Cyclic aminoorganoxysilane compound and process for producing the same

Abstract

A cyclic aminoorganoxysilane compound having the following general formula (1): ##STR00001##
wherein R.sup.1 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R.sup.2 to R.sup.5 each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R.sup.6 to R.sup.8 each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R.sup.9 and R.sup.10 each independently represent a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms optionally containing a heteroatom, m is 0, 1 or 2 and n is 0 or 1.

Claims

1. A cyclic aminoorganoxysilane compound having the following general formula (1): ##STR00008## wherein R.sup.1 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R.sup.2 to R.sup.5 each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R.sup.6 to R.sup.8 each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R.sup.9 and R.sup.10 each independently represent a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, m is 0, 1 or 2 and n is 0 or 1.

2. A process for producing the cyclic aminoorganoxysilane compound according to claim 1, the process comprising distilling a reaction mixture obtained by making an aminoorganoxysilane compound having the following general formula (2): ##STR00009## wherein R.sup.2 to R.sup.5, R.sup.9, R.sup.10, m and n represent the same meanings as those defined above react with an epoxy compound having the following general formula (3): ##STR00010## wherein R.sup.1 and R.sup.6 to R.sup.8 represent the same meanings as those defined above.

3. The process for producing the cyclic aminoorganoxysilane compound according to claim 2, the process further comprising distilling the reaction mixture in the presence of a basic catalyst or an acidic catalyst.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a .sup.1H-NMR spectrum of a compound obtained in Example 1;

(2) FIG. 2 is an IR spectrum of a compound obtained in Example 1;

(3) FIG. 3 is a .sup.1H-NMR spectrum of a compound obtained in Example 2; and

(4) FIG. 4 is an IR spectrum of a compound obtained in Example 2.

DESCRIPTION OF THE PREFERRED EMBODIMENT

(5) Hereinafter, the present invention is described in detail.

(6) The cyclic aminoorganoxysilane compound according to the present invention has the following general formula (1).

(7) ##STR00005##

(8) In the formula (1), R.sup.1 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R.sup.2 to R.sup.5 each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R.sup.6 to R.sup.8 each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R.sup.9 and R.sup.1′ each independently represent a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms optionally containing a heteroatom, m is 0, 1 or 2, and is preferably 0, and n is 0 or 1, and is preferably 0.

(9) Here, examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably having 1 to 10 carbon atoms, and more preferably having 1 to 5 carbon atoms of R.sup.1 include a linear, branched or cyclic alkyl group, alkenyl group, aryl group, aralkyl group or the like.

(10) Specifically, examples of the monovalent hydrocarbon group of the R.sup.1 include: a linear alkyl group such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and icosyl groups; a branched alkyl group such as isopropyl, isobutyl, sec-butyl, tert-butyl, thexyl, and 2-ethylhexyl groups; a cyclic alkyl group such as cyclopentyl, and cyclohexyl groups; an alkenyl group such as vinyl, allyl, butenyl, and pentenyl groups; an aryl group such as phenyl, and tolyl groups; an aralkyl group such as a benzyl group and the like. Particularly, from the viewpoints of availability of raw materials and usefulness of products, an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group and an isopropyl group; an alkenyl group having 2 to 5 carbon atoms such as an allyl group, a butenyl group, and a pentenyl group are preferable.

(11) Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably having 1 to 10 carbon atoms, and more preferably having 1 to 5 carbon atoms of R.sup.2 to R.sup.8 include the same groups as those exemplified for the above-described R.sup.1. Also in this case, particularly from the viewpoints of availability of raw materials and usefulness of products, preferable examples of R.sup.2 to R.sup.5 include an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group, and an alkenyl group having 2 to 5 carbon atoms such as an allyl group, a butenyl group and a pentenyl group, and preferable examples of R.sup.6 to R.sup.8 include a hydrogen atom.

(12) Meanwhile, some or all of the hydrogen atoms in the above-described monovalent hydrocarbon groups of R.sup.1 to R.sup.5 may be substituted with other substituents, and specific examples of such substituents include an alkoxy group such as a methoxy group, an ethoxy group, and an (iso)propoxy group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a cyano group; an amino group; an acyl group having 2 to 10 carbon atoms; a trichlorosilyl group; a trialkylsilyl group, a dialkylmonochlorosilyl group, a monoalkyldichlorosilyl group, a trialkoxysilyl group, a dialkylmonoalkoxysilyl group or a monoalkyldialkoxysilyl group in which each alkyl group or each alkoxy group has 1 to 5 carbon atoms. Two or more of these substituents may be used in combination, and the substitution position and the number of substituents are not particularly limited.

