JP7284719B2 - Method for producing 1,1,3,3-tetraalkoxydisiloxane-1,3-diol - Google Patents

Description

The present invention relates to a method for producing 1,1,3,3-tetraalkoxydisiloxane-1,3-diol compounds.

In recent years, supported metal complexes, in which metal complexes coordinated with trialkoxyhydroxysilanes or 1,1,3,3-tetraalkoxydisiloxane-1,3-diol compounds are supported on inorganic oxides, have been used as catalytically active components. A technique used in a homogeneous catalytic reaction system has been reported (Patent Document 1). These siloxane compounds are synthesized, for example, using tetrachlorosilane or hexachlorodisiloxane as a starting material, followed by an alkoxy group substitution reaction with an alcohol alkali metal salt or the like, followed by hydrolysis of residual chloro groups (Non-Patent Document 1). .

Non-Patent Document 1 describes a method for synthesizing 1,1,3,3-tetra-tert-butoxydisiloxane-1,3-diol. Hexachlorodisiloxane is reacted with 4 equivalents of potassium tert-butoxide, and the resulting tetraalkoxydichlorodisiloxane compound is hydrolyzed by a known method to synthesize in a short step. However, the starting material, hexachlorodisiloxane, is expensive, and there is no known method for selective mass synthesis from monomers such as tetrachlorosilane. Furthermore, in order to introduce a bulky substituent, it is necessary to raise the reaction temperature from 0 ° C. to the boiling point of the solvent. There is a problem that 1,3-diol compounds are not suitable for industrial production.

Patent No. 6090759

Appl. Org. Chem. 2003, 17, 52.

In order to industrially synthesize 1,1,3,3-tetraalkoxydisiloxane-1,3-diol with good yield, the above synthesis method is accompanied by difficulties. For example, hexachlorodisiloxane is expensive and very difficult to synthesize selectively with good yield from monomers such as tetrachlorosilane. Moreover, the dichlorodisiloxane compound isolated as an intermediate is not easy to handle because of its high reactivity. Thus, it is difficult to economically and industrially produce a sufficient amount in the synthesis examples hitherto.

The present invention has been made in view of the above circumstances, and provides a method for producing 1,1,3,3-tetraalkoxydisiloxane-1,3-diols in short steps selectively, efficiently and at low cost. With the goal.

（式中、Ｒは、それぞれ独立に炭素数３～１０の不飽和結合を含んでもよい炭化水素基である。） In order to solve the above problems, the present invention provides a method for producing 1,1,3,3-tetraalkoxydisiloxane-1,3-diol, comprising the following steps (a) and (b),
(a) dialkoxylation of trichlorosilane (1) in formula (I) below followed by dimerization to give 1,1,3,3-tetraalkoxydisiloxane (2); and (b) After halogenating the 1,1,3,3-tetraalkoxydisiloxane (2), 1,1,3,3-tetraalkoxydisiloxane-1,3 in the following formula (I) is obtained by basic hydrolysis. - obtaining the diol (3),
There is provided a method for producing 1,1,3,3-tetraalkoxydisiloxane-1,3-diol, characterized by going through

(Wherein, each R is independently a hydrocarbon group which may contain an unsaturated bond having 3 to 10 carbon atoms.)

With such a production method, 1,1,3,3-tetraalkoxydisiloxane-1,3-diol can be produced selectively, efficiently and at low cost in short steps.

At this time, the R in the formula (I) is preferably a tert-butoxy group.

With such a thing, the effect of this invention can be improved further.

According to the production method of the present invention, 1,1,3,3-tetraalkoxydisiloxane-1,3-diol useful as a ligand for metal complexes can be produced selectively, efficiently and at low cost in a short step. can do.
Therefore, the present invention makes it possible to economically and industrially produce a sufficient amount of 1,1,3,3-tetraalkoxydisiloxane-1,3-diol.
The metal complex having 1,1,3,3-tetraalkoxydisiloxane-1,3-diol as a ligand of the present invention can be easily converted into a silica-supported metal complex as a highly efficient heterogeneous catalyst, and can be used in various ways. It can be suitably used as a catalyst for organic chemical reactions.

