and the alkyl group as R 3 may be substituted with a halogen atom or an alkoxy group having 1 to 6 carbon atoms.
  • R 4 is a hydrocarbon group having 1 to 20 carbon atoms, and X is a halogen atom, and for two OR 4 , they may be the same or different.
  • R 3 is an alkyl group having 1 to 3 carbon atoms substituted with an alkoxy group having 1 to 3 carbon atoms
  • R 4 is an alkyl group having 1 to 3 carbon atoms.
  • (22) The alkoxyhalosilane compound according to (21), wherein R 3 is a methoxymethyl group and R 4 is a methyl group. About.
  • the manufacturing method of the alkoxyhydrosilane which can manufacture a target object with a high yield, the manufacturing method of the alkoxyhalosilane used suitably as a raw material in the manufacturing method of the said alkoxyhydrosilane, and novel of a specific structure And alkoxyhalosilanes can be provided.
  • the alkoxyhydrosilane (A) produced by the method according to the present invention has the following formula (1): H-SiR 1 a (OR 2 ) 3-a (1)
  • R 1 and R 2 are each independently a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a is 1 or 2.
  • It is a compound represented by these.
  • R 1 and R 2 are each independently a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
  • the substituent that the hydrocarbon group as R 1 and R 2 may have is not particularly limited as long as it is a group that does not inhibit the good production of alkoxyhydrosilane. Specific examples include an alkoxy group, a cycloalkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an alkenylthio group, an arylthio group, an aralkylthio group, and a halogen atom.
  • an alkoxy group and a halogen atom are preferable from the usefulness of the resulting hydrosilane.
  • the alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, still more preferably a methoxy group and an ethoxy group, and particularly preferably a methoxy group.
  • An alkoxy group having a small number of carbon atoms and a small stericity tends to favorably advance the hydrogenation reaction.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom and a chlorine atom are preferable in that a side reaction with the hydrogenating agent (D) hardly occurs.
  • the total number of carbon atoms of the hydrocarbon group which may have a substituent as R 1 and R 2 is smaller as the reactive functional group when the total number of carbon atoms is smaller when introduced into the polymer molecular chain. Since reactivity tends to be high, 1 to 12 is preferable, 1 to 6 is more preferable, and 1 to 3 is particularly preferable.
  • the unsubstituted hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-hexyl group, n-octyl group, 2 -Alkyl groups such as ethylhexyl group, n-dodecyl group and n-icosyl group; cycloalkyl groups such as cyclopropyl group and cyclohexyl group; alkenyl groups such as vinyl group, allyl group and isopropenyl group; phenyl group Aromatic hydrocarbon groups such as o-tolyl group, m-tolyl group, p-tolyl group and naphthalen-1-yl group; and aralkyl groups such as benzyl group, phenethyl group and naphthalen-1-ylmethyl group It is done. Among them,
  • R 1 is preferably a hydrocarbon group having 1 to 3 carbon atoms which may have a substituent from the viewpoint of easy availability and production of the raw material of alkoxyhydrosilane (A). Further, R 1 is either substituted by a chlorine atom, that an ether bond preferable from the viewpoint of reactivity.
  • Suitable groups for R 1 include methyl group, ethyl group, n-propyl group, isopropyl group, chloromethyl group, 1-chloroethyl group, 2-chloroethyl group, 1-chloropropyl group, 2-chloropropyl group, Examples include 3-chloropropyl group, methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 2-methoxyethyl group, 1-methoxypropyl group, 2-methoxypropyl group, and 3-methoxypropyl group. Among these, a methoxymethyl group is preferable because the hydrogenation reaction proceeds well.
  • R 2 is preferably a methyl group or an ethyl group, and more preferably a methyl group. That is, the alkoxyhydrosilane (A) is preferably methoxyhydrosilane or ethoxyhydrosilane, and more preferably methoxyhydrosilane.
  • the plurality of groups when there are a plurality of R 1 or (OR 2 ), the plurality of groups may be the same or different from each other, and are preferably the same from the viewpoint of ease of raw material production. .
  • a is 1 or 2. From the viewpoint of availability of raw materials, a is preferably 1. On the other hand, the reactivity of the alkoxysilyl group of the alkoxyhydrosilane (A) can be adjusted and further chemical modification can be performed by the substituent of the organic group on the silicon group. For this reason, a is preferably 2. In producing various chemical products using the obtained alkoxyhydrosilane (A), the number of alkoxy groups contained in the alkoxysilyl group is determined from the reactivity of the alkoxysilyl group derived from the alkoxyhydrosilane (A). Is more preferable. For this reason, a is more preferably 1.
  • alkoxyhydrosilane (A) represented by the formula (1) obtained by the method for producing an alkoxyhydrosilane according to the present invention include methyldimethoxysilane (HSi (CH 3 ) (OCH 3 ) 2 ), methyl diethoxy silane (HSi (CH 3) (OC 2 H 5) 2), ethyl dimethoxy silane (HSi (C 2 H 5) (OCH 3) 2), ethyldiethoxysilane (HSi (C 2 H 5) (OC 2 H 5) 2), n- propyl dimethoxy silane (HSi (n-C 3 H 7) (OCH 3) 2), n- propyl diethoxy silane (HSi (n-C 3 H 7) (OC 2 H 5 2 ), n-hexyldimethoxysilane (HSi (n-C 6 H 13 ) (OCH 3 ) 2 ), n-hexyldiethoxysilane
  • the alkoxy hydrosilane (A) is represented by the following formula (2): X-SiR 1 a (OR 2 ) 3-a (2) (In Formula (2), R 1 , R 2 , and a are the same as in Formula (1), and X is a halogen atom.) It is manufactured using the alkoxyhalosilane (B) represented by these.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • a chlorine atom and a bromine atom are preferable from the viewpoint of availability of raw materials, and a chlorine atom is more preferable in terms of ease of handling.
  • a preferred method for producing the alkoxyhalosilane (B) will be described later.
  • a hydrogen atom bonded to a silicon atom in the compound exemplified as a preferable specific example of the alkoxyhydrosilane (A) represented by the formula (1) is a chlorine atom.
  • the compound substituted by is mentioned.
  • the alkoxyhydrosilane (A) is produced by hydrogenating the halogen atom (X) contained in the alkoxyhalosilane (B) with the hydrogenating agent (D).
  • the type of the hydrogenating agent (D) is not particularly limited as long as the halogen atom (X) in the alkoxyhalosilane (B) can be hydrogenated well, and is appropriately selected from the known hydrogenating agents (D).
  • the hydrogenating agent (D) may be used in combination of two or more.
  • the following formula (D1) MBH 4 ... (D1) (In the formula (D1), M is lithium, sodium, or potassium.)
  • M is lithium, sodium, or potassium.
  • the compound represented by these is mentioned.
  • sodium borohydride, in which M is sodium, is preferable because the alkoxyhydrosilane (A) can be easily produced from the alkoxyhalosilane (B) with a high yield.
  • the amount of hydrogenating agent (D) used is not particularly limited as long as alkoxyhydrosilane (A) can be produced in a desired yield.
  • the amount of the hydrogenating agent (D) used is preferably 0.5 to 10 times the stoichiometric amount capable of hydrogenating 1 mol of the halogen atom (X) contained in the alkoxyhalosilane (B).
  • An amount of 0.0 to 5.0 times is more preferable, and an amount of 1.2 to 3.0 times is particularly preferable.
  • Suitable aprotic organic solvents having an ether bond include cyclic ethers such as tetrahydrofuran, tetrahydropyran, and 1,4-dioxane; dialkyl ethers such as diethyl ether, di-n-butyl ether, and cyclopentyl methyl ether; Alkoxybenzenes such as anisole; alkoxyalkanoic acid esters such as methyl methoxyacetate and ethyl methoxyacetate; 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol dimethyl ether, diethylene glycol dimethyl ether (diglyme), dipropylene glycol Dimethyl ether, triethylene glycol dimethyl ether (triglyme), tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether (Tetraglyme), glycol dialkyl ethers such as tetraethylene glycol dimethyl ether, ethylene glycol
  • alkoxyhydrosilane (A) can be easily produced in a good yield, and recovery and purification after handling and reaction. 1,2-dimethoxyethane is more preferable.
  • the content of the aprotic organic solvent having an ether bond in the solvent (S) is not particularly limited as long as it is 50% by mass or more, but is preferably 70% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass. preferable. As the content of the aprotic organic solvent having an ether bond in the solvent (S) is larger, the hydrogenation reactivity tends to be improved.
  • the type of the other solvent is a hydrogenating agent (D) of the halogen atom (X) contained in the alkoxyhalosilane (B).
  • D hydrogenating agent
  • X halogen atom
  • the other solvent typically, a hydrocarbon organic solvent is preferable in that it hardly reacts with the hydrogenating agent (D).
  • a solvent that is miscible with an aprotic organic solvent having an ether bond is more preferable.
  • the amount of the solvent (S) used is not particularly limited as long as the alkoxyhydrosilane (A) can be produced in a desired yield.
  • the amount of the solvent (S) used is typically preferably 50 to 1000 parts by weight, more preferably 70 to 800 parts by weight, and more preferably 100 to 500 parts by weight with respect to 100 parts by weight of the alkoxyhalosilane (B). Particularly preferred.
  • solvent (S) When there is too little solvent (S), there exists a tendency for progress of hydrogenation to become slow, and when there is too much solvent (S), the removal after reaction becomes complicated.
  • the conditions for reacting the alkoxyhalosilane (B) with the hydrogenating agent (D) described above are not particularly limited as long as the reaction proceeds well.
  • the hydrogenating agent (D) may be added to the alkoxyhalosilane (B), and conversely, the alkoxyhalosilane (B) may be added to the hydrogenating agent (D).
  • the solvent (S) is preferably present in the reaction system.
  • the method for adding the alkoxyhalosilane (B) or the hydrogenating agent (D) is not particularly limited, and the alkoxyhalosilane (B) or the hydrogenating agent (D) may be added alone to the reaction system.
  • a solution or suspension of B) or hydrogenating agent (D) may be added to the reaction system.
  • Alkoxyhalosilane (B) or hydrogenating agent (D) may be added to the reaction system by dividing it once or several times, or may be continuously added to the reaction system by a method such as dropping.
  • the time for adding the alkoxyhalosilane (B) or the hydrogenating agent (D) to the reaction system is not particularly limited, and is appropriately selected according to the progress of the reaction.
  • the temperature at which the alkoxyhalosilane (B) and the hydrogenating agent (D) are reacted is not particularly limited as long as the reaction proceeds well. Typically, it is 0 to 40 ° C.
  • the atmosphere in which the alkoxyhalosilane (B) and the hydrogenating agent (D) are reacted is not particularly limited, but the reaction is preferably performed in an inert gas atmosphere such as nitrogen gas.
  • the reaction between the alkoxyhalosilane (B) and the hydrogenating agent (D) may be carried out under atmospheric pressure, under reduced pressure, or under pressure.
  • the reaction between the alkoxyhalosilane (B) and the hydrogenating agent (D) can be carried out by either a batch method or a continuous method.
  • the time for reacting the alkoxyhalosilane (B) and the hydrogenating agent (D) is not particularly limited as long as the reaction proceeds well. Including the addition time of alkoxyhalosilane (B) or hydrogenating agent (D), it is typically 1 hour to 24 hours, preferably 1 hour 30 minutes to 10 hours, more preferably 2 hours to 5 hours. . If the reaction time is short, there is a concern that the temperature of the reaction system rapidly rises due to heat generated by the reaction. If the reaction time is long, the product may be decomposed. However, when the number of carbon atoms of R 1 in the alkoxyhalosilane (B) represented by the formula (2) is large, the hydrogenation reaction may take a long time. In consideration of this point, the reaction time is preferably appropriately determined while analyzing the progress of the reaction as necessary.
  • the alkoxyhydrosilane (A) produced by the method described above is recovered from the reaction system by a well-known method such as filtration or collection under reduced pressure, and then purified by a method such as distillation, if necessary.
  • the alkoxyhydrosilane (A) produced by such a method is, for example, as proposed in WO2011 / 161915, hydrosilylation reaction using Si—H, hydrolysis and condensation reaction using Si—OR 2. It can be used as a raw material for producing various compounds.
  • the production method of the alkoxyhalosilane (B) represented by the above formula (2) used for the production of the alkoxyhydrosilane is not particularly limited. Since the yield is good, the production method of alkoxyhalosilane (B) is represented by the following formula (3): SiR 1 a (OR 2 ) 4-a (3) (In formula (3), R 1 , R 2 , and a are the same as in formula (2).)
  • a method comprising reacting the alkoxysilane (C) represented by formula (I) with a halogenating agent (E) at a temperature of ⁇ 30 ° C. or higher and 80 ° C.
  • alkoxysilane (C) is SiR 1 a (OR 2 ) 4-a (3) (In formula (3), R 1 , R 2 , and a are the same as in formula (2).) It is a compound represented by these.
  • alkoxysilane (C) As a suitable specific example of alkoxysilane (C), the hydrogen atom couple
  • the halogenating agent is not particularly limited as long as it is a compound that can halogenate one of the alkoxy groups represented by 4-a OR 2 contained in the alkoxysilane (C) with a desired high selectivity. Not.
  • a carboxylic acid halide is preferable because post-treatment after the reaction is easy.
  • a halogen atom (X) a chlorine atom or a bromine atom is preferable in terms of reactivity, and a chlorine atom is more preferable in terms of availability of raw materials and price.
  • a carboxylic acid halide a carboxylic acid chloride or a carboxylic acid bromide is preferable, and a carboxylic acid chloride is more preferable.
  • carboxylic acid halides include monochlorides such as acetyl chloride, propionyl chloride, butanoyl chloride, acryloyl chloride, methacryloyl chloride, benzoyl chloride, oxalyl chloride, adipoyl chloride, succinic acid chloride, sebacic acid chloride, and the like.
  • Examples thereof include dichlorides, trichlorides such as 1,3,5-benzenetricarboxylic acid trichloride, and bromides such as acetyl bromide.
  • acetyl chloride, benzoyl chloride, and acetyl bromide are more preferable in terms of yield of the reaction, and acetyl chloride is particularly preferable in terms of cost.
  • the amount of the halogenating agent (E) used is 1 molar equivalent of the stoichiometric amount of the halogenating agent (E) that generates 1 mol of alkoxyhalosilane (B) from 1 mol of alkoxysilane (C). In some cases, the amount is 1.5 molar equivalents or less, preferably 0.5 to 1.2 molar equivalents, and more preferably 0.7 to 1.1 molar equivalents. If the amount of the halogenating agent (E) used decreases, the halogenation rate decreases, which ultimately leads to a decrease in the yield of the desired hydrosilane. If the amount used increases, the amount of by-produced dihalogenated compounds and trihalogenated compounds increases. Resulting in.
  • the metal salt (F) is preferably a salt composed of a metal cation and an anion.
  • Preferred examples of the metal in the metal salt (F) include alkaline earth metals, transition metals, zinc, aluminum, and boron.
  • Preferred examples of the anion constituting the metal salt (F) include halide ions, BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , ClO 4 ⁇ , CF 3 CO 2 ⁇ , and CF 3 SO 3 ⁇ .
  • Halide ions are more preferable in that by-products other than halosilane can be suppressed.
  • Preferred examples of the metal salt (F) exhibiting Lewis acidity include magnesium chloride (MgCl 2 ), magnesium bromide (MgBr 2 ), boron trifluoride ether complex (BF 3 .O (C 2 H 5 ) 2 ), Boron trichloride (BCl 3 ), aluminum chloride (AlCl 3 ), aluminum bromide (AlBr 3 ), zinc chloride (ZnCl 2 ), zinc bromide (ZnBr 2 ), tin tetrachloride (SnCl 4 ), tin tetrabromide (SnBr 4 ), iron trichloride (FeCl 3 ), iron tribromide (FeBr 3 ), titanium tetrachloride (TiCl 4 ), titanium tetrabromide (TiBr 4 ), and the like.
  • MgCl 2 magnesium chloride
  • MgBr 2 magnesium bromide
  • zinc chloride is preferable in terms of reactivity and ease of handling. For this reason, it is preferable to use the metal salt (F) containing zinc chloride for the reaction between the alkoxysilane (C) and the halogenating agent (E).
  • the amount of the metal salt (F) used is not particularly limited as long as the reaction between the alkoxysilane (C) and the halogenating agent (E) proceeds well.
  • the amount of the metal salt (F) used is typically preferably 0.01 to 20 mol%, more preferably 0.05 to 10 mol%, relative to the amount of the alkoxysilane (C) substance. 1 to 2.0 mol% is particularly preferred. If the amount of the metal salt (F) used is small, the reaction rate is slow, and if it is too large, it is economically disadvantageous.
  • a solvent can be used as necessary.
  • the solvent is not particularly limited as long as the halogenation of the alkoxysilane (C) is not inhibited by reaction with the halogenating agent (E) or the like.
  • Suitable solvents include, for example, aprotic ether solvents such as 1,2-dimethoxyethane, hydrocarbon solvents such as hexane, and aprotic ester solvents such as methyl acetate.
  • a solvent may be used independently or may be used in mixture of multiple.
  • the solvent (S) described above as the solvent used for the production of the alkoxyhalosilane (B) can also be used.
  • the amount of the solvent used is not particularly limited as long as the alkoxyhalosilane (B) can be produced in a desired yield.
  • the amount of the solvent used is preferably 1000 parts by mass or less, more preferably 800 parts by mass or less, and particularly preferably 500 parts by mass or less with respect to 100 parts by mass of the alkoxysilane (C).
  • the removal after the reaction becomes complicated, and it is disadvantageous economically.
  • the reaction between the alkoxysilane (C) and the halogenating agent (E) is performed at a temperature of ⁇ 30 ° C. or higher and 100 ° C. or lower.
  • the reaction temperature may be constant during the reaction or may vary.
  • the temperature at which the alkoxysilane (C) and the halogenating agent (E) are reacted may be at least partially -30 ° C to 100 ° C, and the average temperature during the reaction is -30 ° C to 100 ° C.
  • the temperature during the reaction is preferably within the range of ⁇ 30 ° C. or more and 100 ° C. or less. When the temperatures during the reaction are all lower than ⁇ 30 ° C., the reaction hardly proceeds. If the reaction temperature exceeds 100 ° C. for a long time, the amount of by-produced dihalides and trihalides increases.
  • the temperature at which the alkoxysilane (C) and the halogenating agent (E) are reacted is preferably at least partly ⁇ 10 ° C. or higher and 90 ° C. or lower, and the average temperature during the reaction is ⁇ 10 ° C. It is more preferable that the temperature is 90 ° C. or lower, and it is particularly preferable that all the temperatures during the reaction are within a range of ⁇ 10 ° C. or higher and 90 ° C. or lower. If the reaction temperature is within such a range, the reaction temperature can be adjusted using a commonly used heat medium or refrigerant such as hot water, cold water, or brine, which is economically advantageous.