(13) Examples of the heteroatom in the divalent hydrocarbon group having 1 to 20 carbon atoms, preferably having 1 to 10 carbon atoms, and more preferably having 1 to 5 carbon atoms of R.sup.9 and R.sup.11 which may contain a heteroatom include O, S, NH, and the like.

(14) The above-described divalent hydrocarbon group may be any of linear, branched, and cyclic groups, and specific examples thereof include an alkylene group such as methylene, ethylene, methyl ethylene (propylene), trimethylene, methyl trimethylene, tetramethylene, hexamethylene, octamethylene, decamethylene, and isobutylene groups; an arylene group such as phenylene, and methyl phenylene groups; an aralkylene group such as ethylenephenylene, and ethylenephenylene methylene groups; an oxaalkylene group such as 2-oxapropylene, 2-oxapentylene groups and the like. Particularly, from the viewpoints of availability of raw materials, and usefulness of products, R.sup.9 is preferably an alkylene group having 1 to 3 carbon atoms such as methylene, ethylene, and trimethylene groups, and R.sup.10 is preferably an alkylene group having 1 to 3 carbon atoms such as methylene, ethylene, and trimethylene groups; and a 2-oxapropylene group.

(15) Meanwhile, some or all of the hydrogen atoms in the above-described divalent hydrocarbon groups may be substituted with other substituents, and specific examples of such substituents include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a cyano group; an amino group; an acyl group having 2 to 10 carbon atoms; a trichlorosilyl group; a trialkylsilyl group, a dialkylmonochlorosilyl group, a monoalkyldichlorosilyl group, a trialkoxysilyl group, a dialkylmonoalkoxysilyl group or a monoalkyldialkoxysilyl group in which each alkyl group or each alkoxy group has 1 to 5 carbon atoms. Two or more of these substituents may be used in combination, and the substitution position and the number of substituents are not particularly limited.