As described above, there has been a demand for a method for producing 1,1,3,3-tetraalkoxydisiloxane-1,3-diol compounds at low cost.

As a result of intensive studies to solve the above problems, the present inventors have found that it is necessary to isolate unstable intermediates of chlorosilane compounds by selecting reagents and conditions that can be easily industrially realized. The inventors have found a method for producing a 1,1,3,3-tetraalkoxydisiloxane-1,3-diol compound at low cost and with high efficiency, and completed the present invention.

（式中、Ｒは、それぞれ独立に炭素数３～１０の不飽和結合を含んでもよい炭化水素基である。） That is, the present invention
A method for producing 1,1,3,3-tetraalkoxydisiloxane-1,3-diol including the following steps (a) and (b).
(a) dialkoxylation of trichlorosilane (1) in formula (I) below followed by dimerization to obtain 1,1,3,3-tetraalkoxydisiloxane (2);
(b) After halogenating the 1,1,3,3-tetraalkoxydisiloxane (2), 1,1,3,3-tetraalkoxydisiloxane- in the following formula (I) is obtained by basic hydrolysis. obtaining the 1,3-diol (3).

(Wherein, each R is independently a hydrocarbon group which may contain an unsaturated bond having 3 to 10 carbon atoms.)

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to these.

The present invention is characterized in that the following steps (a) and (b) are sequentially performed.

[Step (a)]
Step (a) is a step of dialkoxylating trichlorosilane (1), followed by dimerization to obtain 1,1,3,3-tetraalkoxydisiloxane (2).

（式中、Ｒは、上記と同じである。） According to one embodiment, in step (a), trichlorosilane (1) undergoes dialkoxylation reaction (a-1) and dimerization reaction (a-2) to form 1, A 1,3,3-tetraalkoxydisiloxane (2) can be obtained. At this time, it goes through dialkoxychlorosilane (4) as an intermediate.

(Wherein, R is the same as above.)

R is a hydrocarbon group which may contain an unsaturated bond having 3 to 10 carbon atoms, and may be a chain, branched or cyclic hydrocarbon group.
If the number of carbon atoms is less than 3, gelation tends to occur during the reaction, and if the number of carbon atoms exceeds 10, the reactivity may decrease.

Examples of R include n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and 1-propenyl groups. , allyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 5-hexenyl group, 1-heptenyl group, 9-decenyl group, 1,3-butandienyl group, 1,3- linear hydrocarbon groups such as pentadienyl group and 1,5-hexadienyl group, isopropyl group, 2-ethylpropyl group, tert-butyl group, sec-butyl group, isobutyl group, t-amyl group, neopentyl group, 1- methylbutyl group, 1-propylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-methylpentyl group, 1-ethylpentyl group, isopropenyl group, 1-methyl-1-propenyl group, 2-methyl-1- propenyl group, 1-methyl-1-butenyl group, 1,1-dimethyl-3-butenyl group, 1-ethyl-1-pentenyl group, 2,6-dimethyl-5-heptenyl group, 2,6-dimethyl-1 ,5-heptadienyl group, 2,6-dimethyl-1,6-heptadienyl group, 6-methyl-2-methylene-5-heptenyl group, 6-methyl-2-methylene-6-heptenyl group, 4-methyl-1 -branched hydrocarbon groups such as pentenyl-3-pentenyl group, cyclopropyl group, 2-methylcyclopropyl group, 2,2,3,3-tetramethylcyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentylmethyl group, 2-cyclopentylethyl group, cyclohexyl group, cyclohexylmethyl group, 2-cyclohexylethyl group, 3-cyclohexylpropyl group, 4-cyclohexylbutyl group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4 -methylcyclohexyl group, cycloheptyl group, norbornyl group, norbornylmethyl group, isobornyl group, menthyl group, fenkyl group, adamantyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 1-cyclohexenyl group, 1- methyl-2-cyclohexenyl group, 2-methyl-2,5-dicyclohexadienyl group, phenyl group, benzyl group, 1-phenylcyclopropyl group, 2-phenylcyclopropyl group, 1-phenylcyclopentyl group, 1- phenylethyl group, 2-phenylethyl group, 1-methyl-2-phenylethyl group, 1-phenylpropyl group, 2-phenylpropyl group, 3-phenylpropyl group, 4-phenylbutyl group, 1,2,3, 4-tetrahydro-2-naphthyl group, 2-phenylethenyl group, 3-phenyl-2-propenyl group, 1-methyl-3-phenylethenyl group, p-tolyl group, m-tolyl group, o-tolyl group , 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-tert-butylphenyl group, 1-naphthyl group, cyclic hydrocarbon groups such as 2-naphthyl group, etc. tert-butyl group is particularly preferred.