  • a commonly used heat medium or refrigerant such as hot water, cold water, or brine
  • At least a part of the reaction between the alkoxysilane (C) and the halogenating agent (E) is 0 ° C. or higher and 20 ° C. or lower, and the average temperature during the reaction is 0 ° C. or higher and 20 ° C. or lower. It is more preferable that all the temperatures during the reaction are in the range of 0 ° C. or higher and 20 ° C. or lower. Sufficient reactivity can be secured by setting the temperature during the reaction to 0 ° C. or higher. In addition, when the reaction temperature is 20 ° C. or less, the amount of by-produced dihalides and trihalogenated substances can be sufficiently suppressed.
  • the method for adding the halogenating agent (E) and the metal salt (F) is not particularly limited, and the halogenating agent (E) or the metal salt (F) may be added to the reaction system alone. Alternatively, a solution or suspension of the metal salt (F) may be added to the reaction system. The halogenating agent (E) and the metal salt (F) may be added to the reaction system by dividing it once or several times, or may be continuously added to the reaction system by a method such as dropping.
  • the time for adding the halogenating agent (E) and the metal salt (F) to the reaction system is not particularly limited, and is appropriately selected according to the progress of the reaction.
  • the order of addition of the halogenating agent (E) and the metal salt (F) is not particularly limited, but the metal salt (F) is added first, and then the halogenating agent (E) is added to suppress the temperature increase during the reaction. It is preferably added continuously to the reaction system by a method such as dropping.
  • the atmosphere in which the alkoxysilane (C) and the halogenating agent (E) are reacted is not particularly limited, but the reaction is preferably performed in an inert gas atmosphere such as nitrogen gas.
  • the reaction between the alkoxysilane (C) and the halogenating agent (E) may be carried out under atmospheric pressure, under reduced pressure, or under pressure.
  • the reaction of the alkoxysilane (C) and the halogenating agent (E) can be carried out by either a batch method or a continuous method.
  • the time for reacting the alkoxysilane (C) and the halogenating agent (E) is not particularly limited. Including the time for dropping the halogenating agent (E) and the subsequent reaction time, it is typically 10 minutes to 24 hours, preferably 30 minutes to 10 hours, and more preferably 1 hour to 5 hours. If the reaction time is short, there is a concern that the temperature of the reaction system rapidly rises due to heat generated by the reaction. Although there is no particular influence on the reaction system due to the long reaction time, it is economically disadvantageous.
  • the alkoxyhalosilane (B) thus produced is directly or purified, preferably purified, and used as a production raw material in the method for producing alkoxyhydrosilane (E) by the above-described method.
  • it can be used for hydrolysis, condensation reaction, etc. using Si—X or Si—OR 2 and is suitably used as a raw material for producing various compounds.
  • the alkoxy halosilane compound (B) represented by the said Formula (2) which is a manufacturing raw material of alkoxy hydrosilane (A) is manufactured.
  • the alkoxyhalosilane compounds (B) the following formula (4): X-SiR 3 (OR 4 ) 2 (4)
  • R 3 is an alkyl group having 1 to 20 carbon atoms, and the alkyl group as R 3 may be substituted with a halogen atom or an alkoxy group having 1 to 6 carbon atoms
  • R 4 is a hydrocarbon group having 1 to 20 carbon atoms
  • X is a halogen atom, and for two OR 4 , they may be the same or different.
  • the alkoxyhalosilane compound represented by these is preferable.
  • the halogen atom as X and the halogen atom as a substituent on the alkyl group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom or a bromine atom is preferable for ease of production, From the availability of raw materials, a chlorine atom is preferable.
  • Specific examples of the alkyl group having 1 to 20 carbon atoms for R 3 and specific examples of the hydrocarbon group having 1 to 20 carbon atoms for R 4 include those described for R 1 and R 2 . This is the same as the specific example of the alkyl group and the specific example of the hydrocarbon group having 1 to 20 carbon atoms.
  • R 3 is an alkyl group having 1 to 3 carbon atoms substituted with a halogen atom (preferably a chlorine atom) from the viewpoint of reactivity when used as a raw material for producing various compounds. It is preferably an alkyl group having 1 to 3 carbon atoms substituted with an alkoxy group having 1 to 3 carbon atoms, and R 4 is preferably an alkyl group having 1 to 3 carbon atoms.
  • R 3 is preferably a methoxymethyl group
  • R 4 is preferably a methyl group.
  • alkoxyhalosilane (A) represented by the formula (4) include methyldimethoxychlorosilane (ClSi (CH 3 ) (OCH 3 ) 2 ), methyldiethoxychlorosilane (ClSi (CH 3 ) (OC) 2 H 5) 2), ethyl dimethoxy chlorosilane (ClSi (C 2 H 5) (OCH 3) 2), ethyl diethoxy chlorosilane (ClSi (C 2 H 5) (OC 2 H 5) 2), n- propyl dimethoxy Chlorosilane (ClSi (n—C 3 H 7 ) (OCH 3 ) 2 ), n-propyldiethoxychlorosilane (ClSi (n—C 3 H 7 ) (OC 2 H 5 ) 2 ), n-hexyldimethoxychlorosilane (ClSi) (NC 6 H 13
  • Example 1 Methoxymethyltrimethoxysilane was used as the aforementioned alkoxysilane (C) (silane (C)).
  • the amount of silane (C) is as described in Table 1.
  • Zinc chloride (ZnCl 2 ) was added as a metal salt (F) at a ratio shown in Table 1 (mol%, number of moles of silane (C)) with respect to silane (C).
  • Acetyl chloride as the halogenating agent (E) was added dropwise to the mixture of silane (C) and metal salt (F) in the amount shown in Table 1.
  • Table 1 shows the initial temperature at the start of dropping and the maximum temperature from the start of dropping to the end of reaction.
  • Example 6 to 13 As the aforementioned alkoxysilane (C) (silane (C)), the types of silane compounds described in Table 2 were used. The amount of silane (C) is as described in Table 2. Zinc chloride (ZnCl 2 ) was added as a metal salt (F) at a ratio shown in Table 2 (mol%, moles of silane (C)) with respect to silane (C). However, in Example 13, the metal salt (F) was not used. In the mixture of silane (C) and metal salt (F), the types and amounts of halogenating agents (E) listed in Table 2 were added dropwise.
  • Zinc chloride (ZnCl 2 ) Zinc chloride (ZnCl 2 ) was added as a metal salt (F) at a ratio shown in Table 2 (mol%, moles of silane (C)) with respect to silane (C). However, in Example 13, the metal salt (F) was not used.
  • the initial temperature at the start of dropping was 5 ° C., and the maximum temperature from the start of dropping to the end of the reaction was less than 20 ° C.
  • the reaction was carried out for 30 minutes while maintaining the temperature after completion of dropping.
  • the composition of the reaction solution after completion of the reaction was analyzed to determine the consumption rate of the halogenating agent and the production ratio of the monohalo form (X 1 ) and dihalo form (X 2 ). These results are shown in Table 2.
  • the measurement results of 1 H-NMR (CDCl 3 ) of the product are shown in Table 3.
  • the 1 H-NMR measurement was performed using JNM-AL400 manufactured by JEOL Ltd.
  • Example 14 As the alkoxyhalosilane (B) (halosilane (B)), 26.83 mmol of the silanes described in Table 4 were used. 1.73 g (44.67 mmol, 1.67 equivalents based on halosilane (B)) of NaBH 4 as the hydrogenating agent (D) was suspended in 14.7 g of the solvent (S) of the type described in Table 4. Thereafter, the halosilane (B) was added dropwise to the suspension of the hydrogenating agent (D) at 20 ° C. over 30 to 90 minutes. After completion of dropping, the reaction was carried out at 20 ° C. for 2 hours. The yield of alkoxyhydrosilane (A) (methoxymethyldimethoxysilane) after the reaction was determined from 1 H-NMR (CDCl 3 ). The obtained yield is shown in Table 4.
  • Example 18 and Comparative Example 4 Changing the solvent (S) to the solvent shown in Table 4, changing the dropping time of the halosilane (B) to 13 hours, and changing the reaction time after the dropping of the halosilane (B) to 6 hours The others were reacted in the same manner as in Example 14. The yield of alkoxyhydrosilane (A) (methoxymethyldimethoxysilane) after the reaction was determined in the same manner as in Example 14. The obtained yield is shown in Table 4.
  • MMDMCS represents methoxymethyldimethoxychlorosilane
  • MMDMBS represents methoxymethyldimethoxybromosilane
  • a desired structure is obtained by reacting an alkoxyhalosilane (B) having a predetermined structure with a hydrogenating agent (D) in a solvent (S) containing 50% by mass or more of an aprotic organic solvent having an ether bond. It can be seen that the alkoxyhydrosilane (A) having the structure as described above is favorably produced.
  • Example 14 and Examples 20 to 24 Type and amount of use of alkoxyhalosilane (B) (halosilane (B)) (mmol), amount of use of hydrogenating agent (D) (equivalent), amount of use of solvent (S) (g), and reaction time And alkoxyhydrosilane (A) (hydrosilane (A)) were synthesized in the same manner as in Example 14 except that they were changed as described in Table 5. The yield of hydrosilane (A) measured in the same manner as in Example 14 is shown in Table 5.
  • MMDMCS Methoxymethyldimethoxychlorosilane
  • MDECS Methyldiethoxychlorosilane
  • nPrDMCS n-propyldimethoxychlorosilane
  • HexDMCS n-hexyldimethoxychlorosilane
  • PhDMCS phenyldimethoxychlorosilane 3-ClC3DMCS: 3-chloropropyldimethoxychlorosilane
  • Example 25 With respect to methoxymethyltrimethoxysilane, 0.011 mol% of zinc chloride was used as a catalyst, and addition of 0.92 mol equivalent of acetyl chloride at 5 ° C. was started. The addition was completed over 1.5 hours while adjusting the addition rate so that the temperature of the reaction system did not exceed 20 ° C. The reaction was further continued for 0.5 hours to obtain methoxymethyldimethoxychlorosilane. To the purified methoxymethyldimethoxychlorosilane, 1.67 molar equivalents of NaBH 4 and 3 times the mass of 1,2-dimethoxyethane were charged into the reaction vessel.
  • Example 25 is a method having only two steps according to the present invention, the monochloroation reaction of methoxymethyltrimethoxysilane and the monohydrolysis reaction of methoxymethyldimethoxychlorosilane.
  • the yield of methoxymethyldimethoxysilane based on the amount of methoxymethyltrimethoxysilane used was as high as 60%.
  • methoxymethyldichlorosilane To the purified methoxymethyldichlorosilane, 2.5 molar equivalents of trimethyl orthoacetate were charged into the reaction vessel. While stirring the contents of the reaction vessel, methoxymethyldimethoxysilane was obtained by slowly adding methoxymethyldichlorosilane so that the internal temperature of the reaction vessel did not exceed 50 ° C.
  • the method of Comparative Example 5 is a method having three steps: a trichlorination reaction of methoxymethyltrimethoxysilane, a monohydrolysis reaction of methoxymethyltrichlorosilane, and a dimethoxylation reaction of methoxymethyldichlorosilane described in Patent Document 2. It is. As a result, in Comparative Example 5, the yield of methoxymethyldimethoxysilane based on the amount of methoxymethyltrimethoxysilane used was as low as 30%.

Abstract

Provided are: a method for producing an alkoxyhydrosilane from which an objective substance can be produced in high yield; a method for producing an alkoxyhalosilane which is suitable for use as a starting material in the method for producing an alkoxyhydrosilane; and a novel alkoxyhalosilane having a specific structure. An alkoxysilane having a given structure is halogenated with a halogenating agent under specific conditions to produce an alkoxyhalosilane having a given structure. The alkoxyhalosilane having a given structure is hydrogenated with a hydrogenating agent in a solvent comprising an aprotic organic solvent having an ether bond, thereby producing an alkoxyhydrosilane having a desired structure.

Description

アルコキシヒドロシランの製造方法、及びアルコキシハロシランの製造方法Method for producing alkoxyhydrosilane and method for producing alkoxyhalosilane
　本発明は、アルコキシヒドロシランの製造方法と、当該製造方法における原料化合物として好適に使用されるアルコキシハロシランの製造方法と、特定の構造のアルコキシハロシランに関する。 The present invention relates to a method for producing alkoxyhydrosilane, a method for producing alkoxyhalosilane suitably used as a raw material compound in the production method, and an alkoxyhalosilane having a specific structure.
　シランカップリング剤のような種々の機能性シラン化合物の原料化合物や、ポリマー分子鎖に反応性の官能基を導入するための原料化合物として、例えば、メチル基のような有機基と、メトキシ基のようなアルコキシ基と、１つの水素原子とを組み合わせて有する、アルコキシヒドロシランが広く用いられている。 Examples of raw material compounds for various functional silane compounds such as silane coupling agents and raw material compounds for introducing reactive functional groups into polymer molecular chains include, for example, organic groups such as methyl groups and methoxy groups. Alkoxyhydrosilanes having a combination of such an alkoxy group and one hydrogen atom are widely used.
　一方、ケイ素原子に結合した炭素原子上に特定の置換基を有するアルコキシヒドロシランも知られており、これらから製造される重合体から高い硬化速度を有する硬化性組成物が得られることが知られている（特許文献１）。 On the other hand, alkoxyhydrosilane having a specific substituent on a carbon atom bonded to a silicon atom is also known, and it is known that a curable composition having a high curing rate can be obtained from a polymer produced therefrom. (Patent Document 1).
　一般に、アルコキシヒドロシランの製造方法としては、対応するトリアルコキシシランの一部のアルコキシ基を複数工程にて選択的に水素化する方法が考えられる。例えば、メトキシメチルトリメトキシシランを触媒の存在下に塩化アセチルと反応させて、メトキシメチルトリクロロシランを得た後、メトキシメチルトリクロロシランとメチルジクロロシランとを反応させてメトキシメチルジクロロシランを得、さらに、メトキシメチルジクロロシランを、オルト酢酸トリメチル、あるいはメタノール及びオルト酢酸トリメチルと反応させてメトキシメチルジメトキシシラン（Ｈ－Ｓｉ（ＣＨ２ＯＣＨ３）（ＯＣＨ３）２）を製造する方法が提案されている（特許文献２（合成例１）、特許文献３（実施例６）、及び特許文献４（実施例３）を参照。）。 In general, as a method for producing alkoxyhydrosilane, a method of selectively hydrogenating a part of alkoxy groups of the corresponding trialkoxysilane in a plurality of steps can be considered. For example, methoxymethyltrimethoxysilane is reacted with acetyl chloride in the presence of a catalyst to obtain methoxymethyltrichlorosilane, then methoxymethyltrichlorosilane and methyldichlorosilane are reacted to obtain methoxymethyldichlorosilane, A method for producing methoxymethyldimethoxysilane (H—Si (CH 2 OCH 3 ) (OCH 3 ) 2 ) by reacting methoxymethyldichlorosilane with trimethyl orthoacetate or methanol and trimethyl orthoacetate has been proposed. (See Patent Document 2 (Synthesis Example 1), Patent Document 3 (Example 6), and Patent Document 4 (Example 3).)
国際公開第２０１０／００４９４８号International Publication No. 2010/004948 国際公開第２０１２／０３６１０９号International Publication No. 2012/036109 国際公開第２０１１／１６１９１５号International Publication No. 2011-161915 国際公開第２０１１／１６１９１６号International Publication No. 2011-161916
　しかし、特許文献１に記載される方法は、工程数が多いことや、オルガノトリハロシランが有する３つのハロゲン原子のうちの１つ又は２つを選択的に水素化する際の収率が低いことに起因して、原料であるオルガノトリメトキシシランの量を基準とする、所望するアルコキシヒドロシランの収率には未だ改善の余地があった。 However, the method described in Patent Document 1 has a large number of steps and a low yield when selectively hydrogenating one or two of the three halogen atoms of organotrihalosilane. As a result, there is still room for improvement in the desired yield of alkoxyhydrosilane based on the amount of organotrimethoxysilane as a raw material.
　本発明は、上記の課題に鑑みなされたものであり、高収率で目的物を製造できるアルコキシヒドロシランの製造方法と、当該アルコキシヒドロシランの製造方法において原料として好適に使用されるアルコキシハロシランの製造方法と、特定の構造の新規なアルコキシハロシランとを提供することを目的とする。 The present invention has been made in view of the above problems, and a method for producing an alkoxyhydrosilane capable of producing a target product in a high yield and a method for producing an alkoxyhalosilane suitably used as a raw material in the method for producing an alkoxyhydrosilane. The object is to provide a method and a novel alkoxyhalosilane of a specific structure.
　本発明者らは、所定の構造のアルコキシシランを特定の条件下においてハロゲン化剤によりハロゲン化して所定の構造のアルコキシハロシランを製造することと、前述の所定の構造のアルコキシハロシランを、エーテル結合を有する非プロトン性有機溶剤を含む溶剤中で、水素化剤を用いて水素化して所望する構造のアルコキシヒドロシランを製造することにより上記の課題を解決できることを見出し、本発明を完成するに至った。 The inventors of the present invention produce an alkoxyhalosilane having a predetermined structure by halogenating an alkoxysilane having a predetermined structure with a halogenating agent under specific conditions, and converting the alkoxyhalosilane having the predetermined structure into an ether. The present inventors have found that the above problems can be solved by producing an alkoxyhydrosilane having a desired structure by hydrogenation using a hydrogenating agent in a solvent containing an aprotic organic solvent having a bond. It was.