(16) Specific examples of the cyclic aminoorganoxysilane compound having the general formula (1) include: 2,2-dimethoxy-6-methoxymethyl-4-(trimethoxysilylmethyl)-1-oxa-4-aza-2-silacyclohexane, 2-methoxy-2-methyl-6-methoxymethyl-4-(dimethoxymethylsilylmethyl)-1-oxa-4-aza-2-silacyclohexane, 2,2-dimethyl-6-methoxymethyl-4-(methoxydimethylsilylmethyl)-1-oxa-4-aza-2-silacyclohexane, 2,2-diethoxy-6-methoxymethyl-4-(triethoxysilylmethyl)-1-oxa-4-aza-2-silacyclohexane, 2-ethoxy-2-methyl-6-methoxymethyl-4-(diethoxymethylsilylmethyl)-1-oxa-4-aza-2-silacyclohexane, 2,2-dimethyl-6-methoxymethyl-4-(ethoxydimethylsilylmethyl)-1-oxa-4-aza-2-silacyclohexane, 2,2-dimethoxy-8-methoxymethyl-6-(3-trimethoxysilylpropyl)-1-oxa-6-aza-2-silacyclooctane, 2-methoxy-2-methyl-8-methoxymethyl-6-(3-dimethoxymethylsilylpropyl)-1-oxa-6-aza-2-silacyclooctane, 2,2-dimethyl-8-methoxymethyl-6-(3-methoxydimethylsilylpropyl)-1-oxa-6-aza-2-silacyclooctane, 2,2-diethoxy-8-methoxymethyl-6-(3-triethoxysilylpropyl)-1-oxa-6-aza-2-silacyclooctane, 2-ethoxy-2-methyl-8-methoxymethyl-6-(3-diethoxymethylsilylpropyl)-1-oxa-6-aza-2-silacyclooctane, 2,2-dimethyl-8-methoxymethyl-6-(3-ethoxydimethylsilylpropyl)−1-oxa-6-aza-2-silacyclooctane, 2,2-dimethoxy-6-allyloxymethyl-4-(trimethoxysilylmethyl)-1-oxa-4-aza-2-silacyclohexane, 2-methoxy-2-methyl-6-allyloxymethyl-4-(dimethoxymethylsilylmethyl)-1-oxa-4-aza-2-silacyclohexane, 2,2-dimethyl-6-allyloxymethyl-4-(methoxydimethylsilylmethyl)-1-oxa-4-aza-2-silacyclohexane, 2,2-diethoxy-6-allyloxymethyl-4-(triethoxysilylmethyl)-1-oxa-4-aza-2-silacyclohexane, 2-ethoxy-2-methyl-6-allyloxymethyl-4-(diethoxymethylsilylmethyl)-1-oxa-4-aza-2-silacyclohexane, 2,2-dimethyl-6-allyloxymethyl-4-(ethoxydimethylsilylmethyl)-1-oxa-4-aza-2-silacyclohexane, 2,2-dimethoxy-8-allyloxymethyl-6-(3-trimethoxysilylpropyl)-1-oxa-6-aza-2-silacyclooctane, 2-methoxy-2-methyl-8-allyloxymethyl-6-(3-dimethoxymethylsilylpropyl)-1-oxa-6-aza-2-silacyclooctane, 2,2-dimethyl-8-allyloxymethyl-6-(3-methoxydimethylsilylpropyl)-1-oxa-6-aza-2-silacyclooctane, 2,2-diethoxy-8-allyloxymethyl-6-(3-triethoxysilylpropyl)-1-oxa-6-aza-2-silacyclooctane, 2-ethoxy-2-methyl-8-allyloxymethyl-6-(3-diethoxymethylsilylpropyl)-1-oxa-6-aza-2-silacyclooctane, 2,2-dimethyl-8-allyloxymethyl-6-(3-ethoxydimethylsilylpropyl)-1-oxa-6-aza-2-silacyclooctane, 2,2-dimethoxy-6-butoxymethyl-4-(trimethoxysilylmethyl)-1-oxa-4-aza-2-silacyclohexane, 2-methoxy-2-methyl-6-butoxymethyl-4-(dimethoxymethylsilylmethyl)-1-oxa-4-aza-2-silacyclohexane, 2,2-dimethyl-6-butoxymethyl-4-(methoxydimethylsilylmethyl)-1-oxa-4-aza-2-silacyclohexane, 2,2-diethoxy-6-butoxymethyl-4-(triethoxysilylmethyl)-1-oxa-4-aza-2-silacyclohexane, 2-ethoxy-2-methyl-6-butoxymethyl-4-(diethoxymethylsilylmethyl)-1-oxa-4-aza-2-silacyclohexane, 2,2-dimethyl-6-butoxymethyl-4-(ethoxydimethylsilylmethyl)-1-oxa-4-aza-2-silacyclohexane, 2,2-dimethoxy-8-butoxymethyl-6-(3-trimethoxysilylpropyl)-1-oxa-6-aza-2-silacyclooctane, 2-methoxy-2-methyl-8-butoxymethyl-6-(3-dimethoxymethylsilylpropyl)-1-oxa-6-aza-2-silacyclooctane, 2,2-dimethyl-8-butoxymethyl-6-(3-methoxydimethylsilylpropyl)-1-oxa-6-aza-2-silacyclooctane, 2,2-diethoxy-8-butoxymethyl-6-(3-triethoxysilylpropyl)-1-oxa-6-aza-2-silacyclooctane, 2-ethoxy-2-methyl-8-butoxymethyl-6-(3-diethoxymethylsilylpropyl)-1-oxa-6-aza-2-silacyclooctane, 2,2-dimethyl-8-butoxymethyl-6-(3-ethoxydimethylsilylpropyl)-1-oxa-6-aza-2-silacyclooctane, 2,2-dimethoxy-6-phenoxymethyl-4-(trimethoxysilylmethyl)-1-oxa-4-aza-2-silacyclohexane, 2-methoxy-2-methyl-6-phenoxymethyl-4-(dimethoxymethylsilylmethyl)-1-oxa-4-aza-2-silacyclohexane, 2,2-dimethyl-6-phenoxymethyl-4-(methoxydimethylsilylmethyl)-1-oxa-4-aza-2-silacyclohexane, 2,2-diethoxy-6-phenoxymethyl-4-(triethoxysilylmethyl)-1-oxa-4-aza-2-silacyclohexane, 2-ethoxy-2-methyl-6-phenoxymethyl-4-(diethoxymethylsilylmethyl)-1-oxa-4-aza-2-silacyclohexane, 2,2-dimethyl-6-phenoxymethyl-4-(ethoxydimethylsilylmethyl)-1-oxa-4-aza-2-silacyclohexane, 2,2-dimethoxy-8-phenoxymethyl-6-(3-trimethoxysilylpropyl)-1-oxa-6-aza-2-silacyclooctane, 2-methoxy-2-methyl-8-phenoxymethyl-6-(3-dimethoxymethylsilylpropyl)-1-oxa-6-aza-2-silacyclooctane, 2,2-dimethyl-8-phenoxymethyl-6-(3-methoxydimethylsilylpropyl)-1-oxa-6-aza-2-silacyclooctane, 2,2-diethoxy-8-phenoxymethyl-6-(3-triethoxysilylpropyl)-1-oxa-6-aza-2-silacyclooctane, 2-ethoxy-2-methyl-8-phenoxymethyl-6-(3-diethoxymethylsilylpropyl)-1-oxa-6-aza-2-silacyclooctane, 2,2-dimethyl-8-phenoxymethyl-6-(3-ethoxydimethylsilylpropyl)-1-oxa-6-aza-2-silacyclooctane and the like.