The dialkoxylation reaction (a-1) is carried out by stirring trichlorosilane (1) in the presence of a base with an alcohol (ROH) having a corresponding R in a solvent.

Bases used in the dialkoxylation reaction step include, for example, lithium hydroxide, lithium carbonate, lithium hydrogen carbonate, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium borohydride, potassium hydride, potassium hydroxide, carbonate Alkali metal salts such as potassium, potassium hydrogen carbonate and dipotassium hydrogen phosphate, or alkaline earth metals such as magnesium hydroxide, magnesium carbonate, calcium hydroxide, calcium carbonate, strontium hydroxide, strontium carbonate, barium hydroxide and barium carbonate metal salts, or amines such as pyridine, triethylamine, ethyldiisopropylamine, diazabicycloundecene, and the like; Among them, trichlorosilane is likely to disproportionate under strong basic conditions and may produce flammable monosilane as a by-product. Pyridine is particularly preferred from the viewpoint of stability. The amount of the base to be used is preferably 1.5 mol or more, more preferably 2 mol to 2.5 mol, per 1 mol of trichlorosilane.

The amount of alcohol used can be arbitrarily determined in consideration of various conditions, but since there are three chloro groups that can be substituted, it is preferably 1.5 mol to 3 mol per 1 mol of trichlorosilane (1). , more preferably 2 mol to 2.5 mol in order to suppress side reactions. From the viewpoint of yield, it is preferable to use 2 mol or more.

Preferred solvents used in the dialkoxylation reaction (a-1) include hydrocarbons such as hexane, heptane, benzene, toluene, xylene and cumene, diethyl ether, di-n-butyl ether, tert-butyl methyl ether and cyclopentylmethyl. Ethers such as ether, tetrahydrofuran and 1,4-dioxane, chlorine solvents such as dichloromethane, chloroform, tetrachloromethane, 1,2-dichloroethane and 1,1,2-trichloroethane, N,N-dimethylformamide (DMF ), N,N-dimethylacetamide (DMA), N,N-dimethylpropionamide, 1,3-dimethyl-2-imidazolidinone (DMI), dimethylsulfoxide (DMSO), hexamethylphosphoric triamide (HMPA) and other aprotic polar solvents, which are used singly or in combination. The amount of the solvent used is not particularly limited, but it is preferably 10 to 100,000 parts, more preferably 100 to 10,000 parts, still more preferably 500 parts, per 100 parts of trichlorosilane (1). 5,000 copies from

The reaction temperature can be arbitrarily set depending on the selected solvent, but is preferably -78°C to the boiling point of the solvent, more preferably -20°C to 25°C. The reaction time can be set arbitrarily, and may be optimized by tracking the progress of the reaction by gas chromatography (GC) or thin layer chromatography (TLC), usually preferably from 30 minutes to 12 hours.

The dimerization reaction (a-2) is carried out by adding a base and water to the dialkoxychlorosilane (4) obtained by the alkoxylation reaction (a-1) and stirring. The dimerization reaction (a-2) may be a one-pot synthesis performed in the same reaction vessel after the alkoxylation reaction (a-1) without isolating the product.

