JP2024059323A - Method for producing oxadisilacyclopentane compound - Google Patents

Abstract

To provide a method for enabling efficient high-yield production of an oxadisilacyclopentane compound.SOLUTION: A method for producing an oxadisilacyclopentane compound represented by the general formula (4) comprises reacting a bisilylethane compound having an acyloxy group represented by the general formula (1) with an amine compound such as allylamine. (In the formulas, R1 to R4 each independently represent an unsubstituted C1-4 monovalent hydrocarbon group; and R5 represents H, or a substituted or unsubstituted C1-20 monovalent hydrocarbon group.)SELECTED DRAWING: None

Description

The present invention relates to a method for producing an oxadisilacyclopentane compound.

Oxadisilacyclopentane compounds are useful as raw materials for heat-resistant materials, electronic materials, optical materials, cosmetics, etc.

As a method for producing an oxadisilacyclopentane compound, for example, a method of reacting 1,2-bis(chlorodimethylsilyl)ethane, obtained by the hydrosilylation reaction of chlorodimethylvinylsilane and chlorodimethylsilane, with water and thermally decomposing the resulting polymer compound (see Patent Document 1), a method of reacting 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane with magnesium (see Non-Patent Document 1), and a method of reacting bis(2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentyl)tin, synthesized from 2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane and tin(II) chloride, with carbon dioxide to obtain the compound as a by-product in the synthesis of a polynuclear tin complex (see Non-Patent Document 2), etc. have been proposed.

Japanese Patent Application Laid-Open No. 5-25182

Pet. Chem. 56,798, 2016 Inorg. Chem. 49, 11133, 2010

In the method of Patent Document 1, it is believed that 2,2,5,5-tetramethyl-1-oxa-2,5-disilacyclopentane is produced by the reaction of 1,2-bis(chlorodimethylsilyl)ethane with water. However, the water used and the hydrogen chloride produced by this reaction act as catalysts to promote a ring-opening reaction of the above product, which quickly produces a polymer compound, and the target 2,2,5,5-tetramethyl-1-oxa-2,5-disilacyclopentane is hardly obtained by this reaction. In order to obtain 2,2,5,5-tetramethyl-1-oxa-2,5-disilacyclopentane from this polymer compound, a thermal decomposition reaction is further required as a second-stage reaction, which increases the number of steps and is therefore not industrially advantageous.
Furthermore, in order to obtain the target oxadisilacyclopentane compound by the above-mentioned pyrolysis, the pyrolysis reaction must be carried out at a temperature of at least 200° C., and in order to obtain the target compound at a practical reaction rate, a temperature of 300° C. or higher is required. Since a large amount of energy is required for the production, this is not industrially advantageous.

Moreover, in the method of Non-Patent Document 1, the reaction must be carried out while adding magnesium from time to time in order to suppress side reactions, which makes the operation complicated and not industrially advantageous.
Furthermore, the method of Non-Patent Document 2 not only requires two-step reactions to obtain the target oxadisilacyclopentane compound, but also has a low yield and requires the use of a highly toxic tin compound, making it industrially unadvantageous.

The present invention has been made in consideration of the above circumstances, and aims to provide a method for producing oxadisilacyclopentane compounds efficiently and with high yield.

As a result of intensive research conducted by the present inventors to achieve the above object, they discovered that an oxadisilacyclopentane compound can be obtained without the need for complicated operations by reacting a bissilylethane compound having an acyloxy group with an amine compound, and that because this method does not use water, the reaction to produce a polymer compound due to the ring-opening reaction of the oxadisilacyclopentane compound in the reaction system is suppressed, and the oxadisilacyclopentane compound can be obtained in good yield without the need for a high-temperature reaction, thus completing the present invention.

