Nitrogen-containing organoxysilane compound and method for producing same

Abstract

This nitrogen-containing organoxysilane compound represented by general formula (1) is a new compound having three or more tertiary amino groups, and can be synthesized using, as a raw material, a secondary amine that can be industrially obtained in various types. (In the formula, R1 and R2 each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1-10 carbon atoms, R3 represents an unsubstituted divalent hydrocarbon group having 1-10 carbon atoms and optionally having a heteroatom interposed therein, R4 and R5 each independently represent a substituted (but excluding a silyl group) or unsubstituted monovalent hydrocarbon group having 1-10 carbon atoms, R4 and R5 are optionally bonded to each other to form a ring together with a nitrogen atom bonded thereto, and n represents an integer of 0-2.)

Description

Nitrogen-containing organoxysilane compound and method for producing same

[0001] The present invention relates to a nitrogen-containing organoxysilane compound useful as a silane coupling agent, a surface treatment agent, a resin additive, a paint additive, an adhesive, etc., and a method for producing the same.

[0002] Nitrogen-containing organoxysilane compounds are useful as, for example, silane coupling agents, surface treatment agents, resin additives, paint additives, adhesives, and rubber modifiers. In particular, when inorganic materials such as metal oxides are added to polymeric materials such as polymers to improve their mechanical properties, it is known that the addition of a nitrogen-containing organoxysilane compound improves the adhesion and dispersibility between the polymeric material and the inorganic material.

[0003] Examples of such nitrogen-containing organoxysilane compounds include organoxysilane compounds having a primary amino group, such as aminopropyltrimethoxysilane, organoxysilane compounds having a secondary amino group, such as N-phenylaminopropyltrimethoxysilane, and organoxysilane compounds having a tertiary amino group, such as dimethylaminopropyltrimethoxysilane.

[0004] Among these nitrogen-containing organoxysilane compounds, organoxysilane compounds having a tertiary amino group that does not have an active proton are particularly advantageous in that when mixed with a polymer material having an active site for an electrophile such as an epoxide or isocyanate, or a nucleophile such as an organolithium or organomagnesium, the active site is less likely to react with the amino group, and therefore are less likely to cause an increase in viscosity or side reactions.

[0005] In particular, it is known that among organoxysilane compounds having tertiary amino groups, the greater the number of tertiary amino groups per organoxysilyl group, the greater the effect of addition. For example, Patent Document 1 describes that a rubber composition using an organoxysilane compound having three tertiary amino groups per organoxysilyl group as a rubber modifier exhibits higher performance than a rubber composition modified with an organoxysilane compound having only one tertiary amino group per organoxysilyl group.

[0006] US Patent Application Publication No. 2014 / 0200306

[0007] However, organoxysilane compounds having three or more tertiary amino groups per organoxysilyl group are difficult to obtain, and the variety of compounds available has been limited, for the following reasons: Generally, organoxysilane compounds having a tertiary amino group are produced by subjecting a haloalkylorganoxysilane compound to a substitution reaction with a secondary amine, but in order to produce an organoxysilane compound having three or more tertiary amino groups, a raw material having a complex structure, such as a secondary amine having at least two tertiary amino groups, must be used, and such raw materials are difficult to obtain industrially and are highly difficult to synthesize.

[0008] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel nitrogen-containing organoxysilane compound having three or more tertiary amino groups and a method for producing the same.

[0009] As a result of extensive research aimed at solving the above-mentioned problems, the present inventors have discovered that organoxysilane compounds having three or more tertiary amino groups, which are highly effective as additives to various materials as silane coupling agents and the like, can be produced by reacting a haloalkylalkoxysilane with 1,4-diazabicyclo[2.2.2]octane and then reacting it with a secondary amine, which is available industrially in a wide variety of types, and have thereby completed the present invention.

[0010] That is, the present invention provides: 1. a nitrogen-containing organoxysilane compound represented by the following general formula (1): (In the formula, R 1 and R 2 each independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms; R 3 represents an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, which may contain a heteroatom; R 4 and R 5 each independently represents a substituted (excluding silyl groups) or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms; R 4 and R 5may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded, and n represents an integer of 0 to 2. 2. A compound represented by the following general formula (2): (In the formula, R 1 ~R 3 and n are as defined above, and X represents a chlorine atom, a bromine atom, or an iodine atom, and and then reacting the compound represented by the following general formula (4) with 1,4-diazabicyclo[2.2.2]octane: (In the formula, R 4 and R 5 (wherein "a" has the same meaning as above) with a secondary amine compound represented by the formula (1).