　すなわち、本発明は、
　（１）下記式（１）：
Ｈ－ＳｉＲ１ ａ（ＯＲ２）３－ａ・・・（１）
（式（１）中、Ｒ１、及びＲ２は、それぞれ独立に、置換基を有していてもよい炭素原子数１～２０の炭化水素基であり、ａは１又は２である。Ｒ１、ＯＲ２のそれぞれについて、それらが複数存在するとき、それらは同じでもよく、異なっていてもよい。）
で表されるアルコキシヒドロシラン（Ａ）を製造するアルコキシヒドロシランの製造方法であって、
　下記式（２）：
Ｘ－ＳｉＲ１ ａ（ＯＲ２）３－ａ・・・（２）
（式（２）中、Ｒ１、Ｒ２、及びａは、式（１）と同様であり、Ｘはハロゲン原子である。Ｒ１、ＯＲ２のそれぞれについて、それらが複数存在するとき、それらは同じでもよく、異なっていてもよい。）
で表されるアルコキシハロシラン（Ｂ）を、エーテル結合を有する非プロトン性有機溶剤を５０質量％以上含む溶剤（Ｓ）中で、水素化剤（Ｄ）を用いて水素化することを含む、製造方法。
　（２）水素化剤（Ｄ）が、下記式（Ｄ１）：
ＭＢＨ４・・・（Ｄ１）
（式（Ｄ１）中、Ｍは、リチウム、ナトリウム、又はカリウムである。）
で表される化合物である、（１）に記載のアルコキシヒドロシランの製造方法。
　（３）Ｍがナトリウムである、（２）に記載のアルコキシヒドロシランの製造方法。
　（４）Ｒ２がメチル基、又はエチル基である、（１）～（３）のいずれか１つに記載のアルコキシヒドロシランの製造方法。
　（５）Ｒ２がメチル基である、（４）に記載のアルコキシヒドロシランの製造方法。
　（６）非プロトン性有機溶剤が、テトラヒドロフラン、１，２－ジメトキシエタン、ジエチレングリコールジメチルエーテル、及びトリエチレングリコールジメチルエーテルからなる群より選択される１種以上を含む、（１）～（５）のいずれか１つに記載のアルコキシヒドロシランの製造方法。
　（７）非プロトン性有機溶剤が、１，２－ジメトキシエタンである、（６）に記載のアルコキシヒドロシランの製造方法。
　（８）Ｒ１が、置換基を有していてもよい炭素原子数１～３の炭化水素基である、（１）～（７）のいずれか１つに記載のアルコキシヒドロシランの製造方法。
　（９）Ｒ１が、塩素原子で置換されているか、エーテル結合を含む、（１）～（８）のいずれか１つに記載のアルコキシヒドロシランの製造方法。
　（１０）Ｒ１が、メトキシメチル基である、（９）に記載のアルコキシヒドロシランの製造方法。
　（１１）ａが１である、（１）～（１０）のいずれか１つに記載のアルコキシヒドロシランの製造方法。
　（１２）下記式（２）：
Ｘ－ＳｉＲ１ ａ（ＯＲ２）３－ａ・・・（２）
（式（２）中、Ｒ１、及びＲ２は、それぞれ独立に、置換基を有していてもよい炭素原子数１～２０の炭化水素基であり、Ｘはハロゲン原子であり、ａは１又は２である。Ｒ１、ＯＲ２のそれぞれについて、それらが複数存在するとき、それらは同じでもよく、異なっていてもよい。）
で表されるアルコキシハロシラン（Ｂ）を製造するアルコキシハロシランの製造方法であって、
　下記式（３）：
ＳｉＲ１ ａ（ＯＲ２）４－ａ・・・（３）
（式（３）中、Ｒ１、及びＲ２、及びａは式（２）と同様である。Ｒ１、ＯＲ２のそれぞれについて、それらが複数存在するとき、それらは同じでもよく、異なっていてもよい。）
で表されるアルコキシシラン（Ｃ）に、－３０℃以上１００℃以下の温度で、ハロゲン化剤（Ｅ）を反応させてアルコキシハロシラン（Ｂ）を生成させることを含み、
　アルコキシシラン（Ｃ）１モルからアルコキシハロシラン（Ｂ）１モルを生成させる、化学量論的なハロゲン化剤（Ｅ）の量を１モル当量とする場合に、ハロゲン化剤（Ｅ）の使用量が１．５モル当量以下である、製造方法。
　（１３）ハロゲン化剤（Ｅ）が、カルボン酸ハライドである、（１２）に記載のアルコキシハロシランの製造方法。
　（１４）Ｘが塩素原子であり、ハロゲン化剤（Ｅ）が、塩化アセチルである、（１３）に記載のアルコキシハロシランの製造方法。
　（１５）アルコキシシラン（Ｃ）に、－１０℃以上９０℃以下の温度で、ハロゲン化剤（Ｅ）を反応させる、（１２）～（１４）のいずれか１つに記載のアルコキシハロシランの製造方法。
　（１６）アルコキシシラン（Ｃ）に、０℃以上２０℃以下の温度で、ハロゲン化剤（Ｅ）を反応させる、（１５）に記載のアルコキシハロシランの製造方法。
　（１７）アルコキシシラン（Ｃ）と、ハロゲン化剤（Ｅ）との反応をルイス酸性を示す金属塩（Ｆ）の存在下に行う、（１２）～（１６）のいずれか１つに記載のアルコキシハロシランの製造方法。
　（１８）金属塩（Ｆ）が塩化亜鉛を含む、（１７）に記載のアルコキシハロシランの製造方法。
　（１９）アルコキシハロシラン（Ｂ）が、（１２）～（１８）のいずれか１つに記載の方法により製造される、（１）～（１１）のいずれか１つに記載のアルコキシヒドロシランの製造方法。
　（２０）下記式（４）：
Ｘ－ＳｉＲ３（ＯＲ４）２・・・（４）
（式（４）中、Ｒ３は、炭素原子数１～２０のアルキル基であり、Ｒ３としてのアルキル基は、ハロゲン原子又は炭素原子数１～６のアルコキシ基で置換されていてもよく、Ｒ４は、炭素原子数１～２０の炭化水素基であり、Ｘはハロゲン原子である。２つのＯＲ４について、それらは同じでもよく、異なっていてもよい。）
で表されるアルコキシハロシラン化合物。
　（２１）Ｒ３が炭素原子数１～３のアルコキシ基で置換された炭素原子数１～３のアルキル基であり、Ｒ４が炭素原子数１～３のアルキル基である、（２０）に記載のアルコキシハロシラン化合物。
　（２２）Ｒ３がメトキシメチル基であり、Ｒ４がメチル基である、（２１）に記載のアルコキシハロシラン化合物。
に関する。 That is, the present invention
(1) The following formula (1):
H-SiR 1 a (OR 2 ) 3-a (1)
(In Formula (1), R 1 and R 2 are each independently a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a is 1 or 2. R For each of 1 and OR 2 , when there are a plurality of them, they may be the same or different.)
A process for producing an alkoxyhydrosilane (A) represented by:
Following formula (2):
X-SiR 1 a (OR 2 ) 3-a (2)
(In Formula (2), R 1 , R 2 , and a are the same as in Formula (1), and X is a halogen atom. When there are a plurality of each of R 1 and OR 2 , May be the same or different.)
Hydrogenating the alkoxyhalosilane (B) represented by the formula (B) with a hydrogenating agent (D) in a solvent (S) containing 50 mass% or more of an aprotic organic solvent having an ether bond, Production method.
(2) The hydrogenating agent (D) is represented by the following formula (D1):
MBH 4 ... (D1)
(In the formula (D1), M is lithium, sodium, or potassium.)
The manufacturing method of the alkoxy hydrosilane as described in (1) which is a compound represented by these.
(3) The method for producing an alkoxyhydrosilane according to (2), wherein M is sodium.
(4) The method for producing an alkoxyhydrosilane according to any one of (1) to (3), wherein R 2 is a methyl group or an ethyl group.
(5) The method for producing an alkoxyhydrosilane according to (4), wherein R 2 is a methyl group.
(6) Any of (1) to (5), wherein the aprotic organic solvent includes one or more selected from the group consisting of tetrahydrofuran, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether The manufacturing method of the alkoxy hydrosilane as described in one.
(7) The method for producing an alkoxyhydrosilane according to (6), wherein the aprotic organic solvent is 1,2-dimethoxyethane.
(8) The method for producing an alkoxyhydrosilane according to any one of (1) to (7), wherein R 1 is a hydrocarbon group having 1 to 3 carbon atoms which may have a substituent.
(9) The method for producing an alkoxyhydrosilane according to any one of (1) to (8), wherein R 1 is substituted with a chlorine atom or contains an ether bond.
(10) The method for producing an alkoxyhydrosilane according to (9), wherein R 1 is a methoxymethyl group.
(11) The method for producing an alkoxyhydrosilane according to any one of (1) to (10), wherein a is 1.
(12) The following formula (2):
X-SiR 1 a (OR 2 ) 3-a (2)
(In the formula (2), R 1 and R 2 are each independently a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, X is a halogen atom, and a is 1 or 2. For each of R 1 and OR 2 , when there are a plurality of them, they may be the same or different.
A method for producing an alkoxyhalosilane for producing an alkoxyhalosilane (B) represented by:
Following formula (3):
SiR 1 a (OR 2 ) 4-a (3)
(In formula (3), R 1 , R 2 , and a are the same as in formula (2). For each of R 1 and OR 2 , when there are a plurality of them, they may be the same or different. May be.)
A reaction with a halogenating agent (E) at a temperature of −30 ° C. or higher and 100 ° C. or lower to produce an alkoxyhalosilane (B).
Use of halogenating agent (E) when 1 mole equivalent of stoichiometric halogenating agent (E) is used to form 1 mol of alkoxyhalosilane (B) from 1 mol of alkoxysilane (C) The manufacturing method whose quantity is 1.5 molar equivalent or less.
(13) The method for producing an alkoxyhalosilane according to (12), wherein the halogenating agent (E) is a carboxylic acid halide.
(14) The method for producing an alkoxyhalosilane according to (13), wherein X is a chlorine atom, and the halogenating agent (E) is acetyl chloride.
(15) The alkoxyhalosilane according to any one of (12) to (14), wherein the halogenating agent (E) is reacted with the alkoxysilane (C) at a temperature of −10 ° C. or higher and 90 ° C. or lower. Production method.
(16) The method for producing an alkoxyhalosilane according to (15), wherein the halogenating agent (E) is reacted with the alkoxysilane (C) at a temperature of 0 ° C. or higher and 20 ° C. or lower.
(17) The reaction according to any one of (12) to (16), wherein the reaction between the alkoxysilane (C) and the halogenating agent (E) is performed in the presence of a metal salt (F) exhibiting Lewis acidity. A method for producing an alkoxyhalosilane.
(18) The method for producing an alkoxyhalosilane according to (17), wherein the metal salt (F) contains zinc chloride.
(19) The alkoxyhydrosilane according to any one of (1) to (11), wherein the alkoxyhalosilane (B) is produced by the method according to any one of (12) to (18) Production method.
(20) The following formula (4):
X-SiR 3 (OR 4 ) 2 (4)
(In formula (4), R 3 is an alkyl group having 1 to 20 carbon atoms, and the alkyl group as R 3 may be substituted with a halogen atom or an alkoxy group having 1 to 6 carbon atoms. , R 4 is a hydrocarbon group having 1 to 20 carbon atoms, and X is a halogen atom, and for two OR 4 , they may be the same or different.
The alkoxyhalosilane compound represented by these.
(21) In (20), R 3 is an alkyl group having 1 to 3 carbon atoms substituted with an alkoxy group having 1 to 3 carbon atoms, and R 4 is an alkyl group having 1 to 3 carbon atoms. The alkoxyhalosilane compound described.
(22) The alkoxyhalosilane compound according to (21), wherein R 3 is a methoxymethyl group and R 4 is a methyl group.
About.
　本発明によれば、高収率で目的物を製造できるアルコキシヒドロシランの製造方法と、当該アルコキシヒドロシランの製造方法において原料として好適に使用されるアルコキシハロシランの製造方法と、特定の構造の新規なアルコキシハロシランとを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the alkoxyhydrosilane which can manufacture a target object with a high yield, the manufacturing method of the alkoxyhalosilane used suitably as a raw material in the manufacturing method of the said alkoxyhydrosilane, and novel of a specific structure And alkoxyhalosilanes can be provided.
≪アルコキシヒドロシランの製造方法≫
　以下、アルコキシヒドロシランの製造方法について説明する。 ≪Method for producing alkoxyhydrosilane≫
Hereinafter, the manufacturing method of alkoxy hydrosilane is demonstrated.
＜アルコキシヒドロシラン（Ａ）＞
　本発明にかかる方法により製造されるアルコキシヒドロシラン（Ａ）は、下記式（１）：
Ｈ－ＳｉＲ１ ａ（ＯＲ２）３－ａ・・・（１）
（式（１）中、Ｒ１、及びＲ２は、それぞれ独立に、置換基を有していてもよい炭素原子数１～２０の炭化水素基であり、ａは１又は２である。）
で表される化合物である。 <Alkoxyhydrosilane (A)>
The alkoxyhydrosilane (A) produced by the method according to the present invention has the following formula (1):
H-SiR 1 a (OR 2 ) 3-a (1)
(In Formula (1), R 1 and R 2 are each independently a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a is 1 or 2.)
It is a compound represented by these.
　Ｒ１、及びＲ２は、それぞれ独立に、置換基を有していてもよい炭素原子数１～２０の炭化水素基である。
　Ｒ１及びＲ２としての炭化水素基が有し得る置換基としては、アルコキシヒドロシランの良好な生成を阻害しない基であれば特に限定されない。具体的には、アルコキシ基、シクロアルコキシ基、アルケニルオキシ基、アリールオキシ基、アラルキルオキシ基、アルキルチオ基、シクロアルキルチオ基、アルケニルチオ基、アリールチオ基、アラルキルチオ基、ハロゲン原子等が挙げられる。上記の置換基のなかでは、アルコキシ基、及びハロゲン原子が、得られるヒドロシランの有用性から好ましい。
　アルコキシ基としては、炭素原子数１～１０のアルコキシ基が好ましく、炭素原子数１～６のアルコキシ基がより好ましく、メトキシ基及びエトキシ基がさらにより好ましく、メトキシ基が特に好ましい。炭素原子数が少なく、立体的に小さいアルコキシ基のほうが、水素化反応が良好に進行する傾向にある。
　ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、及びヨウ素原子が挙げられ、水素化剤（Ｄ）との副反応が生じにくいという点で、フッ素原子、及び塩素原子が好ましい。 R 1 and R 2 are each independently a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
The substituent that the hydrocarbon group as R 1 and R 2 may have is not particularly limited as long as it is a group that does not inhibit the good production of alkoxyhydrosilane. Specific examples include an alkoxy group, a cycloalkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an alkenylthio group, an arylthio group, an aralkylthio group, and a halogen atom. Among the above substituents, an alkoxy group and a halogen atom are preferable from the usefulness of the resulting hydrosilane.
The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, still more preferably a methoxy group and an ethoxy group, and particularly preferably a methoxy group. An alkoxy group having a small number of carbon atoms and a small stericity tends to favorably advance the hydrogenation reaction.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom and a chlorine atom are preferable in that a side reaction with the hydrogenating agent (D) hardly occurs.
　Ｒ１及びＲ２としての置換基を有してもよい炭化水素基の炭素原子数の総数は、ポリマー分子鎖に導入した際に、炭素原子数の総数が少ないほうが、反応性官能基としての反応性が高くなる傾向にあることから、１～１２が好ましく、１～６がより好ましく、１～３が特に好ましい。 The total number of carbon atoms of the hydrocarbon group which may have a substituent as R 1 and R 2 is smaller as the reactive functional group when the total number of carbon atoms is smaller when introduced into the polymer molecular chain. Since reactivity tends to be high, 1 to 12 is preferable, 1 to 6 is more preferable, and 1 to 3 is particularly preferable.
　無置換の炭素原子数１～２０の炭化水素基の好適な例としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｎ－ヘキシル基、ｎ－オクチル基、２－エチルヘキシル基、ｎ－ドデシル基、及びｎ－イコシル基等のアルキル基；シクロプロピル基、及びシクロヘキシル基等のシクロアルキル基；ビニル基、アリル基、及びイソプロぺニル基等のアルケニル基；フェニル基、ｏ－トリル基、ｍ－トリル基、ｐ－トリル基、及びナフタレン－１－イル基等の芳香族炭化水素基；ベンジル基、フェネチル基、及びナフタレン－１－イルメチル基等のアラルキル基が挙げられる。炭素数が多くなりすぎると反応性が低下することから、これらの中では炭素原子数６以下の炭化水素基が好ましく、炭素原子数３以下の炭化水素基がより好ましく、メチル基が特に好ましい。 Preferable examples of the unsubstituted hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-hexyl group, n-octyl group, 2 -Alkyl groups such as ethylhexyl group, n-dodecyl group and n-icosyl group; cycloalkyl groups such as cyclopropyl group and cyclohexyl group; alkenyl groups such as vinyl group, allyl group and isopropenyl group; phenyl group Aromatic hydrocarbon groups such as o-tolyl group, m-tolyl group, p-tolyl group and naphthalen-1-yl group; and aralkyl groups such as benzyl group, phenethyl group and naphthalen-1-ylmethyl group It is done. Among them, a hydrocarbon group having 6 or less carbon atoms is preferable, a hydrocarbon group having 3 or less carbon atoms is more preferable, and a methyl group is particularly preferable.
　Ｒ１としては、アルコキシヒドロシラン（Ａ）の原料の入手や製造が容易である点等から、置換基を有してもよい炭素原子数１～３の炭化水素基が好ましい。
　また、Ｒ１は、塩素原子で置換されているか、エーテル結合を含むのが反応性の観点で好ましい。
　Ｒ１としての好適な基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、クロロメチル基、１－クロロエチル基、２－クロロエチル基、１－クロロプロピル基、２－クロロプロピル基、３－クロロプロピル基、メトキシメチル基、エトキシメチル基、１－メトキシエチル基、２－メトキシエチル基、１－メトキシプロピル基、２－メトキシプロピル基、３－メトキシプロピル基、が挙げられる。
　これらの中では、水素化反応が良好に進行することから、メトキシメチル基が好ましい。 R 1 is preferably a hydrocarbon group having 1 to 3 carbon atoms which may have a substituent from the viewpoint of easy availability and production of the raw material of alkoxyhydrosilane (A).
Further, R 1 is either substituted by a chlorine atom, that an ether bond preferable from the viewpoint of reactivity.
Suitable groups for R 1 include methyl group, ethyl group, n-propyl group, isopropyl group, chloromethyl group, 1-chloroethyl group, 2-chloroethyl group, 1-chloropropyl group, 2-chloropropyl group, Examples include 3-chloropropyl group, methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 2-methoxyethyl group, 1-methoxypropyl group, 2-methoxypropyl group, and 3-methoxypropyl group.
Among these, a methoxymethyl group is preferable because the hydrogenation reaction proceeds well.
　また、得られたアルコキシヒドロシラン（Ａ）を用いて種々の化学製品を製造する際に、アルコキシヒドロシラン（Ａ）に由来するアルコキシシリル基の反応性が良好であることから、式（１）中のＲ２としては、メチル基、又はエチル基が好ましく、メチル基がより好ましい。
　つまり、アルコキシヒドロシラン（Ａ）は、メトキシヒドロシラン、又はエトキシヒドロシランであるのが好ましく、メトキシヒドロシランであるのがより好ましい。 Moreover, when manufacturing various chemical products using the obtained alkoxy hydrosilane (A), since the reactivity of the alkoxy silyl group derived from alkoxy hydrosilane (A) is favorable, in Formula (1), R 2 is preferably a methyl group or an ethyl group, and more preferably a methyl group.
That is, the alkoxyhydrosilane (A) is preferably methoxyhydrosilane or ethoxyhydrosilane, and more preferably methoxyhydrosilane.
　式（１）において、Ｒ１又は（ＯＲ２）が複数である場合に、複数の基は、互いに同一であっても異なっていてもよく、原料製造の容易さから、同一であるのが好ましい。 In the formula (1), when there are a plurality of R 1 or (OR 2 ), the plurality of groups may be the same or different from each other, and are preferably the same from the viewpoint of ease of raw material production. .
　式（１）において、ａは１又は２である。原料の入手性の観点では、ａは１であるのが好ましい。一方で、ケイ素基上の有機基の置換基によってアルコキシヒドロシラン（Ａ）のアルコキシシリル基の反応性の調整や更なる化学修飾が可能である。この理由では、ａは２であるのが好ましい。得られたアルコキシヒドロシラン（Ａ）を用いて種々の化学製品を製造する際に、アルコキシヒドロシラン（Ａ）に由来するアルコキシシリル基の反応性の点からは、アルコキシシリル基に含まれるアルコキシ基の数は多いほうが好ましい。このため、ａは１であるのがより好ましい。 In the formula (1), a is 1 or 2. From the viewpoint of availability of raw materials, a is preferably 1. On the other hand, the reactivity of the alkoxysilyl group of the alkoxyhydrosilane (A) can be adjusted and further chemical modification can be performed by the substituent of the organic group on the silicon group. For this reason, a is preferably 2. In producing various chemical products using the obtained alkoxyhydrosilane (A), the number of alkoxy groups contained in the alkoxysilyl group is determined from the reactivity of the alkoxysilyl group derived from the alkoxyhydrosilane (A). Is more preferable. For this reason, a is more preferably 1.