Bases used in the dimerization reaction (a-2) include, for example, lithium hydroxide, lithium carbonate, lithium hydrogen carbonate, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium borohydride, potassium hydride, water Alkali metal salts such as potassium oxide, potassium carbonate, potassium hydrogen carbonate, dipotassium hydrogen phosphate, or magnesium hydroxide, magnesium carbonate, calcium hydroxide, calcium carbonate, strontium hydroxide, strontium carbonate, barium hydroxide, barium carbonate, etc. or alkaline earth metal salts, or amines such as pyridine, triethylamine, ethyldiisopropylamine, and diazabicycloundecene. Among them, pyridine is preferable in terms of availability, handleability, reactivity and stability of the compound in the reaction system. The amount of the base to be added is preferably 1 mol or more, more preferably 1 mol to 5 mol, per 1 mol of trichlorosilane.

The amount of water added is preferably 100 to 10,000 parts, more preferably 300 to 1,000 parts, per 100 parts of dialkoxychlorosilane (4).

Although the reaction temperature can be set arbitrarily, it is preferably -78°C to the boiling point of the solvent, more preferably -20°C to 25°C. The reaction time can be set arbitrarily, but usually 30 minutes to 4 hours is preferred.

The 1,1,3,3-tetraalkoxydisiloxane obtained by the above reaction may be purified by appropriately selecting from purification methods in ordinary organic synthesis such as distillation, various chromatography, and recrystallization. Distillation is particularly preferred from the viewpoint of industrial economy.

（式中、Ｘはハロゲン原子であり、Ｒは、上記と同じである。） [Step (b)]
According to one embodiment, in step (b), the 1,1,3,3-tetraalkoxydisiloxane (2) undergoes a halogenation reaction (b-1) and a hydrolysis reaction (b-1), as shown by the following formula. It can be converted to 1,1,3,3-tetraalkoxydisiloxane-1,3-diol (3) by b-2). At this time, 1,1,3,3-tetraalkoxy-1,3-dihalodisiloxane (5) is passed through as an intermediate.

(Wherein, X is a halogen atom and R is the same as above.)

The halogen atom for X in the formulas (b-1) and (b-2) is preferably a chlorine atom, a bromine atom or an iodine atom.

Halogenation reaction (b-1) is carried out by adding a halogenating agent to 1,1,3,3-tetraalkoxydisiloxane (2) and stirring in a solvent.

Halogenating agents include, for example, trichloroisocyanuric acid, N-chlorosuccinimide, 1,3-dichloro-5,5-dimethylhydantoin, tribromoisocyanuric acid, N-bromosuccinimide, 1,3-dibromo-5,5-dimethyl At least one can be selected from the group consisting of hydantoin, triiodoisocyanuric acid, N-iodosuccinimide, 1,3-diiodo-5,5-dimethylhydantoin, and the like. Trichloroisocyanuric acid is preferred in terms of cost, ease of handling, reactivity, and ease of removal after the reaction.
The amount of the halogenating agent to be used can be arbitrarily determined in consideration of various conditions and the structure of the halogenating agent. mol to 10 mol, more preferably 1.1 mol to 3 mol.

Preferred solvents used in the halogenation reaction (b-1) include ethers such as diethyl ether, di-n-butyl ether, tert-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran and 1,4-dioxane, dichloromethane, chloroform, It can be selected from the group consisting of chlorinated solvents such as tetrachloromethane, 1,2-dichloroethane and 1,1,2-trichloroethane, acetone, ethyl acetate, isopropyl acetate, acetonitrile and toluene, and these can be used singly or in combination. used. Preferred are tert-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dichloromethane, acetone and ethyl acetate, and more preferred are tert-butyl methyl ether, cyclopentyl methyl ether and tetrahydrofuran. More preferred are tert-butyl methyl ether and cyclopentyl methyl ether. The amount of the solvent used is not particularly limited, but it is preferably 10 parts to 100,000 parts, more preferably 100 parts to 10,000 parts per 100 parts of 1,1,3,3-tetraalkoxydisiloxane (2). 000 parts, more preferably 500 to 5,000 parts.