[0011] According to the present invention, organoxysilane compounds having three or more tertiary amino groups can be provided and produced by using secondary amines, which are commercially available in a wide variety, as raw materials.

[0012] The measurement was carried out using a deuterated chloroform solution of 1-[3-(trimethoxysilyl)propyl]-4-[2-(4-methyl-1-piperazinyl)ethyl]piperazine obtained in Example 1. 1 1 is a H-NMR spectrum of 1-[3-(trimethoxysilyl)propyl]-4-[2-(4-methyl-1-piperazinyl)ethyl]piperazine obtained in Example 1. It is an IR spectrum of 1-[3-(triethoxysilyl)propyl]-4-[2-(morpholino)ethyl]piperazine obtained in Example 1, measured in a deuterated chloroform solution. 1 1 is a H-NMR spectrum of 1-[3-(triethoxysilyl)propyl]-4-[2-(morpholino)ethyl]piperazine obtained in Example 1. 1 is an IR spectrum of 1-[3-(trimethoxysilyl)propyl]-4-[2-(azepanyl)ethyl]piperazine obtained in Example 1, measured in a deuterated chloroform solution. 1 1H-NMR spectrum and IR spectrum of 1-[3-(trimethoxysilyl)propyl]-4-[2-(azepanyl)ethyl]piperazine obtained in Example 1.

[0013] The present invention will be described in detail below. The nitrogen-containing organoxysilane compound according to the present invention is represented by the following general formula (1) (hereinafter referred to as "compound (1)").

[0014]

[0015] In the above general formula (1), R 1 and R 2 R each independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms. 1 and R 2 The monovalent hydrocarbon group may be linear, branched, or cyclic, and specific examples thereof include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, isohexyl, isoheptyl, isooctyl, and tert-octyl; cyclic alkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl, allyl, 1-propenyl, butenyl, and methallyl (2-methyl-2-propenyl); aryl groups such as phenyl, tolyl, and xylyl; and aralkyl groups such as benzyl and phenethyl.

[0016] Among these, R 1 and R 2As the alkyl group, a substituted or unsubstituted linear, branched, or cyclic alkyl group, alkenyl group, aryl group, or aralkyl group having 1 to 5 carbon atoms is preferred, and from the viewpoint of easy availability of raw materials, an unsubstituted linear alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group or an ethyl group is even more preferred. Some or all of the hydrogen atoms of these monovalent hydrocarbon groups may be substituted with other substituents. Examples of such substituents include alkoxy groups having 1 to 3 carbon atoms, such as methoxy, ethoxy, or propoxy; halogen atoms such as fluorine, chlorine, or bromine; aryl groups having 6 to 10 carbon atoms, such as phenyl or tolyl; aralkyl groups having 7 to 10 carbon atoms, such as benzyl or phenethyl; cyano groups, amino groups, ester groups, ether groups, carbonyl groups, acyl groups, and sulfide groups, and these may be used alone or in combination of two or more. The substitution positions of these substituents are not particularly limited, and the number of substituents is also not limited.

[0017] In the above general formula (1), R 3 represents an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms, which may contain a heteroatom. 3 The divalent hydrocarbon group may be linear, branched, or cyclic, and specific examples thereof include alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, isobutylene, hexamethylene, octamethylene, decamethylene, cyclohexylene, and methylenecyclohexylene; alkenylene groups such as butynylene, propenylene, butenylene, hexenylene, and octenylene; arylene groups such as phenylene; and aralkylene groups such as methylenephenylene and methylenephenylenemethylene. 3 As the alkylene group, an unsubstituted linear alkylene group having 1 to 8 carbon atoms is preferred, and from the viewpoint of easy availability of raw materials, a methylene group, a trimethylene group, or an octamethylene group is more preferred. These divalent hydrocarbon groups may have one or more heteroatoms in the molecular chain, such as an ether group, a carbonyl group, an amino group, or a sulfide group.

[0018] In the above general formula (1), R 4 and R 5 R each independently represents a substituted (excluding silyl groups) or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. 4 and R 5 The monovalent hydrocarbon group may be linear, branched, or cyclic, and specific examples thereof include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, isohexyl, isoheptyl, isooctyl, and tert-octyl; cyclic alkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl, allyl, 1-propenyl, butenyl, and methallyl (2-methyl-2-propenyl); aryl groups such as phenyl, tolyl, and xylyl; and aralkyl groups such as benzyl and phenethyl.