　本発明にかかるアルコキシヒドロシランの製造方法によって得られる式（１）で表されるアルコキシヒドロシラン（Ａ）の好適な具体例としては、メチルジメトキシシラン（ＨＳｉ（ＣＨ３）（ＯＣＨ３）２）、メチルジエトキシシラン（ＨＳｉ（ＣＨ３）（ＯＣ２Ｈ５）２）、エチルジメトキシシラン（ＨＳｉ（Ｃ２Ｈ５）（ＯＣＨ３）２）、エチルジエトキシシラン（ＨＳｉ（Ｃ２Ｈ５）（ＯＣ２Ｈ５）２）、ｎ－プロピルジメトキシシラン（ＨＳｉ（ｎ－Ｃ３Ｈ７）（ＯＣＨ３）２）、ｎ－プロピルジエトキシシラン（ＨＳｉ（ｎ－Ｃ３Ｈ７）（ＯＣ２Ｈ５）２）、ｎ－ヘキシルジメトキシシラン（ＨＳｉ（ｎ－Ｃ６Ｈ１３）（ＯＣＨ３）２）、ｎ－ヘキシルジエトキシシラン（ＨＳｉ（ｎ－Ｃ６Ｈ１３）（ＯＣ２Ｈ５）２）、フェニルジメトキシシラン（ＨＳｉ（Ｐｈ）（ＯＣＨ３）２）、フェニルジエトキシシラン（ＨＳｉ（Ｐｈ）（ＯＣ２Ｈ５）２）、クロロメチルジメトキシシラン（ＨＳｉ（ＣＨ２Ｃｌ）（ＯＣＨ３）２）、クロロメチルジエトキシシラン（ＨＳｉ（ＣＨ２Ｃｌ）（ＯＣ２Ｈ５）２）、クロロメチルジイソプロペニルオキシシラン（ＨＳｉ（ＣＨ２Ｃｌ）（ＯＣ（ＣＨ３）＝ＣＨ２）２）、クロロメチルメトキシメチルシラン（ＨＳｉ（ＣＨ２Ｃｌ）（ＯＣＨ３）（ＣＨ３））、クロロメチルエトキシメチルシラン（ＨＳｉ（ＣＨ２Ｃｌ）（ＯＣ２Ｈ５）（ＣＨ３））、ビス（クロロメチル）メトキシシラン（ＨＳｉ（ＣＨ２Ｃｌ）２（ＯＣＨ３））、ビス（クロロメチル）エトキシシラン（ＨＳｉ（ＣＨ２Ｃｌ）２（ＯＣ２Ｈ５））、１－クロロエチルジメトキシシラン（ＨＳｉ（ＣＨＣｌＣＨ３）（ＯＣＨ３）２）、２－クロロエチルジメトキシシラン（ＨＳｉ（ＣＨ２ＣＨ２Ｃｌ）（ＯＣＨ３）２）、１－クロロプロピルジメトキシシラン（ＨＳｉ（ＣＨＣｌＣＨ２ＣＨ３）（ＯＣＨ３）２）、２－クロロプロピルジメトキシシラン（ＨＳｉ（ＣＨ２ＣＨＣｌＣＨ３）（ＯＣＨ３）２）、３－クロロプロピルジメトキシシラン（ＨＳｉ（ＣＨ２ＣＨ２ＣＨ２Ｃｌ）（ＯＣＨ３）２）、フルオロメチルジメトキシシラン（ＨＳｉ（ＣＨ２Ｆ）（ＯＣＨ３）２）、ブロモメチルジメトキシシラン（ＨＳｉ（ＣＨ２Ｂｒ）（ＯＣＨ３）２）、ヨードメチルジメトキシシラン（ＨＳｉ（ＣＨ２Ｉ）（ＯＣＨ３）２）、メトキシメチルジメトキシシラン（ＨＳｉ（ＣＨ２ＯＣＨ３）（ＯＣＨ３）２）、メトキシメチルジエトキシシラン（ＨＳｉ（ＣＨ２ＯＣＨ３）（ＯＣ２Ｈ５）２）、メトキシメチルジイソプロペニルオキシシラン（ＨＳｉ（ＣＨ２ＯＣＨ３）（ＯＣ（ＣＨ３）＝ＣＨ２）２）、（ジメトキシメチル）ジメトキシシラン（ＨＳｉ（ＣＨ（ＯＣＨ３）２）（ＯＣＨ３）２）、エトキシメチルジメトキシシラン（ＨＳｉ（ＣＨ２ＯＣ２Ｈ５）（ＯＣＨ３）２）、エトキシメチルジエトキシシラン（ＨＳｉ（ＣＨ２ＯＣ２Ｈ５）（ＯＣ２Ｈ５）２）、１－メトキシエチルジメトキシシラン（ＨＳｉ（ＣＨ（ＯＣＨ３）ＣＨ３）（ＯＣＨ３）２）、トリメトキシメチルジメトキシシラン（ＨＳｉ（Ｃ（ＯＣＨ３）３）（ＯＣＨ３）２）、（メトキシメチル）メチルメトキシシラン（ＨＳｉ（ＣＨ２ＯＣＨ３）（ＣＨ３）（ＯＣＨ３））、ビス（メトキシメチル）メトキシシラン（ＨＳｉ（ＣＨ２ＯＣＨ３）２（ＯＣＨ３））、及びメチルチオメチルジメトキシシラン（ＨＳｉ（ＣＨ２ＳＣＨ３）（ＯＣＨ３）２）等が挙げられる。ただし、アルコキシヒドロシラン（Ａ）は、これらに限定されない。 Preferable specific examples of the alkoxyhydrosilane (A) represented by the formula (1) obtained by the method for producing an alkoxyhydrosilane according to the present invention include methyldimethoxysilane (HSi (CH 3 ) (OCH 3 ) 2 ), methyl diethoxy silane (HSi (CH 3) (OC 2 H 5) 2), ethyl dimethoxy silane (HSi (C 2 H 5) (OCH 3) 2), ethyldiethoxysilane (HSi (C 2 H 5) (OC 2 H 5) 2), n- propyl dimethoxy silane (HSi (n-C 3 H 7) (OCH 3) 2), n- propyl diethoxy silane (HSi (n-C 3 H 7) (OC 2 H 5 2 ), n-hexyldimethoxysilane (HSi (n-C 6 H 13 ) (OCH 3 ) 2 ), n-hexyldiethoxysilane (HSi (n- C 6 H 13) (OC 2 H 5) 2), phenyl dimethoxy silane (HSi (Ph) (OCH 3 ) 2), phenyl diethoxy silane (HSi (Ph) (OC 2 H 5) 2), chloromethyl dimethoxy silane (HSi (CH 2 Cl) ( OCH 3) 2), chloromethyl diethoxy silane (HSi (CH 2 Cl) ( OC 2 H 5) 2), chloromethyl diisopropenylbenzene silane (HSi (CH 2 Cl) (OC (CH 3 ) ═CH 2 ) 2 ), chloromethylmethoxymethylsilane (HSi (CH 2 Cl) (OCH 3 ) (CH 3 )), chloromethylethoxymethylsilane (HSi (CH 2 Cl) (OC 2 ) H 5) (CH 3)), bis (chloromethyl) silane (HSi (CH 2 Cl) 2 (OCH 3)), bis ( Roromechiru) silane (HSi (CH 2 Cl) 2 (OC 2 H 5)), 1- chloroethyl dimethoxy silane (HSi (CHClCH 3) (OCH 3) 2), 2- chloro-ethyl dimethoxy silane (HSi (CH 2 CH 2 Cl) (OCH 3 ) 2 ), 1-chloropropyldimethoxysilane (HSi (CHClCH 2 CH 3 ) (OCH 3 ) 2 ), 2-chloropropyldimethoxysilane (HSi (CH 2 CHClCH 3 ) (OCH 3 ) 2), 3-chloropropyl dimethoxy silane (HSi (CH 2 CH 2 CH 2 Cl) (OCH 3) 2), fluoromethyl dimethoxy silane (HSi (CH 2 F) (OCH 3) 2), bromo methyldimethoxysilane ( HSi (CH 2 Br) (OCH 3 ) 2 ), iodomethyldi Silane (HSi (CH 2 I) ( OCH 3) 2), methoxymethyl dimethoxy silane (HSi (CH 2 OCH 3) (OCH 3) 2), methoxymethyl diethoxy silane (HSi (CH 2 OCH 3) (OC 2 H 5) 2), methoxymethyl diisopropenylbenzene silane (HSi (CH 2 OCH 3) (OC (CH 3) = CH 2) 2), ( dimethoxymethyl) dimethoxysilane (HSi (CH (OCH 3) 2 ) (OCH 3 ) 2 ), ethoxymethyldimethoxysilane (HSi (CH 2 OC 2 H 5 ) (OCH 3 ) 2 ), ethoxymethyldiethoxysilane (HSi (CH 2 OC 2 H 5 ) (OC 2 H 5 ) 2 ), 1-methoxyethyldimethoxysilane (HSi (CH (OCH 3 ) CH 3 ) (OCH 3 ) 2), trimethoxy methyl silane (HSi (C (OCH 3) 3) (OCH 3) 2), ( methoxymethyl) methyl silane (HSi (CH 2 OCH 3) (CH 3) (OCH 3)), Bis (methoxymethyl) methoxysilane (HSi (CH 2 OCH 3 ) 2 (OCH 3 )), methylthiomethyldimethoxysilane (HSi (CH 2 SCH 3 ) (OCH 3 ) 2 ), and the like can be given. However, alkoxyhydrosilane (A) is not limited to these.
　得られるシランの有用性から、上記の中では、メチルジメトキシシラン、エチルジメトキシシラン、ｎ－プロピルジメトキシシラン、ｎ－ヘキシルジメトキシシラン、フェニルジメトキシシラン、クロロメチルジメトキシシラン、クロロメチルジエトキシシラン、クロロメチルメトキシメチルシラン、ビス（クロロメチル）メトキシシラン、メトキシメチルジメトキシシラン、メトキシメチルジエトキシシラン、（メトキシメチル）メチルメトキシシラン、ビス（メトキシメチル）メトキシシラン、が好ましく、メトキシメチルジメトキシシランがより好ましい。 From the usefulness of the resulting silane, among the above, methyldimethoxysilane, ethyldimethoxysilane, n-propyldimethoxysilane, n-hexyldimethoxysilane, phenyldimethoxysilane, chloromethyldimethoxysilane, chloromethyldiethoxysilane, chloromethyl Methoxymethylsilane, bis (chloromethyl) methoxysilane, methoxymethyldimethoxysilane, methoxymethyldiethoxysilane, (methoxymethyl) methylmethoxysilane, and bis (methoxymethyl) methoxysilane are preferred, and methoxymethyldimethoxysilane is more preferred.
＜アルコキシハロシラン（Ｂ）＞
　上記のアルコキシヒドロシラン（Ａ）は、下記式（２）：
Ｘ－ＳｉＲ１ ａ（ＯＲ２）３－ａ・・・（２）
（式（２）中、Ｒ１、Ｒ２、及びａは、式（１）と同様であり、Ｘはハロゲン原子である。）
で表されるアルコキシハロシラン（Ｂ）を用いて製造される。
　ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、及びヨウ素原子が挙げられ、原料の入手性の観点で塩素原子、臭素原子が好ましく、取り扱いの容易さの面で塩素原子がより好ましい。
　アルコキシハロシラン（Ｂ）の好ましい製造方法については後述する。 <Alkoxyhalosilane (B)>
The alkoxy hydrosilane (A) is represented by the following formula (2):
X-SiR 1 a (OR 2 ) 3-a (2)
(In Formula (2), R 1 , R 2 , and a are the same as in Formula (1), and X is a halogen atom.)
It is manufactured using the alkoxyhalosilane (B) represented by these.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A chlorine atom and a bromine atom are preferable from the viewpoint of availability of raw materials, and a chlorine atom is more preferable in terms of ease of handling.
A preferred method for producing the alkoxyhalosilane (B) will be described later.
　アルコキシハロシラン（Ｂ）の好適な具体例としては、前述の式（１）で表されるアルコキシヒドロシラン（Ａ）の好適な具体例として挙げた化合物における、ケイ素原子に結合する水素原子を塩素原子に置換した化合物が挙げられる。 As a preferable specific example of the alkoxyhalosilane (B), a hydrogen atom bonded to a silicon atom in the compound exemplified as a preferable specific example of the alkoxyhydrosilane (A) represented by the formula (1) is a chlorine atom. The compound substituted by is mentioned.
＜水素化剤（Ｄ）＞
　アルコキシヒドロシラン（Ａ）は、アルコキシハロシラン（Ｂ）に含まれるハロゲン原子（Ｘ）を水素化剤（Ｄ）により水素化して製造される。
　水素化剤（Ｄ）の種類は、アルコキシハロシラン（Ｂ）中のハロゲン原子（Ｘ）を良好に水素化できれば特に限定されず、周知の水素化剤（Ｄ）から適宜選択される。水素化剤（Ｄ）は２種以上を組合わせて用いてよい。 <Hydrogenating agent (D)>
The alkoxyhydrosilane (A) is produced by hydrogenating the halogen atom (X) contained in the alkoxyhalosilane (B) with the hydrogenating agent (D).
The type of the hydrogenating agent (D) is not particularly limited as long as the halogen atom (X) in the alkoxyhalosilane (B) can be hydrogenated well, and is appropriately selected from the known hydrogenating agents (D). The hydrogenating agent (D) may be used in combination of two or more.
　好適な水素化剤としては、下記式（Ｄ１）：
ＭＢＨ４・・・（Ｄ１）
（式（Ｄ１）中、Ｍは、リチウム、ナトリウム、又はカリウムである。）
で表される化合物が挙げられる。式（Ｄ１）で表される化合物の中では、アルコキシハロシラン（Ｂ）から収率良くアルコキシヒドロシラン（Ａ）を生成させやすいことから、Ｍがナトリウムである水素化ホウ素ナトリウムが好ましい。 As a suitable hydrogenating agent, the following formula (D1):
MBH 4 ... (D1)
(In the formula (D1), M is lithium, sodium, or potassium.)
The compound represented by these is mentioned. Among the compounds represented by the formula (D1), sodium borohydride, in which M is sodium, is preferable because the alkoxyhydrosilane (A) can be easily produced from the alkoxyhalosilane (B) with a high yield.
　水素化剤（Ｄ）の使用量は、所望する収率でアルコキシヒドロシラン（Ａ）を製造できれば特に限定されない。水素化剤（Ｄ）の使用量は、アルコキシハロシラン（Ｂ）に含まれるハロゲン原子（Ｘ）１モルを水素化し得る化学量論的な量の、０．５～１０倍量が好ましく、１．０～５．０倍量がより好ましく、１．２～３．０倍量が特に好ましい。 The amount of hydrogenating agent (D) used is not particularly limited as long as alkoxyhydrosilane (A) can be produced in a desired yield. The amount of the hydrogenating agent (D) used is preferably 0.5 to 10 times the stoichiometric amount capable of hydrogenating 1 mol of the halogen atom (X) contained in the alkoxyhalosilane (B). An amount of 0.0 to 5.0 times is more preferable, and an amount of 1.2 to 3.0 times is particularly preferable.
＜溶剤（Ｓ）＞
　アルコキシハロシラン（Ｂ）と、前述の水素化剤（Ｄ）とを反応させる際には、エーテル結合を有する非プロトン性有機溶剤を５０質量％以上含む溶剤（Ｓ）を用いる。
　これにより、アルコキシハロシラン（Ｂ）に含まれるハロゲン原子（Ｘ）の水素化剤（Ｄ）による水素化が良好に進行する。 <Solvent (S)>
When the alkoxyhalosilane (B) is reacted with the hydrogenating agent (D), a solvent (S) containing 50% by mass or more of an aprotic organic solvent having an ether bond is used.
Thereby, hydrogenation of the halogen atom (X) contained in the alkoxyhalosilane (B) with the hydrogenating agent (D) proceeds well.
　エーテル結合を有する非プロトン性有機溶剤の好適な具体例としては、テトラヒドロフラン、テトラヒドロピラン、１，４－ジオキサン等の環状エーテル類；ジエチルエーテル、ジｎ－ブチルエーテル、シクロペンチルメチルエーテル等のジアルキルエーテル類；アニソール等のアルコキシベンゼン類；メトキシ酢酸メチル、メトキシ酢酸エチル等のアルコキシアルカン酸エステル類；１，２－ジメトキシエタン、１，２－ジエトキシエタン、プロピレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル（ジグライム）、ジプロピレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル（トリグライム）、トリプロピレングリコールジメチルエーテル、テトラエチレングリコールジメチルエーテル（テトラグライム）、テトラプロピレングリコールジメチルエーテル等のグリコールジアルキルエーテル；エチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート等のグリコールアルキルエーテルアセテートが挙げられる。これらのエーテル結合を有する非プロトン性有機溶剤は２種以上を組み合わせて用いてもよい。 Specific examples of suitable aprotic organic solvents having an ether bond include cyclic ethers such as tetrahydrofuran, tetrahydropyran, and 1,4-dioxane; dialkyl ethers such as diethyl ether, di-n-butyl ether, and cyclopentyl methyl ether; Alkoxybenzenes such as anisole; alkoxyalkanoic acid esters such as methyl methoxyacetate and ethyl methoxyacetate; 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol dimethyl ether, diethylene glycol dimethyl ether (diglyme), dipropylene glycol Dimethyl ether, triethylene glycol dimethyl ether (triglyme), tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether (Tetraglyme), glycol dialkyl ethers such as tetraethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, glycolate alkyl ether acetates such as dipropylene glycol monomethyl ether acetate. These aprotic organic solvents having an ether bond may be used in combination of two or more.
　これらの中では、アルコキシヒドロシラン（Ａ）を良好な収率で製造しやすいことから、テトラヒドロフラン、１，２－ジメトキシエタン、ジエチレングリコールジメチルエーテル、及びトリエチレングリコールジメチルエーテルが好ましく、取扱いや反応後の回収、精製が容易であることから１，２－ジメトキシエタンがより好ましい。 Among these, tetrahydrofuran, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether are preferable because alkoxyhydrosilane (A) can be easily produced in a good yield, and recovery and purification after handling and reaction. 1,2-dimethoxyethane is more preferable.
