JP7803244B2 - Method for producing oxadisilacyclopentane compounds - Google Patents

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.

Proposed methods for producing oxadisilacyclopentane compounds include, for example, 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), reacting 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane with magnesium (see Non-Patent Document 1), and 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 oxadisilacyclopentane as a by-product in the synthesis of a polynuclear tin complex (see Non-Patent Document 2).

Japanese Patent Application Publication No. 5-25182

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

In the method of Patent Document 1, 2,2,5,5-tetramethyl-1-oxa-2,5-disilacyclopentane is thought to be 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 product, which quickly produces a polymeric compound, and the target 2,2,5,5-tetramethyl-1-oxa-2,5-disilacyclopentane is hardly obtained by this reaction. To obtain 2,2,5,5-tetramethyl-1-oxa-2,5-disilacyclopentane from this polymeric compound, a second-stage reaction, a thermal decomposition reaction, is required, which increases the number of steps and is therefore not industrially advantageous.
Furthermore, to obtain the target oxadisilacyclopentane compound by the above-mentioned thermal decomposition, the thermal decomposition reaction must be carried out at a temperature of at least 200°C or higher, and to obtain the target compound at a practical reaction rate, a temperature of 300°C or higher is required. This requires a large amount of energy for production, and is therefore not industrially advantageous.

Furthermore, in the method of Non-Patent Document 1, the reaction must be carried out while adding magnesium as needed 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 was developed in consideration of the above circumstances, and aims to provide a method for efficiently and efficiently producing oxadisilacyclopentane compounds.

As a result of extensive research to achieve the above-mentioned objective, the inventors discovered that an oxadisilacyclopentane compound can be obtained without the need for complicated procedures by reacting a bissilylethane compound having an acyloxy group with an amine compound. Furthermore, because this method does not use water, the ring-opening reaction of the oxadisilacyclopentane compound in the reaction system to form a polymeric compound is suppressed, and oxadisilacyclopentane compounds can be obtained in good yield without the need for a high-temperature reaction. This discovery led to the completion of the present invention.

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

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

The present invention will be specifically described below.
The method for producing an oxadisilacyclopentane compound of the present invention involves 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 general 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 thereof 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, and methyl and ethyl groups are 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 such substituents include alkoxy groups such as methoxy, ethoxy, and (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; alkenyl groups having 3 to 5 carbon atoms, such as allyl, 1-butenyl, and 1-pentenyl; and aryl groups having 6 to 8 carbon atoms, such as phenyl.

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 products.
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 is, or may be purified by distillation or the like.

In general 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 general formula (3).

Here, the monovalent hydrocarbon group for ^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 such substituents include alkoxy groups such as methoxy, ethoxy, and (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, the monovalent hydrocarbon group for ^R6 is preferably an alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl, n-propyl, or isopropyl; an alkenyl group having 3 to 5 carbon atoms, such as allyl, 1-butenyl, or 1-pentenyl; or an aryl group having 6 to 8 carbon atoms, such as phenyl.

In the general 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 the general 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) of R ⁶ , an aminoethyl group and an aminoethylaminoethyl group are preferred from the viewpoints of easy availability of 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 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, and 2,5-di-tert-butyl-2,5-dimethyl-1-oxa-2,5-disilacyclopentane.

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

When a solvent is used, the order of compounding compound (1), compound (2), and the solvent is 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 for 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 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). Subsequently, intermediate compound (5) undergoes a ring-closure reaction to convert to compound (4) and carboxylic acid compound (7). Because no water is used or produced during this reaction, polymerization due to the ring-opening reaction of the oxadisilacyclopentane compound with water does not proceed. Therefore, the oxadisilacyclopentane compound can be obtained in high yield.

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

The present invention will be explained in more detail below using 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. The two separated layers were separated, and the lower layer was removed, followed by distillation of the upper layer. 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, followed by stirring for 5 hours at the same temperature. After the two-layer separation, the lower layer was removed, and 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 215.3 g (1.0 mol) of 1,2-bis(chlorodimethylsilyl)ethane, and 163.0 g (2.2 mol) of propionic acid was added dropwise over 1 hour at 100-110°C. The mixture was stirred at 165-170°C for 15 hours to obtain a reaction solution of 1,2-bis(propionyloxydimethylsilyl)ethane. Subsequently, 258.0 g (2.5 mol) of diethylenetriamine was added dropwise over 30 minutes at 65-75°C, and the mixture was stirred for 5 hours at that temperature. After removing the lower layer, the upper layer was distilled. 116.2 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 (72% yield).

[Comparative Example 1]
A flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 215.3 g (1.0 mol) of 1,2-bis(chlorodimethylsilyl)ethane, and 900 g (50.0 mol) of water was added dropwise over 1 hour at 50-60°C. The mixture was then stirred at that temperature for 1 hour. After the reaction, the lower layer separated into two layers, and 6.4 g of a 50% by weight aqueous potassium hydroxide solution was added to the upper layer, allowing the resulting polymeric compound to undergo thermal decomposition. The formation of the target 2,2,5,5-tetramethyl-1-oxa-2,5-disilacyclopentane was confirmed only after the internal temperature reached 250°C or higher. After 5 hours of reaction at 370°C, distillation was performed. 78.3 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: 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):
[wherein R ⁶ represents n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-icosyl group , or a group represented by the following general formula (3):
(wherein 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):
(wherein R ¹ to R ⁴ have the same meanings as above.)
A method for producing an oxadisilacyclopentane compound represented by the formula: The method for producing an oxadisilacyclopentane compound according to claim 1, wherein the reaction temperature is 0 to 100°C.