[0019] Among these, R 4 and R 5 As the alkyl group, a substituted or unsubstituted linear, branched, or cyclic alkyl group, alkenyl group, aryl group, or aralkyl group having 1 to 8 carbon atoms is preferred, and from the viewpoint of easy availability of raw materials in particular, an unsubstituted linear alkyl group having 1 to 6 carbon atoms is more preferred, and a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, or an n-hexyl group is even more preferred. Some or all of the hydrogen atoms of these monovalent hydrocarbon groups may be substituted with a substituent other than a silyl group, and examples of such substituents include alkoxy groups having 1 to 3 carbon atoms such as methoxy, ethoxy, or propoxy; halogen atoms such as fluorine, chlorine, or bromine; aryl groups having 6 to 10 carbon atoms such as phenyl or tolyl; aralkyl groups having 7 to 10 carbon atoms such as benzyl or phenethyl; cyano, amino, ester, ether, carbonyl, acyl, or sulfide group, and these may be used alone or in combination. The substitution positions of these substituents are not particularly limited, and the number of substituents is also not limited.

[0020] Also, R 4 and R 5 may be bonded to each other to form a ring structure together with the nitrogen atom to which they are bonded, and examples of such ring structures include a pyrrolidine ring, a piperidine ring, a morpholine ring, and a piperazine ring.

[0021] In the above general formula (1), n ​​represents an integer of 0 to 2, and preferably an integer of 0 to 1.