　溶剤（Ｓ）におけるエーテル結合を有する非プロトン性有機溶剤の含有量は５０質量％以上であれば特に限定されないが、７０質量％以上が好ましく、９０質量％以上がより好ましく、１００質量％が特に好ましい。溶剤（Ｓ）におけるエーテル結合を有する非プロトン性有機溶剤の含有量が多いほど、水素化の反応性が向上する傾向にある。 The content of the aprotic organic solvent having an ether bond in the solvent (S) is not particularly limited as long as it is 50% by mass or more, but is preferably 70% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass. preferable. As the content of the aprotic organic solvent having an ether bond in the solvent (S) is larger, the hydrogenation reactivity tends to be improved.
　溶剤（Ｓ）において、エーテル結合を有する非プロトン性有機溶剤とともに他の溶剤を用いる場合、他の溶剤の種類は、アルコキシハロシラン（Ｂ）に含まれるハロゲン原子（Ｘ）の水素化剤（Ｄ）による水素化を阻害しない限り特に限定されない。
　他の溶剤としては、典型的には、炭化水素系有機溶剤が、水素化剤（Ｄ）と反応しにくい点で好ましい。その中でも、エーテル結合を有する非プロトン性有機溶剤と混和する溶剤がより好ましい。 When another solvent is used together with the aprotic organic solvent having an ether bond in the solvent (S), the type of the other solvent is a hydrogenating agent (D) of the halogen atom (X) contained in the alkoxyhalosilane (B). ) Is not particularly limited as long as hydrogenation by h is not inhibited.
As the other solvent, typically, a hydrocarbon organic solvent is preferable in that it hardly reacts with the hydrogenating agent (D). Among these, a solvent that is miscible with an aprotic organic solvent having an ether bond is more preferable.
　他の溶剤として使用できる炭化水素系有機溶剤の好適な具体例としては、ｎ－ペンタン、ｎ－ヘキサン、ｎ－ヘプタン、ｎ－オクタン等のアルカン；トルエン、キシレン、メシチレン、エチルベンゼン等の芳香族溶剤等が挙げられる。 Specific examples of hydrocarbon organic solvents that can be used as other solvents include alkanes such as n-pentane, n-hexane, n-heptane, and n-octane; aromatic solvents such as toluene, xylene, mesitylene, and ethylbenzene. Etc.
　溶剤（Ｓ）の使用量は、所望する収率でアルコキシヒドロシラン（Ａ）を生成させることができる限り特に限定されない。溶剤（Ｓ）の使用量は、典型的には、アルコキシハロシラン（Ｂ）１００質量部に対して、５０～１０００質量部が好ましく、７０～８００質量部がより好ましく、１００～５００質量部が特に好ましい。溶剤（Ｓ）が少なすぎる場合は、水素化の進行が遅くなる傾向にあり、溶剤（Ｓ）が多すぎる場合は、反応後の除去が煩雑になる。 The amount of the solvent (S) used is not particularly limited as long as the alkoxyhydrosilane (A) can be produced in a desired yield. The amount of the solvent (S) used is typically preferably 50 to 1000 parts by weight, more preferably 70 to 800 parts by weight, and more preferably 100 to 500 parts by weight with respect to 100 parts by weight of the alkoxyhalosilane (B). Particularly preferred. When there is too little solvent (S), there exists a tendency for progress of hydrogenation to become slow, and when there is too much solvent (S), the removal after reaction becomes complicated.
＜反応条件＞
　アルコキシハロシラン（Ｂ）と、前述の水素化剤（Ｄ）とを反応させる条件は、反応が良好に進行する限り特に限定されない。アルコキシハロシラン（Ｂ）に対して水素化剤（Ｄ）を添加してもよく、逆に水素化剤（Ｄ）に対してアルコキシハロシラン（Ｂ）を添加してもよい。アルコキシハロシラン（Ｂ）及び水素化剤（Ｄ）の混合前に、反応系に溶剤（Ｓ）が存在しているのが好ましい。
　アルコキシハロシラン（Ｂ）又は水素化剤（Ｄ）の添加方法は特に限定されず、アルコキシハロシラン（Ｂ）又は水素化剤（Ｄ）を単独で反応系に加えてもよく、アルコキシハロシラン（Ｂ）又は水素化剤（Ｄ）の溶液又は懸濁液を反応系に加えてもよい。
　アルコキシハロシラン（Ｂ）又は水素化剤（Ｄ）は、１度又は数度に分割して反応系に加えられてもよく、滴下等の方法により連続的に反応系に加えられてもよい。アルコキシハロシラン（Ｂ）又は水素化剤（Ｄ）を反応系内に加える時間は特に限定されず、反応の進行状況に応じて適宜選択される。 <Reaction conditions>
The conditions for reacting the alkoxyhalosilane (B) with the hydrogenating agent (D) described above are not particularly limited as long as the reaction proceeds well. The hydrogenating agent (D) may be added to the alkoxyhalosilane (B), and conversely, the alkoxyhalosilane (B) may be added to the hydrogenating agent (D). Before mixing the alkoxyhalosilane (B) and the hydrogenating agent (D), the solvent (S) is preferably present in the reaction system.
The method for adding the alkoxyhalosilane (B) or the hydrogenating agent (D) is not particularly limited, and the alkoxyhalosilane (B) or the hydrogenating agent (D) may be added alone to the reaction system. A solution or suspension of B) or hydrogenating agent (D) may be added to the reaction system.
Alkoxyhalosilane (B) or hydrogenating agent (D) may be added to the reaction system by dividing it once or several times, or may be continuously added to the reaction system by a method such as dropping. The time for adding the alkoxyhalosilane (B) or the hydrogenating agent (D) to the reaction system is not particularly limited, and is appropriately selected according to the progress of the reaction.
　アルコキシハロシラン（Ｂ）と、水素化剤（Ｄ）とを反応させる温度は、反応が良好に進行する限り特に限定されない。典型的には０～４０℃である。 The temperature at which the alkoxyhalosilane (B) and the hydrogenating agent (D) are reacted is not particularly limited as long as the reaction proceeds well. Typically, it is 0 to 40 ° C.
　アルコキシハロシラン（Ｂ）と、水素化剤（Ｄ）とを反応させる雰囲気は特に限定されないが、窒素ガス等の不活性ガス雰囲気下に反応が行われるのが好ましい。
　アルコキシハロシラン（Ｂ）と、水素化剤（Ｄ）との反応は、大気圧下で行われても、減圧下で行われても、加圧下で行われてもよい。
　アルコキシハロシラン（Ｂ）と、水素化剤（Ｄ）との反応は、バッチ式及び連続式のいずれの方法で行うこともできる。 The atmosphere in which the alkoxyhalosilane (B) and the hydrogenating agent (D) are reacted is not particularly limited, but the reaction is preferably performed in an inert gas atmosphere such as nitrogen gas.
The reaction between the alkoxyhalosilane (B) and the hydrogenating agent (D) may be carried out under atmospheric pressure, under reduced pressure, or under pressure.
The reaction between the alkoxyhalosilane (B) and the hydrogenating agent (D) can be carried out by either a batch method or a continuous method.
　アルコキシハロシラン（Ｂ）と、水素化剤（Ｄ）とを反応させる時間は、反応が良好に進行する限り特に限定されない。アルコキシハロシラン（Ｂ）又は水素化剤（Ｄ）の添加時間も含め、典型的には、１時間～２４時間であり、１時間３０分～１０時間が好ましく、２時間～５時間がより好ましい。反応時間が短いと、反応による発熱で反応系の温度が急上昇する懸念がある。反応時間が長いと、生成物が分解する懸念がある。
　ただし、式（２）で表されるアルコキシハロシラン（Ｂ）におけるＲ１の炭素原子数が大きい場合、水素化反応に長時間を要する場合がある。反応時間は、この点を考慮のうえ、必要に応じて反応の進行状況を分析しながら、適宜決定されるのが好ましい。 The time for reacting the alkoxyhalosilane (B) and the hydrogenating agent (D) is not particularly limited as long as the reaction proceeds well. Including the addition time of alkoxyhalosilane (B) or hydrogenating agent (D), it is typically 1 hour to 24 hours, preferably 1 hour 30 minutes to 10 hours, more preferably 2 hours to 5 hours. . If the reaction time is short, there is a concern that the temperature of the reaction system rapidly rises due to heat generated by the reaction. If the reaction time is long, the product may be decomposed.
However, when the number of carbon atoms of R 1 in the alkoxyhalosilane (B) represented by the formula (2) is large, the hydrogenation reaction may take a long time. In consideration of this point, the reaction time is preferably appropriately determined while analyzing the progress of the reaction as necessary.
　以上説明した方法により製造されるアルコキシヒドロシラン（Ａ）は、例えばろ過や減圧捕集等、周知の方法で反応系内から回収された後、必要に応じて、蒸留等の方法により精製される。
　かかる方法により製造されるアルコキシヒドロシラン（Ａ）は、例えば、ＷＯ２０１１／１６１９１５号公報で提案されているように、Ｓｉ－Ｈを利用したヒドロシリル化反応、Ｓｉ－ＯＲ２を利用した加水分解、縮合反応等に使用することができ、種々の化合物の製造原料として好適に使用される。 The alkoxyhydrosilane (A) produced by the method described above is recovered from the reaction system by a well-known method such as filtration or collection under reduced pressure, and then purified by a method such as distillation, if necessary.
The alkoxyhydrosilane (A) produced by such a method is, for example, as proposed in WO2011 / 161915, hydrosilylation reaction using Si—H, hydrolysis and condensation reaction using Si—OR 2. It can be used as a raw material for producing various compounds.
≪アルコキシハロシラン（Ｂ）の製造方法≫
　アルコキシヒドロシランの製造に用いられる、前述の式（２）で表されるアルコキシハロシラン（Ｂ）の製造方法は特に限定されない。
　収率が良好であることから、アルコキシハロシラン（Ｂ）の製造方法は、下記式（３）：
ＳｉＲ１ ａ（ＯＲ２）４－ａ・・・（３）
（式（３）中、Ｒ１、及びＲ２、及びａは式（２）と同様である。）
で表されるアルコキシシラン（Ｃ）に、－３０℃以上８０℃以下の温度で、ハロゲン化剤（Ｅ）を反応させてアルコキシハロシラン（Ｂ）を生成させることを含む方法が好ましい。
　この方法では、アルコキシシラン（Ｃ）１モルからアルコキシハロシラン（Ｂ）１モルを生成させる、化学量論的なハロゲン化剤（Ｅ）の量を１モル当量とする場合に、１．５モル当量以下である量のハロゲン化剤（Ｅ）が使用される。 ≪Method for producing alkoxyhalosilane (B) ≫
The production method of the alkoxyhalosilane (B) represented by the above formula (2) used for the production of the alkoxyhydrosilane is not particularly limited.
Since the yield is good, the production method of alkoxyhalosilane (B) is represented by the following formula (3):
SiR 1 a (OR 2 ) 4-a (3)
(In formula (3), R 1 , R 2 , and a are the same as in formula (2).)
A method comprising reacting the alkoxysilane (C) represented by formula (I) with a halogenating agent (E) at a temperature of −30 ° C. or higher and 80 ° C. or lower to produce an alkoxyhalosilane (B) is preferable.
In this method, when 1 mole equivalent of the stoichiometric halogenating agent (E) for producing 1 mole of alkoxyhalosilane (B) from 1 mole of alkoxysilane (C) is 1.5 moles. An amount of halogenating agent (E) that is less than or equal to the equivalent is used.
＜アルコキシシラン（Ｃ）＞
　上記のアルコキシシラン（Ｃ）は、ＳｉＲ１ ａ（ＯＲ２）４－ａ・・・（３）
（式（３）中、Ｒ１、及びＲ２、及びａは式（２）と同様である。）
で表される化合物である。 <Alkoxysilane (C)>
The alkoxysilane (C) is SiR 1 a (OR 2 ) 4-a (3)
(In formula (3), R 1 , R 2 , and a are the same as in formula (2).)
It is a compound represented by these.
　アルコキシシラン（Ｃ）の好適な具体例としては、前述の式（１）で表されるアルコキシヒドロシラン（Ａ）の好適な具体例として挙げた化合物における、ケイ素原子に結合する水素原子を、ＯＲ２基（Ｒ２は式（２）と同様である。）に置換した化合物が挙げられる。 As a suitable specific example of alkoxysilane (C), the hydrogen atom couple | bonded with a silicon atom in the compound quoted as a suitable specific example of alkoxyhydrosilane (A) represented by the above-mentioned Formula (1) is OR 2. And a compound substituted with a group (R 2 is the same as in formula (2)).
＜ハロゲン化剤（Ｅ）＞
　ハロゲン化剤としては、アルコキシシラン（Ｃ）に含まれる４－ａ個のＯＲ２で表されるアルコキシ基のうちの１つを所望する程度に高い選択率でハロゲン化できる化合物であれば特に限定されない。 <Halogenating agent (E)>
The halogenating agent is not particularly limited as long as it is a compound that can halogenate one of the alkoxy groups represented by 4-a OR 2 contained in the alkoxysilane (C) with a desired high selectivity. Not.
　このようなハロゲン化剤の好適な例としては、反応後の後処理の容易であることから、カルボン酸ハライドが好ましい。前述の通りアルコキシハロシラン（Ｂ）に関する式（２）において、ハロゲン原子（Ｘ）としては塩素原子又は臭素原子が反応性の面で好ましく、塩素原子が原料入手性や価格の面でより好ましい。このため、カルボン酸ハライドとしても、カルボン酸クロリド又はカルボン酸ブロミドが好ましく、カルボン酸クロリドがより好ましい。 As a suitable example of such a halogenating agent, a carboxylic acid halide is preferable because post-treatment after the reaction is easy. As described above, in the formula (2) relating to the alkoxyhalosilane (B), as the halogen atom (X), a chlorine atom or a bromine atom is preferable in terms of reactivity, and a chlorine atom is more preferable in terms of availability of raw materials and price. For this reason, also as a carboxylic acid halide, a carboxylic acid chloride or a carboxylic acid bromide is preferable, and a carboxylic acid chloride is more preferable.
　カルボン酸ハライドの好ましい具体例としては、塩化アセチル、塩化プロピオニル、塩化ブタノイル、塩化アクリロイル、塩化メタクリロイル、塩化ベンゾイル等の一塩化物、塩化オキサリル、塩化アジポイル、コハク酸塩化物、セバシン酸塩化物等の二塩化物、１，３，５－ベンゼントリカルボン酸三塩化物等の三塩化物、及び臭化アセチル等の臭化物等が挙げられる。これらの中では、塩化アセチル、塩化ベンゾイル、臭化アセチルが反応の収率面でより好ましく、塩化アセチルが価格の面で特に好ましい。 Preferred specific examples of carboxylic acid halides include monochlorides such as acetyl chloride, propionyl chloride, butanoyl chloride, acryloyl chloride, methacryloyl chloride, benzoyl chloride, oxalyl chloride, adipoyl chloride, succinic acid chloride, sebacic acid chloride, and the like. Examples thereof include dichlorides, trichlorides such as 1,3,5-benzenetricarboxylic acid trichloride, and bromides such as acetyl bromide. Among these, acetyl chloride, benzoyl chloride, and acetyl bromide are more preferable in terms of yield of the reaction, and acetyl chloride is particularly preferable in terms of cost.
　ハロゲン化剤（Ｅ）の使用量は、アルコキシシラン（Ｃ）１モルからアルコキシハロシラン（Ｂ）１モルを生成させる、化学量論的なハロゲン化剤（Ｅ）の量を１モル当量とする場合に、１．５モル当量以下である量であり、０．５～１．２モル当量が好ましく、０．７～１．１モル当量がより好ましい。
　ハロゲン化剤（Ｅ）の使用量は、少なくなるとハロゲン化率が下がることから最終的に所望のヒドロシランの収率低下に繋がり、多くなるとジハロゲン化体やトリハロゲン化の体の副生量が増加してしまう。 The amount of the halogenating agent (E) used is 1 molar equivalent of the stoichiometric amount of the halogenating agent (E) that generates 1 mol of alkoxyhalosilane (B) from 1 mol of alkoxysilane (C). In some cases, the amount is 1.5 molar equivalents or less, preferably 0.5 to 1.2 molar equivalents, and more preferably 0.7 to 1.1 molar equivalents.
If the amount of the halogenating agent (E) used decreases, the halogenation rate decreases, which ultimately leads to a decrease in the yield of the desired hydrosilane. If the amount used increases, the amount of by-produced dihalogenated compounds and trihalogenated compounds increases. Resulting in.
＜ルイス酸性を示す金属塩（Ｆ）＞
　アルコキシシラン（Ｃ）とハロゲン化剤（Ｅ）との反応は、ルイス酸性を示す金属塩（Ｆ）の存在下に行われるのが好ましい。 <Metal salt exhibiting Lewis acidity (F)>
The reaction between the alkoxysilane (C) and the halogenating agent (E) is preferably performed in the presence of a metal salt (F) exhibiting Lewis acidity.
　金属塩（Ｆ）は、金属カチオンとアニオンとからなる塩であることが好ましい。金属塩（Ｆ）における金属としては、アルカリ土類金属、遷移金属、亜鉛、アルミニウム、及び、ホウ素が好ましく挙げられる。金属塩（Ｆ）を構成するアニオンとしては、ハロゲン化物イオン、ＢＦ４ －、ＰＦ６ －、ＳｂＦ６ －、ＣｌＯ４ －、ＣＦ３ＣＯ２ －、及び、ＣＦ３ＳＯ３ －が好ましく挙げられ、ハロシラン以外の副生を抑制できる点で、ハロゲン化物イオンがより好ましい。 The metal salt (F) is preferably a salt composed of a metal cation and an anion. Preferred examples of the metal in the metal salt (F) include alkaline earth metals, transition metals, zinc, aluminum, and boron. Preferred examples of the anion constituting the metal salt (F) include halide ions, BF 4 − , PF 6 − , SbF 6 − , ClO 4 − , CF 3 CO 2 − , and CF 3 SO 3 − . Halide ions are more preferable in that by-products other than halosilane can be suppressed.
　ルイス酸性を示す金属塩（Ｆ）の好ましい例としては、塩化マグネシウム（ＭｇＣｌ２）、臭化マグネシウム（ＭｇＢｒ２）、三フッ化ホウ素エーテル錯体（ＢＦ３・Ｏ（Ｃ２Ｈ５）２）、三塩化ホウ素（ＢＣｌ３）、塩化アルミニウム（ＡｌＣｌ３）、臭化アルミニウム（ＡｌＢｒ３）、塩化亜鉛（ＺｎＣｌ２）、臭化亜鉛（ＺｎＢｒ２）、四塩化スズ（ＳｎＣｌ４）、四臭化スズ（ＳｎＢｒ４）、三塩化鉄（ＦｅＣｌ３）、三臭化鉄（ＦｅＢｒ３）、四塩化チタン（ＴｉＣｌ４）、四臭化チタン（ＴｉＢｒ４）、等が挙げられる。
　これらの中では塩化亜鉛が反応性や取り扱いの容易さの面で好ましい。このため、アルコキシシラン（Ｃ）とハロゲン化剤（Ｅ）との反応には、塩化亜鉛を含む金属塩（Ｆ）を用いるのが好ましい。 Preferred examples of the metal salt (F) exhibiting Lewis acidity include magnesium chloride (MgCl 2 ), magnesium bromide (MgBr 2 ), boron trifluoride ether complex (BF 3 .O (C 2 H 5 ) 2 ), Boron trichloride (BCl 3 ), aluminum chloride (AlCl 3 ), aluminum bromide (AlBr 3 ), zinc chloride (ZnCl 2 ), zinc bromide (ZnBr 2 ), tin tetrachloride (SnCl 4 ), tin tetrabromide (SnBr 4 ), iron trichloride (FeCl 3 ), iron tribromide (FeBr 3 ), titanium tetrachloride (TiCl 4 ), titanium tetrabromide (TiBr 4 ), and the like.