The reaction temperature can be arbitrarily set depending on the selected solvent, but is preferably -40°C to the boiling point of the solvent, more preferably -20°C to 50°C. The reaction time may be optimized by tracking the progress of the reaction by gas chromatography (GC) or thin layer chromatography (TLC), but usually 30 minutes to 12 hours is preferred.

In the hydrolysis reaction (b-2), a base and water are added to the 1,1,3,3-tetraalkoxy-1,3-dihalodisiloxane (5) obtained by the halogenation reaction (b-1). This is done by agitating. The hydrolysis reaction (b-2) may be a one-pot synthesis performed in the same reaction vessel after the halogenation reaction (b-1) without isolating the product.

Bases used for hydrolysis include, for example, lithium hydroxide, lithium carbonate, lithium hydrogen carbonate, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium borohydride, potassium hydride, potassium hydroxide, potassium carbonate, hydrogen carbonate. alkali metal salts such as potassium and dipotassium hydrogen phosphate, or alkaline earth metal salts such as magnesium hydroxide, magnesium carbonate, calcium hydroxide, calcium carbonate, strontium hydroxide, strontium carbonate, barium hydroxide and barium carbonate, or Amines such as pyridine, triethylamine, ethyldiisopropylamine, and diazabicycloundecene are included. Among them, preferred are sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine, and more preferred are pyridine and triethylamine, in terms of availability, handling, reactivity and stability of the compound in the reaction system. The amount of the base to be added is preferably 2 mol or more, more preferably 3 mol to 10 mol, per 1 mol of dihalodisiloxane.

The amount of water added is preferably 0.1 part to 1,000 parts, more preferably 100 parts of 1,1,3,3-tetraalkoxy-1,3-dihalodisiloxane (5). 10 to 100 parts.

Although the reaction temperature can be set arbitrarily, it is preferably -78°C to the boiling point of the solvent, more preferably -20°C to 25°C. Although the reaction time can be set arbitrarily, it is usually preferably from 30 minutes to 6 hours.

The 1,1,3,3-tetraalkoxydisiloxane-1,3-diol obtained by the above reaction may be purified by appropriately selecting from purification methods in ordinary organic synthesis such as various chromatography and recrystallization. good. Recrystallization is particularly preferred from the viewpoint of industrial economy.

As described above, a simple and efficient 1,1,3,3-tetraalkoxydisiloxane-1 such as 1,1,3,3-tetra-tert-butoxydisiloxane-1,3-diol is prepared. , 3-diols are provided. In particular, it is possible to produce a high-yield, high-purity product in one pot without the need to isolate unstable intermediates such as halides, and the industrial economy is excellent.

The metal complex containing the silicone compound of the present invention as a ligand can be suitably used as a catalyst for various organic synthesis reactions such as hydrosilylation reaction and hydrogen reduction.

EXAMPLES The present invention will be specifically described below using Examples and Comparative Examples, but the present invention is not limited to these.

In the examples below, ^t Bu represents a tert-butyl group. The molecular structure was determined by nuclear magnetic resonance spectroscopy ( ¹ H-NMR) using AVANCE III (Bruker Biospin Co.).