（式中、Ｒ¹～Ｒ⁴は、それぞれ独立して、非置換の炭素数１～４の１価炭化水素基を表し、Ｒ⁵は、水素原子または置換もしくは非置換の炭素数１～２０の１価炭化水素基を表す。）
で示されるアシロキシ基を有するビスシリルエタン化合物と、下記一般式（２）

［式中、Ｒ⁶は、水素原子、置換もしくは非置換の炭素数１～２０の１価炭化水素基または下記一般式（３）で示される基を表す。

（式中、ｍは、０～５の整数を表し、ｎは、１～５の整数を表し、破線は、結合手を表す。）]
で示されるアミン化合物とを反応させる、下記一般式（４）

（式中、Ｒ¹～Ｒ⁴は、前記と同じ意味を表す。）
で示されるオキサジシラシクロペンタン化合物の製造方法、
２． 反応温度が、０～１００℃である１のオキサジシラシクロペンタン化合物の製造方法
を提供する。 That is, the present invention provides
1. The following general formula (1)

(In the formula, R ¹ to R ⁴ each independently represent an unsubstituted monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ⁵ represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.)
and a bissilylethane compound having an acyloxy group represented by the following general formula (2):

In the formula, R ⁶ represents a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or a group represented by the following general formula (3):

(In the formula, m represents an integer of 0 to 5, n represents an integer of 1 to 5, and the dashed line represents a bond.)
and reacting an amine compound represented by the following general formula (4):

(In the formula, R ¹ to R ⁴ have the same meanings as above.)
A method for producing an oxadisilacyclopentane compound represented by the formula:
2. The present invention provides a method for producing the oxadisilacyclopentane compound of 1, in which the reaction temperature is 0 to 100° C.

According to the present invention, oxadisilacyclopentane compounds can be produced efficiently and with high yield without producing polymeric compounds or requiring complicated operations.

The present invention will be specifically described below.
The method for producing an oxadisilacyclopentane compound of the present invention comprises reacting a bissilylethane compound having an acyloxy group represented by the following general formula (1) (hereinafter referred to as "compound (1)") with an amine compound represented by the following general formula (2) (hereinafter referred to as "compound (2)").

In formula (1), R ¹ to R ⁴ each independently represent an unsubstituted monovalent hydrocarbon group having 1 to 4 carbon atoms.
Here, the monovalent hydrocarbon groups of R ¹ to R ⁴ may be linear, branched or cyclic, and examples of such groups include alkyl and alkenyl groups.
Specific examples thereof include linear alkyl groups such as methyl, ethyl, n-propyl, and n-butyl groups; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl groups; cyclic alkyl groups such as cyclopropyl and cyclobutyl groups; and alkenyl groups such as vinyl, allyl, 1-propenyl, isopropenyl, and 1-butenyl groups.
Among these, alkyl groups having 1 to 3 carbon atoms are preferred, with methyl and ethyl groups being more preferred.

In general formula (1), R ⁵ represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.

Here, the monovalent hydrocarbon group for ^R5 may be linear, branched, or cyclic, and examples thereof include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms; an alkenyl group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 2 to 6 carbon atoms; an aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms; and an aralkyl group having 7 to 20 carbon atoms, preferably 7 to 10 carbon atoms.
Specific examples thereof include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, and n-icosyl groups; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, thexyl, and 2-ethylhexyl groups; cyclic alkyl groups such as cyclopentyl and cyclohexyl groups; alkenyl groups such as vinyl, allyl, 1-butenyl, and 1-pentenyl groups; aryl groups such as phenyl and tolyl groups; and aralkyl groups such as benzyl groups.
In addition, some or all of the hydrogen atoms of these monovalent hydrocarbon groups may be substituted, and specific examples of the substituents include alkoxy groups such as methoxy, ethoxy, (n- or iso)propoxy groups; halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms; cyano groups; amino groups; and acyl groups having 2 to 10 carbon atoms.
Among these, from the viewpoints of availability of raw materials and usefulness of the product, preferred monovalent hydrocarbon groups for ^R5 are alkyl groups having 1 to 3 carbon atoms, such as methyl, ethyl, n-propyl, and isopropyl groups; alkenyl groups having 3 to 5 carbon atoms, such as allyl, 1-butenyl, and 1-pentenyl groups; and aryl groups having 6 to 8 carbon atoms, such as phenyl groups.