Among these, zinc chloride is preferable in terms of reactivity and ease of handling. For this reason, it is preferable to use the metal salt (F) containing zinc chloride for the reaction between the alkoxysilane (C) and the halogenating agent (E).
　金属塩（Ｆ）の使用量は、アルコキシシラン（Ｃ）とハロゲン化剤（Ｅ）との反応が良好に進行する限り特に限定されない。
　金属塩（Ｆ）の使用量は、典型的には、アルコキシシラン（Ｃ）の物質量に対して、０．０１～２０モル％が好ましく、０．０５～１０モル％がより好ましく、０．１～２．０モル％が特に好ましい。金属塩（Ｆ）の使用量が少ないと反応速度が遅くなり、多すぎると経済的に不利である。 The amount of the metal salt (F) used is not particularly limited as long as the reaction between the alkoxysilane (C) and the halogenating agent (E) proceeds well.
The amount of the metal salt (F) used is typically preferably 0.01 to 20 mol%, more preferably 0.05 to 10 mol%, relative to the amount of the alkoxysilane (C) substance. 1 to 2.0 mol% is particularly preferred. If the amount of the metal salt (F) used is small, the reaction rate is slow, and if it is too large, it is economically disadvantageous.
＜溶剤＞
　上記の方法によりアルコキシハロシラン（Ｂ）を製造する場合、必要に応じて、溶剤を用いることができる。溶剤としては、ハロゲン化剤（Ｅ）との反応等により、アルコキシシラン（Ｃ）のハロゲン化を阻害しなければ特に限定されない。
　好適に使用される溶剤としては、例えば、１，２－ジメトキシエタン等の非プロトン性エーテル系溶剤、ヘキサン等の炭化水素系溶剤、及び酢酸メチル等の非プロトン性エステル系溶剤等が挙げられる。溶剤は単独で用いても、複数を混合して用いてもよい。
　アルコキシハロシラン（Ｂ）の製造に引き続き、アルコキシヒドロシラン（Ａ）を前述の方法に従って製造する場合、アルコキシハロシラン（Ｂ）の製造に用いる溶剤として前述した、溶剤（Ｓ）を用いることもできる。 <Solvent>
When the alkoxyhalosilane (B) is produced by the above method, a solvent can be used as necessary. The solvent is not particularly limited as long as the halogenation of the alkoxysilane (C) is not inhibited by reaction with the halogenating agent (E) or the like.
Suitable solvents include, for example, aprotic ether solvents such as 1,2-dimethoxyethane, hydrocarbon solvents such as hexane, and aprotic ester solvents such as methyl acetate. A solvent may be used independently or may be used in mixture of multiple.
Subsequent to the production of the alkoxyhalosilane (B), when the alkoxyhydrosilane (A) is produced according to the method described above, the solvent (S) described above as the solvent used for the production of the alkoxyhalosilane (B) can also be used.
　溶剤を用いる場合、溶剤の使用量は、所望する収率でアルコキシハロシラン（Ｂ）を生成させることができる限り特に限定されない。溶剤の使用量は、典型的には、アルコキシシラン（Ｃ）１００質量部に対して、１０００質量部以下が好ましく、８００質量部以下がより好ましく、５００質量部以下が特に好ましい。溶剤が多すぎる場合は、反応後の除去が煩雑になり、また経済的にも不利である。 When the solvent is used, the amount of the solvent used is not particularly limited as long as the alkoxyhalosilane (B) can be produced in a desired yield. Typically, the amount of the solvent used is preferably 1000 parts by mass or less, more preferably 800 parts by mass or less, and particularly preferably 500 parts by mass or less with respect to 100 parts by mass of the alkoxysilane (C). When there is too much solvent, the removal after the reaction becomes complicated, and it is disadvantageous economically.
＜反応条件＞
　アルコキシシラン（Ｃ）と、ハロゲン化剤（Ｅ）との反応は、－３０℃以上１００℃以下の温度で行われる。反応温度は、反応中一定であっても、変化していてもよい。
　アルコキシシラン（Ｃ）と、ハロゲン化剤（Ｅ）との反応を行う温度は、その少なくとも一部が－３０℃以上１００℃以下であればよく、反応中の平均温度が－３０℃以上１００℃以下であるのが好ましく、反応中の温度が、全て－３０℃以上１００℃以下の範囲内であるのがより好ましい。反応中の温度が全て－３０℃未満であると、反応がほとんど進行しなくなる。反応温度が１００℃を超える時間が長くなると、ジハロゲン化体やトリハロゲン化体の副生量が増加してしまう。 <Reaction conditions>
The reaction between the alkoxysilane (C) and the halogenating agent (E) is performed at a temperature of −30 ° C. or higher and 100 ° C. or lower. The reaction temperature may be constant during the reaction or may vary.
The temperature at which the alkoxysilane (C) and the halogenating agent (E) are reacted may be at least partially -30 ° C to 100 ° C, and the average temperature during the reaction is -30 ° C to 100 ° C. The temperature during the reaction is preferably within the range of −30 ° C. or more and 100 ° C. or less. When the temperatures during the reaction are all lower than −30 ° C., the reaction hardly proceeds. If the reaction temperature exceeds 100 ° C. for a long time, the amount of by-produced dihalides and trihalides increases.
　また、アルコキシシラン（Ｃ）と、ハロゲン化剤（Ｅ）との反応を行う温度は、その少なくとも一部が－１０℃以上９０℃以下であるのが好ましく、反応中の平均温度が－１０℃以上９０℃以下であるのがより好ましく、反応中の温度が、全て－１０℃以上９０℃以下の範囲内であるのが特に好ましい。反応温度がかかる範囲内であれば、温水、冷水、ブライン等の、汎用される熱媒や冷媒を用いて反応温度の調製が可能であり、経済的に有利である。 Further, the temperature at which the alkoxysilane (C) and the halogenating agent (E) are reacted is preferably at least partly −10 ° C. or higher and 90 ° C. or lower, and the average temperature during the reaction is −10 ° C. It is more preferable that the temperature is 90 ° C. or lower, and it is particularly preferable that all the temperatures during the reaction are within a range of −10 ° C. or higher and 90 ° C. or lower. If the reaction temperature is within such a range, the reaction temperature can be adjusted using a commonly used heat medium or refrigerant such as hot water, cold water, or brine, which is economically advantageous.
　さらに、アルコキシシラン（Ｃ）と、ハロゲン化剤（Ｅ）との反応は、その少なくとも一部が０℃以上２０℃以下であるのが好ましく、反応中の平均温度が０℃以上２０℃以下であるのがより好ましく、反応中の温度が、全て０℃以上２０℃以下の範囲内であるのが特に好ましい。反応中の温度を０℃以上とすることで十分な反応性を確保できる。また反応温度が２０℃以下とすることで、ジハロゲン化体やトリハロゲン化の体の副生量を十分に抑制できる。 Furthermore, it is preferable that at least a part of the reaction between the alkoxysilane (C) and the halogenating agent (E) is 0 ° C. or higher and 20 ° C. or lower, and the average temperature during the reaction is 0 ° C. or higher and 20 ° C. or lower. It is more preferable that all the temperatures during the reaction are in the range of 0 ° C. or higher and 20 ° C. or lower. Sufficient reactivity can be secured by setting the temperature during the reaction to 0 ° C. or higher. In addition, when the reaction temperature is 20 ° C. or less, the amount of by-produced dihalides and trihalogenated substances can be sufficiently suppressed.
　ハロゲン化剤（Ｅ）及び金属塩（Ｆ）の添加方法は特に限定されず、ハロゲン化剤（Ｅ）又は金属塩（Ｆ）を単独で反応系に加えてもよく、ハロゲン化剤（Ｅ）又は金属塩（Ｆ）の溶液又は懸濁液を反応系に加えてもよい。
　ハロゲン化剤（Ｅ）及び金属塩（Ｆ）は、１度又は数度に分割して反応系に加えられてもよく、滴下等の方法により連続的に反応系に加えられてもよい。ハロゲン化剤（Ｅ）及び金属塩（Ｆ）を反応系内に加える時間は特に限定されず、反応の進行状況に応じて適宜選択される。
　ハロゲン化剤（Ｅ）及び金属塩（Ｆ）の添加順序も特に限定されないが、反応時の昇温を抑制するため、金属塩（Ｆ）を先に添加し、その後ハロゲン化剤（Ｅ）を滴下等の方法により連続的に反応系に添加されることが好ましい。 The method for adding the halogenating agent (E) and the metal salt (F) is not particularly limited, and the halogenating agent (E) or the metal salt (F) may be added to the reaction system alone. Alternatively, a solution or suspension of the metal salt (F) may be added to the reaction system.
The halogenating agent (E) and the metal salt (F) may be added to the reaction system by dividing it once or several times, or may be continuously added to the reaction system by a method such as dropping. The time for adding the halogenating agent (E) and the metal salt (F) to the reaction system is not particularly limited, and is appropriately selected according to the progress of the reaction.
The order of addition of the halogenating agent (E) and the metal salt (F) is not particularly limited, but the metal salt (F) is added first, and then the halogenating agent (E) is added to suppress the temperature increase during the reaction. It is preferably added continuously to the reaction system by a method such as dropping.
　アルコキシシラン（Ｃ）と、ハロゲン化剤（Ｅ）とを反応させる雰囲気は特に限定されないが、窒素ガス等の不活性ガス雰囲気下に反応が行われるのが好ましい。
　アルコキシシラン（Ｃ）と、ハロゲン化剤（Ｅ）との反応は、大気圧下で行われても、減圧下で行われても、加圧下で行われてもよい。
　アルコキシシラン（Ｃ）と、ハロゲン化剤（Ｅ）との反応は、バッチ式及び連続式のいずれの方法で行うこともできる。 The atmosphere in which the alkoxysilane (C) and the halogenating agent (E) are reacted is not particularly limited, but the reaction is preferably performed in an inert gas atmosphere such as nitrogen gas.
The reaction between the alkoxysilane (C) and the halogenating agent (E) may be carried out under atmospheric pressure, under reduced pressure, or under pressure.
The reaction of the alkoxysilane (C) and the halogenating agent (E) can be carried out by either a batch method or a continuous method.
　アルコキシシラン（Ｃ）とハロゲン化剤（Ｅ）とを反応させる時間は特に限定されない。ハロゲン化剤（Ｅ）を滴下する時間、及びその後の反応時間を含め、典型的には、１０分～２４時間であり、３０分～１０時間が好ましく、１時間～５時間がより好ましい。反応時間が短いと、反応による発熱で反応系の温度が急上昇する懸念がある。反応時間が長いことによる反応系への影響は特にないが、経済的に不利である。 The time for reacting the alkoxysilane (C) and the halogenating agent (E) is not particularly limited. Including the time for dropping the halogenating agent (E) and the subsequent reaction time, it is typically 10 minutes to 24 hours, preferably 30 minutes to 10 hours, and more preferably 1 hour to 5 hours. If the reaction time is short, there is a concern that the temperature of the reaction system rapidly rises due to heat generated by the reaction. Although there is no particular influence on the reaction system due to the long reaction time, it is economically disadvantageous.
　このようにして生成するアルコキシハロシラン（Ｂ）は、そのまま又は精製され、好ましくは精製され、前述の方法による、アルコキシヒドロシラン（Ｅ）の製造方法における製造原料として供される。その他、Ｓｉ－ＸやＳｉ－ＯＲ２を利用した加水分解、縮合反応等に使用することができ、種々の化合物の製造原料として好適に使用される。 The alkoxyhalosilane (B) thus produced is directly or purified, preferably purified, and used as a production raw material in the method for producing alkoxyhydrosilane (E) by the above-described method. In addition, it can be used for hydrolysis, condensation reaction, etc. using Si—X or Si—OR 2 and is suitably used as a raw material for producing various compounds.
≪アルコキシハロシラン化合物≫
　以上説明した方法により、アルコキシヒドロシラン（Ａ）の製造原料である上記式（２）で表されるアルコキシハロシラン化合物（Ｂ）が製造される。
　アルコキシハロシラン化合物（Ｂ）の中では、アルコキシヒドロシラン（Ａ）を製造する際に副反応が生じにくい点等から、下記式（４）：
Ｘ－ＳｉＲ３（ＯＲ４）２・・・（４）
（式（４）中、Ｒ３は、炭素原子数１～２０のアルキル基であり、Ｒ３としてのアルキル基はハロゲン原子又は炭素原子数１～６のアルコキシ基で置換されていてもよく、Ｒ４は、炭素原子数１～２０の炭化水素基であり、Ｘはハロゲン原子である。２つのＯＲ４について、それらは同じでもよく、異なっていてもよい。）
で表されるアルコキシハロシラン化合物が好ましい。
　Ｘとしてのハロゲン原子と、アルキル基上の置換基としてのハロゲン原子としては、それぞれフッ素原子、塩素原子、臭素原子、及びヨウ素原子が挙げられ、製造の容易さから塩素原子又は臭素原子が好ましく、原料の入手性から塩素原子が好ましい。
　Ｒ３についての炭素原子１～２０のアルキル基の具体例や、Ｒ４についての炭素原子１～２０の炭化水素基の具体例は、Ｒ１及びＲ２について説明した、炭素原子１～２０のアルキル基の具体例や、炭素原子１～２０の炭化水素基の具体例と同様である。 ≪Alkoxyhalosilane compound≫
By the method demonstrated above, the alkoxy halosilane compound (B) represented by the said Formula (2) which is a manufacturing raw material of alkoxy hydrosilane (A) is manufactured.
Among the alkoxyhalosilane compounds (B), the following formula (4):
X-SiR 3 (OR 4 ) 2 (4)
(In Formula (4), R 3 is an alkyl group having 1 to 20 carbon atoms, and the alkyl group as R 3 may be substituted with a halogen atom or an alkoxy group having 1 to 6 carbon atoms; R 4 is a hydrocarbon group having 1 to 20 carbon atoms, and X is a halogen atom, and for two OR 4 , they may be the same or different.
The alkoxyhalosilane compound represented by these is preferable.
Examples of the halogen atom as X and the halogen atom as a substituent on the alkyl group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom or a bromine atom is preferable for ease of production, From the availability of raw materials, a chlorine atom is preferable.
Specific examples of the alkyl group having 1 to 20 carbon atoms for R 3 and specific examples of the hydrocarbon group having 1 to 20 carbon atoms for R 4 include those described for R 1 and R 2 . This is the same as the specific example of the alkyl group and the specific example of the hydrocarbon group having 1 to 20 carbon atoms.
　式（４）について、いずれも種々の化合物の製造原料として使用する際の反応性の観点から、Ｒ３がハロゲン原子（好ましくは塩素原子）で置換された炭素原子数１～３のアルキル基であるか、炭素原子数１～３のアルコキシ基で置換された炭素原子数１～３のアルキル基であるのが好ましく、且つＲ４が炭素原子数１～３のアルキル基であるのが好ましい。 In formula (4), R 3 is an alkyl group having 1 to 3 carbon atoms substituted with a halogen atom (preferably a chlorine atom) from the viewpoint of reactivity when used as a raw material for producing various compounds. It is preferably an alkyl group having 1 to 3 carbon atoms substituted with an alkoxy group having 1 to 3 carbon atoms, and R 4 is preferably an alkyl group having 1 to 3 carbon atoms.
　また、式（４）について、該当する反応性ケイ素基を有機重合体に導入することにより、例えばＷＯ２０１２／０３６１０９号公報に記載のような優れた伸び物性と速硬化性とを有する硬化性組成物を提供できることから、Ｒ３がメトキシメチル基であるのが好ましく、且つＲ４がメチル基であるのが好ましい。 Moreover, about formula (4), by introducing a corresponding reactive silicon group into an organic polymer, for example, a curable composition having excellent elongation properties and rapid curing properties as described in, for example, WO2012 / 036109. R 3 is preferably a methoxymethyl group, and R 4 is preferably a methyl group.