(17) Examples of the process for producing the cyclic aminoorganoxysilane compound having the general formula (1) according to the present invention include a process comprising distilling a reaction mixture obtained by making an aminoorganoxysilane compound having the following general formula (2) (hereinafter, abbreviated as the compound (2)) react with an epoxy compound having the following general formula (3) (hereinafter, abbreviated as the compound (3)):

(18) ##STR00006##
wherein R.sup.1 to R.sup.10, m and n represent the same meanings as described above.

(19) More specifically, it is considered that as shown in the following scheme, in the first step, the compound (2) is made to react with the compound (3) to form an aminoorganoxysilane compound having a hydroxyl group, and in the second step, that is, in the step of distilling a reaction solution containing the aminoorganoxysilane compound having a hydroxyl group, intramolecular dealcoholization cyclization occurs to form a target cyclic aminoorganoxysilane compound.

(20) ##STR00007##

(21) Specific examples of the compound (2) include bis(trimethoxysilylmethyl)amine, bis(dimethoxymethylsilylmethyl)amine, bis(methoxydimethylsilylmethyl)amine, bis(triethoxysilylmethyl)amine, bis(diethoxymethylsilylmethyl)amine, bis(ethoxydimethylsilylmethyl)amine, bis(3-trimethoxysilylpropyl)amine, bis(3-dimethoxymethylsilylpropyl)amine, bis(3-methoxydimethylsilylpropyl)amine, bis(3-triethoxysilylpropyl)amine, bis(3-diethoxymethylsilylpropyl)amine, bis(3-ethoxydimethylsilylpropyl)amine and the like.

(22) Specific examples of the compound (3) include glycidyl methyl ether, allyl glycidyl ether, butyl glycidyl ether, glycidyl phenyl ether and the like.

(23) The compounding ratio of the compound (2) and the compound (3) is not particularly limited, but from the viewpoint of reactivity and productivity, preferably 0.2 to 5.0 mol and more preferably 0.5 to 2.0 mol of the compound (3) is used per 1 mol of the compound (2).

(24) Although the first step reaction proceeds even without a catalyst, a basic catalyst or an acidic catalyst may be used for the purpose of improving the reaction rate.

(25) Specific examples of the basic catalyst include sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, a methanol solution of sodium methoxide, an ethanol solution of sodium ethoxide and the like.

(26) On the other hand, specific examples of the acidic catalyst include an inorganic acid such as sulfuric acid, hydrochloric acid, and nitric acid; a sulfonic acid compound such as methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid, and trifluoromethanesulfonic acid as well as salts thereof and the like.

(27) The amount of the catalyst to be used is not particularly limited, but from the viewpoint of reactivity and productivity, preferably 0.0001 to 0.2 mol and more preferably 0.001 to 0.1 mol of the catalyst is used per 1 mol of the compound (2).

(28) Meanwhile, though the reaction in the first step proceeds even without a solvent, a solvent can also be used. Examples of the solvent used include a hydrocarbon-based solvent such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene, and xylene; an ether-based solvent such as diethyl ether, tetrahydrofuran, and dioxane; an ester-based solvent such as ethyl acetate, and butyl acetate; an aprotic polar solvent such as acetonitrile, N,N-dimethylformamide, and N-methylpyrrolidone; a chlorinated hydrocarbon-based solvent such as dichloromethane, and chloroform; an alcohol-based solvent such as methanol, ethanol, 1-propanol, and 2-propanol and the like. These solvents may be used singly or in combination of two or more kinds.