Specific examples of compound (1) include 1,2-bis(acetoxydimethylsilyl)ethane, 1,2-bis(propionyloxydimethylsilyl)ethane, 1,2-bis(butyryloxydimethylsilyl)ethane, 1,2-bis(isobutyryloxydimethylsilyl)ethane, 1,2-bis(stearoyloxydimethylsilyl)ethane, 1,2-bis(benzoyloxydimethylsilyl)ethane, 1,2-bis(acryloyloxydimethylsilyl)ethane, 1,2-bis(methacryloyloxydimethylsilyl)ethane, 1,2-bis(acetoxydiethylsilyl)ethane, 1,2-bis(propionyloxydiethylsilyl)ethane, 1 ,2-bis(butyryloxydiethylsilyl)ethane, 1,2-bis(isobutyryloxydiethylsilyl)ethane, 1,2-bis(stearoyloxydimethylsilyl)ethane, 1,2-bis(benzoyloxydiethylsilyl)ethane, 1,2-bis(acryloyloxydiethylsilyl)ethane, 1,2-bis(methacryloyloxydiethylsilyl)ethane, 1,2-bis(acetoxydipropylsilyl)ethane, 1,2-bis(propionyloxydipropylsilyl)ethane, 1,2-bis(butyryloxydipropylsilyl)ethane, 1,2-bis(isobutyryloxydipropyl ... 1,2-bis(benzoyloxydipropylsilyl)ethane, 1,2-bis(acryloyloxydipropylsilyl)ethane, 1,2-bis(methacryloyloxydipropylsilyl)ethane, 1,2-bis(acetoxydiisopropylsilyl)ethane, 1,2-bis(propionyloxydiisopropylsilyl)ethane, 1,2-bis(butyryloxydiisopropylsilyl)ethane, 1,2-bis(isobutyryloxydiisopropylsilyl)ethane, 1,2-bis(stearoyloxydiisopropylsilyl)ethane, 1,2-bis(benzoyloxydiisopropylsilyl)ethane, 1, Examples include 2-bis(acryloyloxydiisopropylsilyl)ethane, 1,2-bis(methacryloyloxydiisopropylsilyl)ethane, 1,2-bis(acetoxydibutylsilyl)ethane, 1,2-bis(propionyloxydibutylsilyl)ethane, 1,2-bis(butyryloxydibutylsilyl)ethane, 1,2-bis(isobutyryloxydibutylsilyl)ethane, 1,2-bis(stearoyloxydibutylsilyl)ethane, 1,2-bis(benzoyloxydibutylsilyl)ethane, 1,2-bis(acryloyloxydibutylsilyl)ethane, and 1,2-bis(methacryloyloxydibutylsilyl)ethane.

Among these, 1,2-bis(acetoxydimethylsilyl)ethane and 1,2-bis(propionyloxydimethylsilyl)ethane are preferred from the viewpoints of availability of raw materials and usefulness of the product.
These compounds may be commercially available or may be produced. When produced, they may be obtained according to a known method, for example, by a method of subjecting a carboxylic acid compound and a 1,2-bis(chlorosilyl)ethane compound to a dehydrochlorination reaction. When produced, the reaction product may be used as it is, or may be used after purification such as distillation.

In formula (2), R ⁶ represents a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or a group represented by the following formula (3).

Here, the monovalent hydrocarbon group of ^R6 may be linear, branched or cyclic, and examples thereof include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms; an alkenyl group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 2 to 6 carbon atoms; an aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms; and an aralkyl group having 7 to 20 carbon atoms, preferably 7 to 10 carbon atoms.
Specific examples thereof include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, and n-icosyl groups; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, thexyl, and 2-ethylhexyl groups; cyclic alkyl groups such as cyclopentyl and cyclohexyl groups; alkenyl groups such as vinyl, allyl, 1-butenyl, and 1-pentenyl groups; aryl groups such as phenyl and tolyl groups; and aralkyl groups such as benzyl groups.
In addition, some or all of the hydrogen atoms of these monovalent hydrocarbon groups may be substituted, and specific examples of the substituents include alkoxy groups such as methoxy, ethoxy, (n- or iso)propoxy groups; halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms; cyano groups; amino groups; and acyl groups having 2 to 10 carbon atoms.
Among these, from the viewpoints of availability of raw materials and usefulness of the product, preferred monovalent hydrocarbon groups for ^R6 are alkyl groups having 1 to 3 carbon atoms, such as methyl, ethyl, n-propyl, and isopropyl groups; alkenyl groups having 3 to 5 carbon atoms, such as allyl, 1-butenyl, and 1-pentenyl groups; and aryl groups having 6 to 8 carbon atoms, such as phenyl groups.