[0022] Specific examples of compound (1) include 4-[(trimethoxysilyl)methyl]-N,N-dimethyl-1-piperazineethanamine, 4-[(trimethoxysilyl)methyl]-N,N-diethyl-1-piperazineethanamine, 4-[(trimethoxysilyl)methyl]-N,N-dipropyl-1-piperazineethanamine, 4-[(trimethoxysilyl)methyl]-N,N-dibutyl-1-piperazineethanamine, 4-[(trimethoxysilyl)methyl]-N,N-dipentyl-1-piperazineethanamine, 4-[(trimethoxysilyl)methyl]-N,N-dipentyl-1-piperazineethanamine, 4-[(trimethoxysilyl)methyl]-N,N-dipropyl-1-piperazineethanamine, 4-[(trimethoxysilyl)methyl]-N,N-dibutyl ... ]-N,N-dihexyl-1-piperazineethanamine, 4-[(triethoxysilyl)methyl]-N,N-dimethyl-1-piperazineethanamine, 4-[(triethoxysilyl)methyl]-N,N-diethyl-1-piperazineethanamine, 4-[(triethoxysilyl)methyl]-N,N-dipropyl-1-piperazineethanamine, 4-[(triethoxysilyl)methyl]-N,N-dibutyl-1-piperazineethanamine, 4-[(triethoxysilyl)methyl]-N,N-dipentyl-1-piperazineethanamine, 4-[(triethoxysilyl)methyl]-N,N-dipentyl-1-piperazineethanamine, 4-[3-(trimethoxysilyl)propyl]-N,N-dihexyl-1-piperazineethanamine, 4-[3-(trimethoxysilyl)propyl]-N,N-dimethyl-1-piperazineethanamine, 4-[3-(trimethoxysilyl)propyl]-N,N-diethyl-1-piperazineethanamine, 4-[3-(trimethoxysilyl)propyl]-N,N-dipropyl-1-piperazineethanamine, 4-[3-(trimethoxysilyl)propyl]-N,N-dibutyl-1-piperazineethanamine, 4-[3-(trimethoxysilyl)propyl]-N,N-dipeptide butyl-1-piperazineethanamine, 4-[3-(trimethoxysilyl)propyl]-N,N-dihexyl-1-piperazineethanamine, 4-[3-(triethoxysilyl)propyl]-N,N-dimethyl-1-piperazineethanamine, 4-[3-(triethoxysilyl)propyl]-N,N-diethyl-1-piperazineethanamine, 4-[3-(triethoxysilyl)propyl]-N,N-dipropyl-1-piperazineethanamine, 4-[3-(triethoxysilyl)propyl]-N,N-dibutyl-1-piperazineethanamine,4-[3-(triethoxysilyl)propyl]-N,N-dipentyl-1-piperazineethanamine, 4-[3-(triethoxysilyl)propyl]-N,N-dihexyl-1-piperazineethanamine, 4-[8-(trimethoxysilyl)octyl]-N,N-dimethyl-1-piperazineethanamine, 4-[8-(trimethoxysilyl)octyl]-N,N-diethyl-1-piperazineethanamine, 4-[8-(trimethoxysilyl)octyl]-N,N-dipropyl-1-piperazineethanamine, 4-[8-(trimethoxysilyl)octyl] -N,N-dibutyl-1-piperazineethanamine, 4-[8-(trimethoxysilyl)octyl]-N,N-dipentyl-1-piperazineethanamine, 4-[8-(trimethoxysilyl)octyl]-N,N-dihexyl-1-piperazineethanamine, 4-[8-(triethoxysilyl)octyl]-N,N-dimethyl-1-piperazineethanamine, 4-[8-(triethoxysilyl)octyl]-N,N-diethyl-1-piperazineethanamine, 4-[8-(triethoxysilyl)octyl]-N,N-dipropyl-1-piperazineethanamine 4-[(trialkoxysilyl)alkyl]-N,N-dialkyl-1-piperazineethanamine compounds such as 4-[8-(triethoxysilyl)octyl]-N,N-dibutyl-1-piperazineethanamine, 4-[8-(triethoxysilyl)octyl]-N,N-dipentyl-1-piperazineethanamine, and 4-[8-(triethoxysilyl)octyl]-N,N-dihexyl-1-piperazineethanamine; 4-[(trialkoxysilyl)alkyl]-N,N-dialkyl-1-piperazineethanamine compounds such as 4-[(dimethoxymethylsilyl)methyl]-N,N-dimethyl-1-piperazineethanamine, ...triethoxysilyl)octyl]-N,N-dipentyl-1-piperazineethanamine, and 4-[8-(triethoxysilyl)octyl]-N,N-dihexyl-1-piperazineethanamine; ethyl]-N,N-diethyl-1-piperazineethanamine, 4-[(dimethoxymethylsilyl)methyl]-N,N-dipropyl-1-piperazineethanamine, 4-[(dimethoxymethylsilyl)methyl]-N,N-dibutyl-1-piperazineethanamine, 4-[(dimethoxymethylsilyl)methyl]-N,N-dipentyl-1-piperazineethanamine, 4-[(dimethoxymethylsilyl)methyl]-N,N-dihexyl-1-piperazineethanamine, 