[Example 1]
Step (a): Synthesis of 1,1,3,3-tetra-tert-butoxydisiloxane (2a) Under a nitrogen atmosphere, 27.1 g of trichlorosilane, 160.0 g of toluene was added, and 32.4 g of pyridine was added dropwise with stirring while maintaining the internal temperature at 20°C or lower. After stirring the reaction mixture at 25° C. for 1 hour, 31.6 g of tert-butyl alcohol was added dropwise while maintaining the internal temperature at 20° C. or less. After the reaction mixture was stirred at 25°C for 1 hour, 15.8 g of pyridine was added while keeping the internal temperature below 20°C. 20.0 g of water was added dropwise, and the mixture was stirred at 25° C. for 1 hour, filtered, water was added to the filtrate, and the desired product was extracted with toluene. The separated organic layer was washed with a saturated aqueous solution of sodium bicarbonate, dried over sodium sulfate, and filtered. Volatile components were removed from the filtrate under reduced pressure (140°C, 1 kPa). 20.88 g of product are obtained. The product was identified by ¹ H-NMR measurement and found to be a compound represented by the following formula (2a). Yield was 57.0%. ¹ H-NMR (400 MHz, CDCl ₃ ): δ 1.34 (s, 36H), 4.48 (s, 2H)

Step (b): Synthesis of 1,1,3,3-tetra-tert-butoxydisiloxane-1,3-diol (3a) 36.7 g of 1,1,3,3-tetra-tert-butoxydisiloxane (2a) obtained in step (a) and 200 mL of tert-butyl methyl ether were added, stirred at 25° C., and trichloroisocyanuric acid was added thereto. 25.6 g was added. After stirring at 25° C. for 12 hours, a mixture of 50.6 g of triethylamine and 100 mL of water was added dropwise while cooling with ice. After the reaction mixture was stirred at 25° C. for 1 hour, the organic layer was separated. The organic layer was washed with 1N hydrochloric acid and saturated brine, dried over sodium sulfate, filtered, and the filtrate was concentrated to obtain a white solid crude product. Recrystallization from a mixed solvent of methylene chloride and pentane gave 37.9 g of a white solid product at 25°C. The product was identified by ¹ H-NMR measurement and found to be compound (3a) represented by the following formula. Yield was 95.0%. ¹ H-NMR (400 MHz, CDCl ₃ ): δ 1.35 (s, 36H), 2.68-2.86 (br, 2H)

[Comparative Example 1]
In a nitrogen atmosphere, 27.1 g of trichlorosilane and 160.0 g of toluene were added to a flask equipped with a thermometer, a dropping funnel, and a nitrogen inlet tube. was added dropwise with stirring. After the reaction mixture was stirred at 25°C for 1 hour, it was ice-cooled again, and 18.4 g of ethanol was added dropwise while maintaining the internal temperature at 20°C or lower. The reaction mixture was again warmed to room temperature and stirred for 1 hour, then 15.8 g of pyridine was added while maintaining the internal temperature below 20°C. 20.0 g of water was added dropwise, and the reaction solution gelled while stirring at 25°C.

Although 1,1,3,3-tetraalkoxydisiloxane-1,3-diol was obtained from Example 1 above, in Comparative Example 1 above, the reaction solution gelled and 1,1,3,3-tetra No alkoxydisiloxane-1,3-diol was obtained.

Thus, according to the present invention, 1,1,3,3-tetraalkoxydisiloxane-1,3-diol can be produced selectively, efficiently and at low cost in short steps.

In addition, this invention is not limited to the said embodiment. The above-described embodiment is an example, and any device having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect is the present invention. included in the technical scope of

Claims (2)

A method for producing 1,1,3,3-tetraalkoxydisiloxane-1,3-diol, comprising the following steps (a) and (b),
(a) dialkoxylation of trichlorosilane (1) in formula (I) below followed by dimerization to obtain 1,1,3,3-tetraalkoxydisiloxane (2);
(b) After halogenating the 1,1,3,3-tetraalkoxydisiloxane (2), 1,1,3,3-tetraalkoxydisiloxane- in the following formula (I) is obtained by basic hydrolysis. obtaining the 1,3-diol (3),
A method for producing 1,1,3,3-tetraalkoxydisiloxane-1,3-diol, characterized by going through

(Wherein, each R is independently a hydrocarbon group which may contain an unsaturated bond having 3 to 10 carbon atoms.) 2. The method for producing 1,1,3,3-tetraalkoxydisiloxane-1,3-diol according to claim 1, wherein said R in said formula (I) is a tert- butyl group.