In formula (3), m is an integer of 0 to 5, preferably an integer of 0, 1 or 2, and more preferably an integer of 0 or 1.
In formula (3), n is an integer of 1 to 5, preferably an integer of 1, 2, 3 or 4, and more preferably an integer of 2 or 3.
A preferred combination of m and n is when m is an integer of 0 or 1, and n is an integer of 2 or 3.

Specific examples of the group represented by formula (3) include an aminoethyl group, an aminopropyl group, an aminoethylaminoethyl group, an aminopropylaminopropyl group, and an aminoethylaminoethylaminoethyl group.
Among these, as the group represented by general formula (3) for R ⁶ , an aminoethyl group and an aminoethylaminoethyl group are preferred from the viewpoints of availability of the raw materials and usefulness of the product.

Specific examples of the compound (2) include ammonia, methylamine, ethylamine, butylamine, allylamine, aniline, ethylenediamine, propylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, and tripropylenetetramine.
Among these, allylamine, ethylenediamine, and diethylenetriamine are preferred from the viewpoint of availability of raw materials.

Specific examples of the oxadisilacyclopentane compound represented by the above general formula (4) (hereinafter referred to as "compound (4)") obtained by the above reaction include 2,2,5,5-tetramethyl-1-oxa-2,5-disilacyclopentane, 2,2,5,5-tetraethyl-1-oxa-2,5-disilacyclopentane, 2,2,5,5-tetrapropyl-1-oxa-2,5-disilacyclopentane, 2,2,5,5-tetraisopropyl-1-oxa-2,5-disilacyclopentane, 2,2,5,5-tetrabutyl-1-oxa-2,5-disilacyclopentane, 2,5-diethyl-2,5-dimethyl-1-oxa-2,5-disilacyclopentane, 2,5-ditert-butyl-2,5-dimethyl-1-oxa-2,5-disilacyclopentane, and the like.

The mixing ratio of the above compound (1) and compound (2) is not particularly limited, but from the standpoint of reactivity and productivity, 0.6 to 20.0 moles of compound (2) per mole of acyloxy group of compound (1) is preferred, and 0.8 to 10.0 moles is more preferred.

The above reaction can be carried out without a solvent.
In this case, compound (1) may be added to compound (2), or compound (2) may be added to compound (1).

The above reaction can also be carried out using a solvent.
Specific examples of the solvent include any solvent that does not inhibit the reaction, such as pentane, hexane, octane, decane, dodecane, tetradecane, cyclohexane, heptane, isooctane, benzene, toluene, xylene, mesitylene, tetralin, and other hydrocarbon solvents; diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and other ether solvents; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and other ester solvents; acetonitrile, N,N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, and other aprotic polar solvents; dichloromethane, chloroform, and other chlorinated hydrocarbon solvents; and methanol, ethanol, and other alcohol solvents. These may be used alone or in combination of two or more.

When a solvent is used, the order of compound (1), compound (2), and the solvent may be arbitrary, but it is preferable to mix a mixture of compound (2) and the solvent with compound (1), and it is more preferable to add compound (1) to a mixture of compound (2) and the solvent.

The reaction temperature of the above reaction is not particularly limited, but is preferably 0 to 100°C, more preferably 15 to 85°C, even more preferably 20 to 80°C, and even more preferably 20 to 70°C.
The reaction time is not particularly limited, but is preferably 1 to 15 hours, more preferably 1 to 10 hours, even more preferably 1 to 7 hours, and even more preferably 1 to 5 hours.
The above reaction may be carried out in air or in an inert gas atmosphere such as nitrogen or argon.

In the present invention, the reaction in which compound (1) is converted into the target compound (4) is presumed to proceed as shown in the following reaction formula.