4-[(diethoxymethylsilyl)methyl]-N,N-dimethyl-1-piperazineethanamine,4-[(diethoxymethylsilyl)methyl]-N,N-diethyl-1-piperazineethanamine, 4-[(diethoxymethylsilyl)methyl]-N,N-dipropyl-1-piperazineethanamine, 4-[(diethoxymethylsilyl)methyl]-N,N-dibutyl-1-piperazineethanamine, 4-[(diethoxymethylsilyl)methyl]-N,N-dipentyl-1-piperazineethanamine, 4-[(diethoxymethylsilyl)methyl]-N,N-dihexyl-1-piperazineethanamine, 4-[3-(dimethoxymethylsilyl)propyl ]-N,N-dimethyl-1-piperazineethanamine, 4-[3-(dimethoxymethylsilyl)propyl]-N,N-diethyl-1-piperazineethanamine, 4-[3-(dimethoxymethylsilyl)propyl]-N,N-dipropyl-1-piperazineethanamine, 4-[3-(dimethoxymethylsilyl)propyl]-N,N-dibutyl-1-piperazineethanamine, 4-[3-(dimethoxymethylsilyl)propyl]-N,N-dipentyl-1-piperazineethanamine, 4-[3-(dimethoxymethylsilyl)propyl]-N,N-dihexyl Sil-1-piperazineethanamine, 4-[3-(diethoxymethylsilyl)propyl]-N,N-dimethyl-1-piperazineethanamine, 4-[3-(diethoxymethylsilyl)propyl]-N,N-diethyl-1-piperazineethanamine, 4-[3-(diethoxymethylsilyl)propyl]-N,N-dipropyl-1-piperazineethanamine, 4-[3-(diethoxymethylsilyl)propyl]-N,N-dibutyl-1-piperazineethanamine, 4-[3-(diethoxymethylsilyl)propyl]-N,N-dipentyl-1-piperazine 1-piperazineethanamine, 4-[3-(diethoxymethylsilyl)propyl]-N,N-dihexyl-1-piperazineethanamine, 4-[8-(dimethoxymethylsilyl)octyl]-N,N-dimethyl-1-piperazineethanamine, 4-[8-(dimethoxymethylsilyl)octyl]-N,N-diethyl-1-piperazineethanamine, 4-[8-(dimethoxymethylsilyl)octyl]-N,N-dipropyl-1-piperazineethanamine, 4-[8-(dimethoxymethylsilyl)octyl]-N,N-dibutyl-1-piperazineethanamine,4-[8-(dimethoxymethylsilyl)octyl]-N,N-dipentyl-1-piperazineethanamine, 4-[8-(dimethoxymethylsilyl)octyl]-N,N-dihexyl-1-piperazineethanamine, 4-[8-(diethoxymethylsilyl)octyl]-N,N-dimethyl-1-piperazineethanamine, 4-[8-(diethoxymethylsilyl)octyl]-N,N-diethyl-1-piperazineethanamine, 4-[8-(diethoxymethylsilyl)octyl]-N,N-dipropyl-1-piperazineethanamine, 4-[8-(diethoxymethylsilyl)octyl]-N,N-dibutyl-1-piperazineethanamine, 4-[8-(diethoxymethylsilyl)octyl]-N,N-dibutyl-1-piperazineethanamine, 4-[(dialkoxyalkylsilyl)alkyl]-N,N-dialkyl-1-piperazineethanamine compounds such as 4-[(dialkoxyalkylsilyl)alkyl]-N,N-dialkyl-1-piperazineethanamine, 4-[8-(diethoxymethylsilyl)octyl]-N,N-dipentyl-1-piperazineethanamine, and 4-[8-(diethoxymethylsilyl)octyl]-N,N-dihexyl-1-piperazineethanamine; 4-[(methoxydimethylsilyl)methyl]-N,N-dimethyl-1-piperazineethanamine, 4-[(methoxydimethylsilyl)methyl]-N,N-diethyl-1-piperazineethanamine, 4-[(methoxydimethylsilyl)methyl]-N,N-dipropyl-1-piperazineethanamine, and 4-[(methoxydimethylsilyl)methyl]-N,N-dibutyl-1-piperazineethanamine, 4-[(methoxydimethylsilyl)methyl]-N,N-dipentyl-1-piperazineethanamine, 4-[(methoxydimethylsilyl)methyl]-N,N-dihexyl-1-piperazineethanamine, 4-[(ethoxydimethylsilyl)methyl]-N,N-dimethyl-1-piperazineethanamine, 4-[(ethoxydimethylsilyl)methyl]-N,N-diethyl-1-piperazineethanamine, 4-[(ethoxydimethylsilyl)methyl]-N,N-dipropyl-1-piperazineethanamine, 4-[(ethoxydimethylsilyl)methyl]-N,N-dibutyl-1-piperazineethanamine, 4-[(ethoxydimethylsilyl)methyl]-N,N-dipentyl-1-piperazineethanamine, 4-[(ethoxydimethylsilyl)methyl]-N,N-dihexyl-1-piperazineethanamine,4-[3-(methoxydimethylsilyl)propyl]-N,N-dimethyl-1-piperazineethanamine, 4-[3-(methoxydimethylsilyl)propyl]-N,N-diethyl-1-piperazineethanamine, 4-[3-(methoxydimethylsilyl)propyl]-N,N-dipropyl-1-piperazineethanamine, 