(29) In the distillation process of the second step, although ordinary distillation processes can be used, in order to accelerate the reaction rate of the dealcoholation reaction, or in order to crack the intermolecular dealcoholation-condensed polymer compound present in the reaction solution and to convert it into a target cyclic aminoorganoxysilane compound, it is preferable to perform the distillation in the presence of a basic catalyst or an acidic catalyst.

(30) As the basic catalyst and the acidic catalyst in this case, the same ones as described above can be used.

(31) The amount of the catalyst to be used is not particularly limited, but from the viewpoint of reactivity and productivity, preferably 0.0001 to 0.2 mol and more preferably 0.001 to 0.1 mol of the catalyst is used per 1 mol of the compound (3).

(32) Meanwhile, in the second step, the reaction solution obtained in the first step may be distilled as it is or the solvent may be further added to the reaction solution for distillation.

(33) Further, examples of the solvent in this case include a hydrocarbon-based solvent such as pentane, hexane, cyclohexane, heptane, isooctane, decane, tridecane, octadecane, eicosane, benzene, toluene, xylene, and dodecylbenzene; an ether-based solvent such as diethyl ether, tetrahydrofuran, dioxane, and diphenyl ether; an ester-based solvent such as ethyl acetate, butyl acetate, methyl stearate, and methyl oleate; an aprotic polar solvent such as acetonitrile, N,N-dimethylformamide, and N-methylpyrrolidone; a chlorinated hydrocarbon-based solvent such as dichloromethane, and chloroform; an alcohol-based solvent such as methanol, ethanol, 1-propanol, 2-propanol, 1-decanol, 1-octadecanol, 2-hexyl-1-decanol, oleyl alcohol, and 1-docosanol and the like. These solvents may be used singly or in combination of two or more kinds.

EXAMPLES

(34) Hereinafter, the present invention is described more specifically with reference to Examples, but the present invention is not limited to the following Examples.

(35) Meanwhile, the .sup.1H-NMR spectrum was measured with deuterated chloroform solvent at 600 MHz, and the IR spectrum was measured by D-ATR.

Example 1

(36) 102.5 g (0.3 mol) of bis(3-trimethoxysilylpropyl)amine and 19.2 g of methanol were charged in a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer and the mixture was heated to 60° C. After the internal temperature was stabilized, 29.1 g (0.33 mol) of glycidyl methyl ether was added dropwise over 1 hour and the mixture was stirred at that temperature for 2 hours.

(37) After completion of stirring, 0.6 g of a methanol solution of 28% by weight sodium methoxide was added to the reaction solution and the mixture was distilled to obtain 83.6 g of a fraction having a boiling point of 174 to 176° C./0.3 kPa.

(38) Mass spectrum, .sup.1H-NMR spectrum and IR spectrum of the obtained fraction were measured. The .sup.1H-NMR spectrum is shown in FIG. 1, and the IR spectrum is shown in FIG. 2.

(39) Mass Spectrum

(40) m/z 397, 366, 248, 160, 121, 91

(41) From these results, it was confirmed that the obtained compound was 2,2-dimethoxy-8-methoxymethyl-6-(3-trimethoxysilylpropyl)-1-oxa-6-aza-2-silacyclooctane.

Example 2

(42) 136.6 g (0.4 mol) of bis(3-trimethoxysilylpropyl)amine and 25.6 g of methanol were charged in a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer and the mixture was heated to 60° C. After the internal temperature was stabilized, 57.3 g (0.44 mol) of butyl glycidyl ether was added dropwise over 1 hour and the mixture was stirred at that temperature for 2 hours.

(43) After completion of stirring, 0.8 g of a methanol solution of 28% by weight sodium methoxide was added to the reaction solution and the mixture was distilled to obtain 146.7 g of a fraction having a boiling point of 179 to 182° C./0.2 kPa.

(44) Mass spectrum, .sup.1H-NMR spectrum and IR spectrum of the obtained fraction were measured. The .sup.1H-NMR spectrum is shown in FIG. 3, and the IR spectrum is shown in FIG. 4.

(45) Mass Spectrum

(46) m/z 439, 408, 366, 290, 160, 121, 91

(47) From these results, it was confirmed that the obtained compound was 2,2-dimethoxy-8-butoxymethyl-6-(3-trimethoxysilylpropyl)-1-oxa-6-aza-2-silacyclooctane.

(48) Japanese Patent Application No. 2018-116813 is incorporated herein by reference.

(49) Although some preferred embodiments have been described, many modifications and variations may be made thereto in light of the above teachings. It is therefore to be understood that the invention may be practiced otherwise than as specifically described without departing from the scope of the appended claims.