　式（４）で表されるアルコキシハロシラン（Ａ）の好適な具体例としては、メチルジメトキシクロロシラン（ＣｌＳｉ（ＣＨ３）（ＯＣＨ３）２）、メチルジエトキシクロロシラン（ＣｌＳｉ（ＣＨ３）（ＯＣ２Ｈ５）２）、エチルジメトキシクロロシラン（ＣｌＳｉ（Ｃ２Ｈ５）（ＯＣＨ３）２）、エチルジエトキシクロロシラン（ＣｌＳｉ（Ｃ２Ｈ５）（ＯＣ２Ｈ５）２）、ｎ－プロピルジメトキシクロロシラン（ＣｌＳｉ（ｎ－Ｃ３Ｈ７）（ＯＣＨ３）２）、ｎ－プロピルジエトキシクロロシラン（ＣｌＳｉ（ｎ－Ｃ３Ｈ７）（ＯＣ２Ｈ５）２）、ｎ－ヘキシルジメトキシクロロシラン（ＣｌＳｉ（ｎ－Ｃ６Ｈ１３）（ＯＣＨ３）２）、ｎ－ヘキシルジエトキシクロロシラン（ＣｌＳｉ（ｎ－Ｃ６Ｈ１３）（ＯＣ２Ｈ５）２）、フェニルジメトキシクロロシラン（ＣｌＳｉ（Ｐｈ）（ＯＣＨ３）２）、フェニルジエトキシクロロシラン（ＣｌＳｉ（Ｐｈ）（ＯＣ２Ｈ５）２）、クロロメチルジメトキシクロロシラン（ＣｌＳｉ（ＣＨ２Ｃｌ）（ＯＣＨ３）２）、クロロメチルジエトキシクロロシラン（ＣｌＳｉ（ＣＨ２Ｃｌ）（ＯＣ２Ｈ５）２）、クロロメチルメトキシメチルクロロシラン（ＣｌＳｉ（ＣＨ２Ｃｌ）（ＯＣＨ３）（ＣＨ３））、クロロメチルエトキシメチルクロロシラン（ＣｌＳｉ（ＣＨ２Ｃｌ）（ＯＣ２Ｈ５）（ＣＨ３））、ビス（クロロメチル）メトキシクロロシラン（ＣｌＳｉ（ＣＨ２Ｃｌ）２（ＯＣＨ３））、ビス（クロロメチル）エトキシクロロシラン（ＣｌＳｉ（ＣＨ２Ｃｌ）２（ＯＣ２Ｈ５））、１－クロロエチルジメトキシクロロシラン（ＣｌＳｉ（ＣＨＣｌＣＨ３）（ＯＣＨ３）２）、２－クロロエチルジメトキシクロロシラン（ＣｌＳｉ（ＣＨ２ＣＨ２Ｃｌ）（ＯＣＨ３）２）、１－クロロプロピルジメトキシクロロシラン（ＣｌＳｉ（ＣＨＣｌＣＨ２ＣＨ３）（ＯＣＨ３）２）、２－クロロプロピルジメトキシクロロシラン（ＣｌＳｉ（ＣＨ２ＣＨＣｌＣＨ３）（ＯＣＨ３）２）、３－クロロプロピルジメトキシクロロシラン（ＣｌＳｉ（ＣＨ２ＣＨ２ＣＨ２Ｃｌ）（ＯＣＨ３）２）、フルオロメチルジメトキシクロロシラン（ＣｌＳｉ（ＣＨ２Ｆ）（ＯＣＨ３）２）、ブロモメチルジメトキシクロロシラン（ＣｌＳｉ（ＣＨ２Ｂｒ）（ＯＣＨ３）２）、ヨードメチルジメトキシクロロシラン（ＣｌＳｉ（ＣＨ２Ｉ）（ＯＣＨ３）２）、メトキシメチルジメトキシクロロシラン（ＣｌＳｉ（ＣＨ２ＯＣＨ３）（ＯＣＨ３）２）、（ジメトキシメチル）ジメトキシクロロシラン（ＣｌＳｉ（ＣＨ（ＯＣＨ３）２）（ＯＣＨ３）２）、エトキシメチルジメトキシクロロシラン（ＣｌＳｉ（ＣＨ２ＯＣ２Ｈ５）（ＯＣＨ３）２）、エトキシメチルジエトキシクロロシラン（ＣｌＳｉ（ＣＨ２ＯＣ２Ｈ５）（ＯＣ２Ｈ５）２）、１－メトキシエチルジメトキシクロロシラン（ＣｌＳｉ（ＣＨ（ＯＣＨ３）ＣＨ３）（ＯＣＨ３）２）、トリメトキシメチルジメトキシクロロシラン（ＣｌＳｉ（Ｃ（ＯＣＨ３）３）（ＯＣＨ３）２）、（メトキシメチル）メチルメトキシクロロシラン（ＣｌＳｉ（ＣＨ２ＯＣＨ３）（ＣＨ３）（ＯＣＨ３））、ビス（メトキシメチル）メトキシクロロシラン（ＣｌＳｉ（ＣＨ２ＯＣＨ３）２（ＯＣＨ３））、及びメチルチオメチルジメトキシクロロシラン（ＣｌＳｉ（ＣＨ２ＳＣＨ３）（ＯＣＨ３）２）等が挙げられる。 Preferable specific examples of the alkoxyhalosilane (A) represented by the formula (4) include methyldimethoxychlorosilane (ClSi (CH 3 ) (OCH 3 ) 2 ), methyldiethoxychlorosilane (ClSi (CH 3 ) (OC) 2 H 5) 2), ethyl dimethoxy chlorosilane (ClSi (C 2 H 5) (OCH 3) 2), ethyl diethoxy chlorosilane (ClSi (C 2 H 5) (OC 2 H 5) 2), n- propyl dimethoxy Chlorosilane (ClSi (n—C 3 H 7 ) (OCH 3 ) 2 ), n-propyldiethoxychlorosilane (ClSi (n—C 3 H 7 ) (OC 2 H 5 ) 2 ), n-hexyldimethoxychlorosilane (ClSi) (NC 6 H 13 ) (OCH 3 ) 2 ), n-hexyldiethoxychlorosilane (ClSi (n- C 6 H 13) (OC 2 H 5) 2), phenyl dimethoxy chlorosilane (ClSi (Ph) (OCH 3 ) 2), phenyl diethoxy chlorosilane (ClSi (Ph) (OC 2 H 5) 2), chloromethyl dimethoxy chlorosilane (ClSi (CH 2 Cl) ( OCH 3) 2), chloromethyl diethoxy chlorosilane (ClSi (CH 2 Cl) ( OC 2 H 5) 2), chloromethyl methoxymethyl chlorosilane (ClSi (CH 2 Cl) ( OCH 3) (CH 3)), chloromethyl ethoxymethyl chlorosilane (ClSi (CH 2 Cl) ( OC 2 H 5) (CH 3)), bis (chloromethyl) methoxy chlorosilane (ClSi (CH 2 Cl) 2 (OCH 3 )), Bis (chloromethyl) ethoxychlorosilane (ClSi) CH 2 Cl) 2 (OC 2 H 5)), 1- chloroethyl dimethoxy chlorosilane (ClSi (CHClCH 3) (OCH 3) 2), 2- chloroethyl dimethoxy chlorosilane (ClSi (CH 2 CH 2 Cl ) (OCH 3 2 ), 1-chloropropyldimethoxychlorosilane (ClSi (CHClCH 2 CH 3 ) (OCH 3 ) 2 ), 2-chloropropyldimethoxychlorosilane (ClSi (CH 2 CHClCH 3 ) (OCH 3 ) 2 ), 3-chloropropyl Dimethoxychlorosilane (ClSi (CH 2 CH 2 CH 2 Cl) (OCH 3 ) 2 ), fluoromethyldimethoxychlorosilane (ClSi (CH 2 F) (OCH 3 ) 2 ), bromomethyldimethoxychlorosilane (ClSi (CH 2 Br) ( OCH 3 ) 2), iodomethyl dimethoxy chlorosilane (ClSi (CH 2 I) ( OCH 3) 2), methoxymethyl dimethoxy chlorosilane (ClSi (CH 2 OCH 3) (OCH 3) 2), ( dimethoxymethyl) dimethoxy chlorosilane (ClSi (CH (OCH 3 ) 2 ) (OCH 3 ) 2 ), ethoxymethyldimethoxychlorosilane (ClSi (CH 2 OC 2 H 5 ) (OCH 3 ) 2 ), ethoxymethyldiethoxychlorosilane (ClSi (CH 2 OC 2 H 5 ) ( OC 2 H 5 ) 2 ), 1-methoxyethyldimethoxychlorosilane (ClSi (CH (OCH 3 ) CH 3 ) (OCH 3 ) 2 ), trimethoxymethyldimethoxychlorosilane (ClSi (C (OCH 3 ) 3 ) (OCH 3 ) 2 ), (methoxymethyl) Tylmethoxychlorosilane (ClSi (CH 2 OCH 3 ) (CH 3 ) (OCH 3 )), bis (methoxymethyl) methoxychlorosilane (ClSi (CH 2 OCH 3 ) 2 (OCH 3 )), and methylthiomethyldimethoxychlorosilane (ClSi) (CH 2 SCH 3 ) (OCH 3 ) 2 ) and the like.
　以下に、具体的な実施例を挙げて本発明をより詳細に説明するが、本発明は、下記実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with specific examples, but the present invention is not limited to the following examples.
〔実施例１～５、及び比較例１〕
　前述のアルコキシシラン（Ｃ）（シラン（Ｃ））として、メトキシメチルトリメトキシシランを用いた。シラン（Ｃ）の量は、表１に記載される通りである。
　シラン（Ｃ）に対して、表１に記載の割合（モル％、対シラン（Ｃ）のモル数）で、金属塩（Ｆ）として塩化亜鉛（ＺｎＣｌ２）を加えた。シラン（Ｃ）と金属塩（Ｆ）との混合物中にハロゲン化剤（Ｅ）としての塩化アセチルを表１に記載の量、滴下した。
　滴下開始時の初期温度と、滴下開始から反応終了までの間の最高温度とを表１に記す。
　滴下終了後、滴下終了後の温度を保持して３０分間反応を行った。
　反応終了後の反応液の組成を分析し、ハロゲン化剤の消費率、並びにモノクロロ体（Ｃｌ１）、ジクロロ体（Ｃｌ２）、トリクロロ体（Ｃｌ３）、及び原料シラン（Ｃ）の生成比を求めた。これらの結果を表１に記す。 [Examples 1 to 5 and Comparative Example 1]
Methoxymethyltrimethoxysilane was used as the aforementioned alkoxysilane (C) (silane (C)). The amount of silane (C) is as described in Table 1.
Zinc chloride (ZnCl 2 ) was added as a metal salt (F) at a ratio shown in Table 1 (mol%, number of moles of silane (C)) with respect to silane (C). Acetyl chloride as the halogenating agent (E) was added dropwise to the mixture of silane (C) and metal salt (F) in the amount shown in Table 1.
Table 1 shows the initial temperature at the start of dropping and the maximum temperature from the start of dropping to the end of reaction.
After completion of dropping, the reaction was carried out for 30 minutes while maintaining the temperature after completion of dropping.
The composition of the reaction solution after the completion of the reaction was analyzed, the consumption rate of the halogenating agent, and the production ratio of monochloro isomer (Cl 1 ), dichloro isomer (Cl 2 ), trichloro isomer (Cl 3 ), and raw silane (C) Asked. These results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１から、所定の構造のシラン（Ｃ）を、－３０℃以上８０℃以下の温度で反応させることにより、モノハロゲン置換体である、所望する構造のアルコキシハロシランを高い選択性で製造できることが分かる。
　他方、比較例１からは、反応温度が－３０℃未満であると、シラン（Ｃ）のハロゲン化反応がほとんど進行しないことが分かる。
　また、実施例１～４と、実施例５との比較により、ルイス酸性を示す金属塩（Ｆ）の使用により、ハロゲン化剤（Ｅ）の利用効率を高められることが分かる。
　さらに、実施例１及び３と、実施例２、４、及び５との比較により、反応温度を２０℃以下に保つことで、ジクロロ体（Ｃｌ２）、トリクロロ体（Ｃｌ３）、の副生量が抑えられることが分かる。 From Table 1, by reacting silane (C) having a predetermined structure at a temperature of −30 ° C. or more and 80 ° C. or less, alkoxyhalosilane having a desired structure, which is a monohalogen substitution product, can be produced with high selectivity. I understand.
On the other hand, it can be seen from Comparative Example 1 that when the reaction temperature is lower than −30 ° C., the halogenation reaction of silane (C) hardly proceeds.
Further, comparison between Examples 1 to 4 and Example 5 shows that the use efficiency of the halogenating agent (E) can be increased by using the metal salt (F) exhibiting Lewis acidity.
Furthermore, by comparing Examples 1 and 3 with Examples 2, 4, and 5, by maintaining the reaction temperature at 20 ° C. or less, by-products of dichloro form (Cl 2 ) and trichloro form (Cl 3 ) are obtained. It can be seen that the amount is suppressed.
〔実施例６～実施例１３〕
　前述のアルコキシシラン（Ｃ）（シラン（Ｃ））として、表２に記載の種類のシラン化合物を用いた。シラン（Ｃ）の量は、表２に記載される通りである。
　シラン（Ｃ）に対して、表２に記載の割合（モル％、対シラン（Ｃ）のモル数）で、金属塩（Ｆ）として塩化亜鉛（ＺｎＣｌ２）を加えた。ただし、実施例１３では、金属塩（Ｆ）を用いなかった。
　シラン（Ｃ）と金属塩（Ｆ）との混合物中に表２に記載の種類及び量のハロゲン化剤（Ｅ）を、滴下した。
　滴下開始時の初期温度は５℃であり、滴下開始から反応終了までの間の最高温度は２０℃未満であった。
　滴下終了後、滴下終了後の温度を保持して３０分間反応を行った。
　反応終了後の反応液の組成を分析し、ハロゲン化剤の消費率、並びにモノハロ体（Ｘ１）、ジハロ体（Ｘ２）の生成比を求めた。これらの結果を表２に記す。
　また、生成物についての１Ｈ－ＮＭＲ（ＣＤＣｌ３）の測定結果を表３に記す。
　なお、１Ｈ－ＮＭＲの測定は、日本電子（株）製、ＪＮＭ－ＡＬ４００を用いて行った。 [Examples 6 to 13]
As the aforementioned alkoxysilane (C) (silane (C)), the types of silane compounds described in Table 2 were used. The amount of silane (C) is as described in Table 2.
Zinc chloride (ZnCl 2 ) was added as a metal salt (F) at a ratio shown in Table 2 (mol%, moles of silane (C)) with respect to silane (C). However, in Example 13, the metal salt (F) was not used.
In the mixture of silane (C) and metal salt (F), the types and amounts of halogenating agents (E) listed in Table 2 were added dropwise.
The initial temperature at the start of dropping was 5 ° C., and the maximum temperature from the start of dropping to the end of the reaction was less than 20 ° C.
After completion of dropping, the reaction was carried out for 30 minutes while maintaining the temperature after completion of dropping.
The composition of the reaction solution after completion of the reaction was analyzed to determine the consumption rate of the halogenating agent and the production ratio of the monohalo form (X 1 ) and dihalo form (X 2 ). These results are shown in Table 2.
The measurement results of 1 H-NMR (CDCl 3 ) of the product are shown in Table 3.
The 1 H-NMR measurement was performed using JNM-AL400 manufactured by JEOL Ltd.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２中の原料シラン（Ｃ）についての略称は以下の通りである。
ＭＭＴＭＳ：メトキシメチルトリメトキシシラン
ＭＴＥＳ：メチルトリエトキシシラン
ｎＰｒＴＭＳ：ｎ－プロピルトリメトキシシラン
ｎＨｅｘＴＭＳ：ｎ－ヘキシルトリメトキシシラン
ＰｈＴＭＳ：フェニルトリメトキシシラン
３－ＣｌＣ３ＴＭＳ：３－クロロプロピルトリメトキシシラン
　また、ハロゲン化剤（Ｅ）についての略称は以下の通りである。
ＡｃＣｌ：塩化アセチル
ＢｚＣｌ：塩化ベンゾイル
ＡｃＢｒ：臭化アセチル Abbreviations for the raw material silane (C) in Table 2 are as follows.
MMTMS: methoxymethyltrimethoxysilane MTES: methyltriethoxysilane nPrTMS: n-propyltrimethoxysilane nHexTMS: n-hexyltrimethoxysilane PhTMS: phenyltrimethoxysilane 3-ClC3TMS: 3-chloropropyltrimethoxysilane Abbreviations for the agent (E) are as follows.
AcCl: Acetyl chloride BzCl: Benzoyl chloride AcBr: Acetyl bromide
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
〔実施例１４〕
　アルコキシハロシラン（Ｂ）（ハロシラン（Ｂ））として、表４に記載の種類のシラン２６．８３ｍｍｏｌを用いた。水素化剤（Ｄ）であるＮａＢＨ４１．７３ｇ（４４．６７ｍｍｏｌ、ハロシラン（Ｂ）に対して１．６７当量）を、表４に記載の種類の溶剤（Ｓ）１４．７ｇに懸濁させた後、ハロシラン（Ｂ）を、水素化剤（Ｄ）の懸濁液に２０℃で３０分～９０分間かけて滴下した。滴下終了後、２０℃にて２時間反応を行った。
　反応後のアルコキシヒドロシラン（Ａ）（メトキシメチルジメトキシシラン）の収率を、１Ｈ－ＮＭＲ（ＣＤＣｌ３）より求めた。
　求められた収率を表４に記す。 Example 14
As the alkoxyhalosilane (B) (halosilane (B)), 26.83 mmol of the silanes described in Table 4 were used. 1.73 g (44.67 mmol, 1.67 equivalents based on halosilane (B)) of NaBH 4 as the hydrogenating agent (D) was suspended in 14.7 g of the solvent (S) of the type described in Table 4. Thereafter, the halosilane (B) was added dropwise to the suspension of the hydrogenating agent (D) at 20 ° C. over 30 to 90 minutes. After completion of dropping, the reaction was carried out at 20 ° C. for 2 hours.
The yield of alkoxyhydrosilane (A) (methoxymethyldimethoxysilane) after the reaction was determined from 1 H-NMR (CDCl 3 ).
The obtained yield is shown in Table 4.
〔実施例１５～１７、実施例１９、及び比較例３〕
　ハロシラン（Ｂ）を５．０ｍｍｏｌ、水素化剤（Ｄ）であるＮａＢＨ４を０．３１ｇ（８．３ｍｍｏｌ、ハロシラン（Ｂ）に対して１．６７当量）、溶剤（Ｓ）を２．５ｇ、それぞれ用いることの他は、実施例１４と同様に反応を行った。
　反応後のアルコキシヒドロシラン（Ａ）（メトキシメチルジメトキシシラン）の収率を、実施例１４と同様にして求めた。
　求められた収率を表４に記す。 [Examples 15 to 17, Example 19, and Comparative Example 3]
Halosilane (B) 5.0 mmol, hydrogenating agent (D) NaBH 4 0.31 g (8.3 mmol, 1.67 equivalents to halosilane (B)), solvent (S) 2.5 g, The reaction was performed in the same manner as in Example 14 except for using each.
The yield of alkoxyhydrosilane (A) (methoxymethyldimethoxysilane) after the reaction was determined in the same manner as in Example 14.
The obtained yield is shown in Table 4.
〔実施例１８、及び比較例４〕
　溶剤（Ｓ）を、表４に記載の溶剤に変えることと、ハロシラン（Ｂ）の滴下時間を１３時間に変えることと、ハロシラン（Ｂ）の滴下後の反応時間を６時間に変えることとの他は、実施例１４と同様に反応を行った。
　反応後のアルコキシヒドロシラン（Ａ）（メトキシメチルジメトキシシラン）の収率を、実施例１４と同様にして求めた。
　求められた収率を表４に記す。 Example 18 and Comparative Example 4
Changing the solvent (S) to the solvent shown in Table 4, changing the dropping time of the halosilane (B) to 13 hours, and changing the reaction time after the dropping of the halosilane (B) to 6 hours The others were reacted in the same manner as in Example 14.
The yield of alkoxyhydrosilane (A) (methoxymethyldimethoxysilane) after the reaction was determined in the same manner as in Example 14.
The obtained yield is shown in Table 4.
〔比較例２〕
　溶剤（Ｓ）を用いないことの他は、実施例１４と同様に反応を行った。
　反応後のメトキシメチルジメトキシシランの収率を、実施例１４と同様にして求めた。
　求められた収率を表４に記す。 [Comparative Example 2]
The reaction was conducted in the same manner as in Example 14 except that the solvent (S) was not used.
The yield of methoxymethyldimethoxysilane after the reaction was determined in the same manner as in Example 14.
The obtained yield is shown in Table 4.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表４中、ＭＭＤＭＣＳは、メトキシメチルジメトキシクロロシランを表し、ＭＭＤＭＢＳは、メトキシメチルジメトキシブロモシランを表す。 In Table 4, MMDMCS represents methoxymethyldimethoxychlorosilane, and MMDMBS represents methoxymethyldimethoxybromosilane.
　表４から、所定の構造のアルコキシハロシラン（Ｂ）を、エーテル結合を有する非プロトン性有機溶剤を５０質量％以上含む溶剤（Ｓ）中で水素化剤（Ｄ）と反応させることにより、所望する構造のアルコキシヒドロシラン（Ａ）が良好に生成することが分かる。 From Table 4, a desired structure is obtained by reacting an alkoxyhalosilane (B) having a predetermined structure with a hydrogenating agent (D) in a solvent (S) containing 50% by mass or more of an aprotic organic solvent having an ether bond. It can be seen that the alkoxyhydrosilane (A) having the structure as described above is favorably produced.