First, compound (1) reacts with compound (2) to produce intermediate compound (5) and amide compound (6), which are then converted into compound (4) and carboxylic acid compound (7) in a ring-closing reaction. In this reaction, water is not used during the reaction, and water is not produced during the reaction, so a polymerization reaction due to a ring-opening reaction of the oxadisilacyclopentane compound by water does not proceed. Therefore, the oxadisilacyclopentane compound can be obtained in high yield.

The reaction liquid thus obtained can be filtered or separated as necessary, and the desired product can be obtained by conventional methods such as distillation or removal of low-boiling compounds.

The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[Example 1]
A flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer was charged with 227.0 g (2.2 mol) of diethylenetriamine, and 262.5 g (1.0 mol) of 1,2-bis(acetoxydimethylsilyl)ethane was added dropwise over 30 minutes at 65-75°C, followed by stirring for 5 hours at that temperature. After removing the lower layer which separated into two layers, the upper layer was distilled. 131.0 g of 2,2,5,5-tetramethyl-1-oxa-2,5-disilacyclopentane was obtained as a fraction with a boiling point of 49-50°C/6.0 kPa (yield 82%).

[Example 2]
A flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer was charged with 227.0 g (2.2 mol) of diethylenetriamine, and 290.5 g (1.0 mol) of 1,2-bis(propionyloxydimethylsilyl)ethane was added dropwise over 30 minutes, and the mixture was stirred for 5 hours at the same temperature. After removing the lower layer, which separated into two layers, the upper layer was distilled. 132.1 g of 2,2,5,5-tetramethyl-1-oxa-2,5-disilacyclopentane was obtained as a fraction with a boiling point of 49-50°C/6.0 kPa (yield 82%).

[Example 3]
A flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer was charged with 215.3g (1.0 mol) of 1,2-bis(chlorodimethylsilyl)ethane, and 163.0g (2.2 mol) of propionic acid was added dropwise at 100-110°C over 1 hour, followed by stirring at 165-170°C for 15 hours to obtain a reaction solution of 1,2-bis(propionyloxydimethylsilyl)ethane. Subsequently, 258.0g (2.5 mol) of diethylenetriamine was added dropwise at 65-75°C over 30 minutes, and the mixture was stirred at that temperature for 5 hours. After removing the lower layer, which separated into two layers, the upper layer was distilled. 116.2g of 2,2,5,5-tetramethyl-1-oxa-2,5-disilacyclopentane was obtained as a fraction with a boiling point of 49-50°C/6.0kPa (yield 72%).

[Comparative Example 1]
215.3g (1.0 mol) of 1,2-bis(chlorodimethylsilyl)ethane was charged into a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, and 900g (50.0 mol) of water was dropped at 50-60°C over 1 hour, and the mixture was stirred at that temperature for 1 hour. After the reaction, the lower layer, which separated into two layers, was removed, and 6.4g of a 50% by mass aqueous potassium hydroxide solution was added to the upper layer, and the generated polymer compound was subjected to a thermal decomposition reaction. The generation of the target 2,2,5,5-tetramethyl-1-oxa-2,5-disilacyclopentane was confirmed when the internal temperature reached 250°C or higher. After a 5-hour reaction at 370°C, distillation was performed. 78.3g of 2,2,5,5-tetramethyl-1-oxa-2,5-disilacyclopentane was obtained as a fraction with a boiling point of 49-50°C/6.0kPa (yield 49%).

Claims (2)

The following general formula (1)

(In the formula, R ¹ to R ⁴ each independently represent an unsubstituted monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ⁵ represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.)
and a bissilylethane compound having an acyloxy group represented by the following general formula (2):

In the formula, R ⁶ represents a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or a group represented by the following general formula (3):

(In the formula, m represents an integer of 0 to 5, n represents an integer of 1 to 5, and the dashed line represents a bond.)
and reacting an amine compound represented by the following general formula (4):

(In the formula, R ¹ to R ⁴ have the same meanings as above.)
A method for producing an oxadisilacyclopentane compound represented by the following formula: The method for producing an oxadisilacyclopentane compound according to claim 1, wherein the reaction temperature is 0 to 100°C.