〔実施例１４、及び実施例２０～２４〕
　アルコキシハロシラン（Ｂ）(ハロシラン（Ｂ）)の種類及び使用量（ｍｍｏｌ）と、水素化剤（Ｄ）の使用量（当量）と、溶剤（Ｓ）の使用量（ｇ）と、反応時間とを、表５に記載されるように変更することの他は、実施例１４と同様にしてアルコキシヒドロシラン（Ａ）（ヒドロシラン（Ａ））を合成した。実施例１４と同様に測定したヒドロシラン（Ａ）の収率を表５に記す。
Figure JPOXMLDOC01-appb-T000005
 [Example 14 and Examples 20 to 24]
Type and amount of use of alkoxyhalosilane (B) (halosilane (B)) (mmol), amount of use of hydrogenating agent (D) (equivalent), amount of use of solvent (S) (g), and reaction time And alkoxyhydrosilane (A) (hydrosilane (A)) were synthesized in the same manner as in Example 14 except that they were changed as described in Table 5. The yield of hydrosilane (A) measured in the same manner as in Example 14 is shown in Table 5.
Figure JPOXMLDOC01-appb-T000005
　表５中の原料ハロシラン（Ｂ）についての略称は以下の通りである。
ＭＭＤＭＣＳ：メトキシメチルジメトキシクロロシラン
ＭＤＥＣＳ：メチルジエトキシクロロシラン
ｎＰｒＤＭＣＳ：ｎ－プロピルジメトキシクロロシラン
ＨｅｘＤＭＣＳ：ｎ－ヘキシルジメトキシクロロシラン
ＰｈＤＭＣＳ：フェニルジメトキシクロロシラン
３－ＣｌＣ３ＤＭＣＳ：３－クロロプロピルジメトキシクロロシラン Abbreviations for the raw material halosilane (B) in Table 5 are as follows.
MMDMCS: Methoxymethyldimethoxychlorosilane MDECS: Methyldiethoxychlorosilane nPrDMCS: n-propyldimethoxychlorosilane HexDMCS: n-hexyldimethoxychlorosilane PhDMCS: phenyldimethoxychlorosilane 3-ClC3DMCS: 3-chloropropyldimethoxychlorosilane
〔実施例２５〕
　メトキシメチルトリメトキシシランに対し、触媒として０．０１１モル％の塩化亜鉛を用い、５℃で０．９２モル当量の塩化アセチルの添加を開始した。反応系の温度が２０℃を超えないよう添加速度を調節しながら１．５時間かけて添加を終了させた。さらに０．５時間反応を行い、メトキシメチルジメトキシクロロシランを得た。
　精製したメトキシメチルジメトキシクロロシランに対して、１．６７モル当量のＮａＢＨ４及び質量で３倍量の１，２－ジメトキシエタンを反応容器に仕込んだ。反応容器の内容物を撹拌して懸濁させながら、２０℃でメトキシメチルジメトキシクロロシランを３０分かけて添加した。さらに２時間反応を行い、メトキシメチルジメトキシシランを得た。
　実施例２５の方法は、本発明内容に従った、メトキシメチルトリメトキシシランのモノクロロ化反応と、メトキシメチルジメトキシクロロシランのモノヒドロ化反応と、２つのみの工程を有する方法である。
　その結果、実施例２５では、メトキシメチルトリメトキシシランの使用量を基準とするメトキシメチルジメトキシシランの収率は６０％と、非常に高かった。 Example 25
With respect to methoxymethyltrimethoxysilane, 0.011 mol% of zinc chloride was used as a catalyst, and addition of 0.92 mol equivalent of acetyl chloride at 5 ° C. was started. The addition was completed over 1.5 hours while adjusting the addition rate so that the temperature of the reaction system did not exceed 20 ° C. The reaction was further continued for 0.5 hours to obtain methoxymethyldimethoxychlorosilane.
To the purified methoxymethyldimethoxychlorosilane, 1.67 molar equivalents of NaBH 4 and 3 times the mass of 1,2-dimethoxyethane were charged into the reaction vessel. While stirring and suspending the contents of the reaction vessel, methoxymethyldimethoxychlorosilane was added at 20 ° C. over 30 minutes. The reaction was further continued for 2 hours to obtain methoxymethyldimethoxysilane.
The method of Example 25 is a method having only two steps according to the present invention, the monochloroation reaction of methoxymethyltrimethoxysilane and the monohydrolysis reaction of methoxymethyldimethoxychlorosilane.
As a result, in Example 25, the yield of methoxymethyldimethoxysilane based on the amount of methoxymethyltrimethoxysilane used was as high as 60%.
〔比較例５〕
　メトキシメチルトリメトキシシランに対し、触媒として０．０２モル％量の塩化亜鉛を用い、４モル当量の塩化アセチルを作用させた。加熱還流条件下で３６時間反応を行い、メトキシメチルトリクロロシランを得た。
　蒸留により精製されたメトキシメチルトリクロロシランと、１モル当量のメチルジクロロシランを混合した後、０．０５モル当量の塩化メチルトリブチルアンモニウムの存在下に、加熱還流条件で３時間反応を行い、メトキシメチルジクロロシランを得た。
　精製したメトキシメチルジクロロシランに対して、２．５モル当量のオルト酢酸トリメチルを反応容器に仕込んだ。反応容器の内容物を撹拌しながら、反応容器の内温が５０℃を超えないように、メトキシメチルジクロロシランをゆっくりと添加することで、メトキシメチルジメトキシシランを得た。 [Comparative Example 5]
To methoxymethyltrimethoxysilane, 0.02 mol% of zinc chloride was used as a catalyst, and 4 molar equivalents of acetyl chloride were allowed to act. Reaction was performed for 36 hours under heating and refluxing conditions to obtain methoxymethyltrichlorosilane.
After mixing methoxymethyltrichlorosilane purified by distillation and 1 molar equivalent of methyldichlorosilane, the reaction is carried out in the presence of 0.05 molar equivalent of methyltributylammonium chloride under heating and refluxing conditions for 3 hours. Dichlorosilane was obtained.
To the purified methoxymethyldichlorosilane, 2.5 molar equivalents of trimethyl orthoacetate were charged into the reaction vessel. While stirring the contents of the reaction vessel, methoxymethyldimethoxysilane was obtained by slowly adding methoxymethyldichlorosilane so that the internal temperature of the reaction vessel did not exceed 50 ° C.
　比較例５の方法は、特許文献２に記載のメトキシメチルトリメトキシシランのトリクロロ化反応と、メトキシメチルトリクロロシランのモノヒドロ化反応と、メトキシメチルジクロロシランのジメトキシ化反応と、３つの工程を有する方法である。
　その結果、比較例５では、メトキシメチルトリメトキシシランの使用量を基準とするメトキシメチルジメトキシシランの収率は３０％と、低かった。 The method of Comparative Example 5 is a method having three steps: a trichlorination reaction of methoxymethyltrimethoxysilane, a monohydrolysis reaction of methoxymethyltrichlorosilane, and a dimethoxylation reaction of methoxymethyldichlorosilane described in Patent Document 2. It is.
As a result, in Comparative Example 5, the yield of methoxymethyldimethoxysilane based on the amount of methoxymethyltrimethoxysilane used was as low as 30%.

Claims (22)

  1. 　下記式（１）：
    Ｈ－ＳｉＲ１ ａ（ＯＲ２）３－ａ・・・（１）
    （式（１）中、Ｒ１、及びＲ２は、それぞれ独立に、置換基を有していてもよい炭素原子数１～２０の炭化水素基であり、ａは１又は２である。Ｒ１、ＯＲ２のそれぞれについて、それらが複数存在するとき、それらは同じでもよく、異なっていてもよい。）
    で表されるアルコキシヒドロシラン（Ａ）を製造するアルコキシヒドロシランの製造方法であって、
    　下記式（２）：
    Ｘ－ＳｉＲ１ ａ（ＯＲ２）３－ａ・・・（２）
    （式（２）中、Ｒ１、Ｒ２、及びａは、式（１）と同様であり、Ｘはハロゲン原子である。Ｒ１、ＯＲ２のそれぞれについて、それらが複数存在するとき、それらは同じでもよく、異なっていてもよい。）
    で表されるアルコキシハロシラン（Ｂ）を、エーテル結合を有する非プロトン性有機溶剤を５０質量％以上含む溶剤（Ｓ）中で、水素化剤（Ｄ）を用いて水素化することを含む、製造方法。     Following formula (1):
    H-SiR 1 a (OR 2 ) 3-a (1)
    (In Formula (1), R 1 and R 2 are each independently a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a is 1 or 2. R For each of 1 and OR 2 , when there are a plurality of them, they may be the same or different.)
    A process for producing an alkoxyhydrosilane (A) represented by:
    Following formula (2):
    X-SiR 1 a (OR 2 ) 3-a (2)
    (In Formula (2), R 1 , R 2 , and a are the same as in Formula (1), and X is a halogen atom. When there are a plurality of each of R 1 and OR 2 , May be the same or different.)
    Hydrogenating the alkoxyhalosilane (B) represented by the formula (B) with a hydrogenating agent (D) in a solvent (S) containing 50 mass% or more of an aprotic organic solvent having an ether bond, Production method.
  2. 　前記水素化剤（Ｄ）が、下記式（Ｄ１）：
    ＭＢＨ４・・・（Ｄ１）
    （式（Ｄ１）中、Ｍは、リチウム、ナトリウム、又はカリウムである。）
    で表される化合物である、請求項１に記載のアルコキシヒドロシランの製造方法。     The hydrogenating agent (D) is represented by the following formula (D1):
    MBH 4 ... (D1)
    (In the formula (D1), M is lithium, sodium, or potassium.)
    The manufacturing method of the alkoxy hydrosilane of Claim 1 which is a compound represented by these.
  3. 　前記Ｍがナトリウムである、請求項２に記載のアルコキシヒドロシランの製造方法。 The method for producing an alkoxyhydrosilane according to claim 2, wherein the M is sodium.
  4. 　前記Ｒ２がメチル基、又はエチル基である、請求項１～３のいずれか１項に記載のアルコキシヒドロシランの製造方法。 The method for producing an alkoxyhydrosilane according to any one of claims 1 to 3, wherein R 2 is a methyl group or an ethyl group.
  5. 　前記Ｒ２がメチル基である、請求項４に記載のアルコキシヒドロシランの製造方法。 The method for producing an alkoxyhydrosilane according to claim 4, wherein R 2 is a methyl group.
  6. 　前記非プロトン性有機溶剤が、テトラヒドロフラン、１，２－ジメトキシエタン、ジエチレングリコールジメチルエーテル、及びトリエチレングリコールジメチルエーテルからなる群より選択される１種以上を含む、請求項１～５のいずれか１項に記載のアルコキシヒドロシランの製造方法。 6. The aprotic organic solvent according to claim 1, wherein the aprotic organic solvent includes one or more selected from the group consisting of tetrahydrofuran, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether. A process for producing an alkoxyhydrosilane.
  7. 　前記非プロトン性有機溶剤が、１，２－ジメトキシエタンである、請求項６に記載のアルコキシヒドロシランの製造方法。 The method for producing an alkoxyhydrosilane according to claim 6, wherein the aprotic organic solvent is 1,2-dimethoxyethane.
  8. 　前記Ｒ１が、置換基を有していてもよい炭素原子数１～３の炭化水素基である、請求項１～７のいずれか１項に記載のアルコキシヒドロシランの製造方法。 The method for producing an alkoxyhydrosilane according to any one of claims 1 to 7, wherein R 1 is an optionally substituted hydrocarbon group having 1 to 3 carbon atoms.
  9. 　前記Ｒ１が、塩素原子で置換されているか、エーテル結合を含む、請求項１～８のいずれか１項に記載のアルコキシヒドロシランの製造方法。 The method for producing an alkoxyhydrosilane according to any one of claims 1 to 8, wherein R 1 is substituted with a chlorine atom or contains an ether bond.
  10. 　前記Ｒ１が、メトキシメチル基である、請求項９に記載のアルコキシヒドロシランの製造方法。 The method for producing an alkoxyhydrosilane according to claim 9, wherein R 1 is a methoxymethyl group.
  11. 　前記ａが１である、請求項１～１０のいずれか１項に記載のアルコキシヒドロシランの製造方法。 The method for producing an alkoxyhydrosilane according to any one of claims 1 to 10, wherein a is 1.
  12. 　下記式（２）：
    Ｘ－ＳｉＲ１ ａ（ＯＲ２）３－ａ・・・（２）
    （式（２）中、Ｒ１、及びＲ２は、それぞれ独立に、置換基を有していてもよい炭素原子数１～２０の炭化水素基であり、Ｘはハロゲン原子であり、ａは１又は２である。Ｒ１、ＯＲ２のそれぞれについて、それらが複数存在するとき、それらは同じでもよく、異なっていてもよい。）
    で表されるアルコキシハロシラン（Ｂ）を製造するアルコキシハロシランの製造方法であって、
    　下記式（３）：
    ＳｉＲ１ ａ（ＯＲ２）４－ａ・・・（３）
    （式（３）中、Ｒ１、及びＲ２、及びａは式（２）と同様である。Ｒ１、ＯＲ２のそれぞれについて、それらが複数存在するとき、それらは同じでもよく、異なっていてもよい。）
    で表されるアルコキシシラン（Ｃ）に、－３０℃以上１００℃以下の温度で、ハロゲン化剤（Ｅ）を反応させて前記アルコキシハロシラン（Ｂ）を生成させることを含み、
    　前記アルコキシシラン（Ｃ）１モルから前記アルコキシハロシラン（Ｂ）１モルを生成させる、化学量論的な前記ハロゲン化剤（Ｅ）の量を１モル当量とする場合に、前記ハロゲン化剤（Ｅ）の使用量が１．５モル当量以下である、製造方法。     Following formula (2):
    X-SiR 1 a (OR 2 ) 3-a (2)
    (In the formula (2), R 1 and R 2 are each independently a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, X is a halogen atom, and a is 1 or 2. For each of R 1 and OR 2 , when there are a plurality of them, they may be the same or different.
    A method for producing an alkoxyhalosilane for producing an alkoxyhalosilane (B) represented by:
    Following formula (3):
    SiR 1 a (OR 2 ) 4-a (3)
    (In formula (3), R 1 , R 2 , and a are the same as in formula (2). For each of R 1 and OR 2 , when there are a plurality of them, they may be the same or different. May be.)
    And reacting the halogenating agent (E) at a temperature of −30 ° C. or higher and 100 ° C. or lower to the alkoxysilane (C) represented by the formula:
    When the stoichiometric amount of the halogenating agent (E) for generating 1 mol of the alkoxyhalosilane (B) from 1 mol of the alkoxysilane (C) is 1 molar equivalent, the halogenating agent ( The manufacturing method whose usage-amount of E) is 1.5 molar equivalent or less.
  13. 　前記ハロゲン化剤（Ｅ）が、カルボン酸ハライドである、請求項１２に記載のアルコキシハロシランの製造方法。 The method for producing an alkoxyhalosilane according to claim 12, wherein the halogenating agent (E) is a carboxylic acid halide.
  14. 　前記Ｘが塩素原子であり、前記ハロゲン化剤（Ｅ）が、塩化アセチルである、請求項１３に記載のアルコキシハロシランの製造方法。 The method for producing an alkoxyhalosilane according to claim 13, wherein the X is a chlorine atom and the halogenating agent (E) is acetyl chloride.
  15. 　前記アルコキシシラン（Ｃ）に、－１０℃以上９０℃以下の温度で、前記ハロゲン化剤（Ｅ）を反応させる、請求項１２～１４のいずれか１項に記載のアルコキシハロシランの製造方法。 The method for producing an alkoxyhalosilane according to any one of claims 12 to 14, wherein the halogenating agent (E) is reacted with the alkoxysilane (C) at a temperature of -10 ° C or higher and 90 ° C or lower.
  16. 　前記アルコキシシラン（Ｃ）に、０℃以上２０℃以下の温度で、前記ハロゲン化剤（Ｅ）を反応させる、請求項１５に記載のアルコキシハロシランの製造方法。 The method for producing an alkoxyhalosilane according to claim 15, wherein the halogenating agent (E) is reacted with the alkoxysilane (C) at a temperature of 0 ° C or higher and 20 ° C or lower.
  17. 　前記アルコキシシラン（Ｃ）と、前記ハロゲン化剤（Ｅ）との反応をルイス酸性を示す金属塩（Ｆ）の存在下に行う、請求項１２～１６のいずれか１項に記載のアルコキシハロシランの製造方法。 The alkoxyhalosilane according to any one of claims 12 to 16, wherein the reaction between the alkoxysilane (C) and the halogenating agent (E) is carried out in the presence of a metal salt (F) exhibiting Lewis acidity. Manufacturing method.
  18. 　前記金属塩（Ｆ）が塩化亜鉛を含む、請求項１７に記載のアルコキシハロシランの製造方法。 The method for producing an alkoxyhalosilane according to claim 17, wherein the metal salt (F) contains zinc chloride.
  19. 　前記（Ｂ）アルコキシハロシランが、請求項１２～１８のいずれか１項に記載の方法により製造される、請求項１～１１のいずれか１項に記載のアルコキシヒドロシランの製造方法。 The method for producing an alkoxyhydrosilane according to any one of claims 1 to 11, wherein the (B) alkoxyhalosilane is produced by the method according to any one of claims 12 to 18.
  20. 　下記式（４）：
    Ｘ－ＳｉＲ３（ＯＲ４）２・・・（４）
    （式（４）中、Ｒ３は、炭素原子数１～２０のアルキル基であり、Ｒ３としての前記アルキル基はハロゲン原子又は炭素原子数１～６のアルコキシ基で置換されていてもよく、Ｒ４は、炭素原子数１～２０の炭化水素基であり、Ｘはハロゲン原子である。２つのＯＲ４について、それらは同じでもよく、異なっていてもよい。）
    で表されるアルコキシハロシラン化合物。     Following formula (4):
    X-SiR 3 (OR 4 ) 2 (4)
    (In Formula (4), R 3 is an alkyl group having 1 to 20 carbon atoms, and the alkyl group as R 3 may be substituted with a halogen atom or an alkoxy group having 1 to 6 carbon atoms. , R 4 is a hydrocarbon group having 1 to 20 carbon atoms, and X is a halogen atom, and for two OR 4 , they may be the same or different.
    The alkoxyhalosilane compound represented by these.
  21. 　前記Ｒ３が、炭素原子数１～３のアルコキシ基で置換された炭素原子数１～３のアルキル基であり、前記Ｒ４が炭素原子数１～３のアルキル基である、請求項２０に記載のアルコキシハロシラン化合物。 The R 3 is an alkyl group having 1 to 3 carbon atoms substituted with an alkoxy group having 1 to 3 carbon atoms, and the R 4 is an alkyl group having 1 to 3 carbon atoms. The alkoxyhalosilane compound described.
  22. 　前記Ｒ３がメトキシメチル基であり、前記Ｒ４がメチル基である、請求項２１に記載のアルコキシハロシラン化合物。 The alkoxyhalosilane compound according to claim 21, wherein R 3 is a methoxymethyl group, and R 4 is a methyl group.
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