4-[3-(methoxydimethylsilyl)propyl]-N,N-dibutyl-1-piperazineethanamine, 4-[3-(methoxydimethylsilyl)propyl]-N,N-dipentyl-1-piperazineethanamine, 4-[3-(methoxydimethylsilyl)propyl]-N,N-dipentyl-1-piperazineethanamine 4-[3-(ethoxydimethylsilyl)propyl]-N,N-dihexyl-1-piperazineethanamine, 4-[3-(ethoxydimethylsilyl)propyl]-N,N-dimethyl-1-piperazineethanamine, 4-[3-(ethoxydimethylsilyl)propyl]-N,N-diethyl-1-piperazineethanamine, 4-[3-(ethoxydimethylsilyl)propyl]-N,N-dipropyl-1-piperazineethanamine, 4-[3-(ethoxydimethylsilyl)propyl]-N,N-dibutyl-1-piperazineethanamine, 4-[3-(ethoxydimethylsilyl)propyl]- N,N-dipentyl-1-piperazineethanamine, 4-[3-(ethoxydimethylsilyl)propyl]-N,N-dihexyl-1-piperazineethanamine, 4-[8-(methoxydimethylsilyl)octyl]-N,N-dimethyl-1-piperazineethanamine, 4-[8-(methoxydimethylsilyl)octyl]-N,N-diethyl-1-piperazineethanamine, 4-[8-(methoxydimethylsilyl)octyl]-N,N-dipropyl-1-piperazineethanamine, 4-[8-(methoxydimethylsilyl)octyl]-N,N-dibutyl-1- Piperazineethanamine, 4-[8-(methoxydimethylsilyl)octyl]-N,N-dipentyl-1-piperazineethanamine, 4-[8-(methoxydimethylsilyl)octyl]-N,N-dihexyl-1-piperazineethanamine, 4-[8-(ethoxydimethylsilyl)octyl]-N,N-dimethyl-1-piperazineethanamine, 4-[8-(ethoxydimethylsilyl)octyl]-N,N-diethyl-1-piperazineethanamine, 4-[8-(ethoxydimethylsilyl)octyl]-N,N-dipropyl-1-piperazineethanamine,4-[(alkoxydialkylsilyl)alkyl]-N,N-dialkyl-1-piperazineethanamine compounds such as 4-[8-(ethoxydimethylsilyl)octyl]-N,N-dibutyl-1-piperazineethanamine, 4-[8-(ethoxydimethylsilyl)octyl]-N,N-dipentyl-1-piperazineethanamine, and 4-[8-(ethoxydimethylsilyl)octyl]-N,N-dihexyl-1-piperazineethanamine; 1-[(trimethoxysilyl)methyl]-4-[2-(pyrrolidinyl)ethyl]piperazine, 1- [(Trimethoxysilyl)methyl]-4-[2-(piperidinyl)ethyl]piperazine, 1-[(trimethoxysilyl)methyl]-4-[2-(azepanyl)ethyl]piperazine, 1-[(trimethoxysilyl)methyl]-4-[2-(morpholinyl)ethyl]piperazine, 1-[(trimethoxysilyl)methyl]-4-[2-(4-methyl-1-piperazinyl)ethyl]piperazine, 1-[(trimethoxysilyl)methyl]-4-[2-(4-ethyl-1-piperazinyl)ethyl]piperazine, 1-[(triethoxysilyl)methyl ]-4-[2-(pyrrolidinyl)ethyl]piperazine, 1-[(triethoxysilyl)methyl]-4-[2-(piperidinyl)ethyl]piperazine, 1-[(triethoxysilyl)methyl]-4-[2-(azepanyl)ethyl]piperazine, 1-[(triethoxysilyl)methyl]-4-[2-(morpholinyl)ethyl]piperazine, 1-[(triethoxysilyl)methyl]-4-[2-(4-methyl-1-piperazinyl)ethyl]piperazine, 1-[triethoxysilyl)methyl]-4-[2-(4-ethyl-1-piperazinyl) ethyl]piperazine, 1-[(trimethoxysilyl)propyl]-4-[2-(pyrrolidinyl)ethyl]piperazine, 1-[3-(trimethoxysilyl)propyl]-4-[2-(piperidinyl)ethyl]piperazine, 1-[3-(trimethoxysilyl)propyl]-4-[2-(pazepanyl)ethyl]piperazine, 1-[3-(trimethoxysilyl)propyl]-4-[2-(morpholinyl)ethyl]piperazine, 1-[3-(trimethoxysilyl)propyl]-4-[2-(4-methyl-1-piperazinyl)ethyl]piperazine,1-[3-(trimethoxysilyl)propyl]-4-[2-(4-ethyl-1-piperazinyl)ethyl]piperazine, 1-[3-(triethoxysilyl)propyl]-4-[2-(pyrrolidinyl)ethyl]piperazine, 1-[3-(triethoxysilyl)propyl]-4-[2-(piperidinyl)ethyl]piperazine, 1-[3-(triethoxysilyl)propyl]-4-[2-(azepanyl)ethyl]piperazine, 1-[3-(triethoxysilyl)propyl]-4-[2-(morpholinyl)ethyl]piperazine, 1-[ 3-(triethoxysilyl)propyl]-4-[2-(4-methyl-1-piperazinyl)ethyl]piperazine, 1-[3-(triethoxysilyl)propyl]-4-[2-(4-ethyl-1-piperazinyl)ethyl]piperazine, 1-[8-(trimethoxysilyl)octyl]-4-[2-(pyrrolidinyl)ethyl]piperazine, 1-[8-(trimethoxysilyl)octyl]-4-[2-(piperidinyl)ethyl]piperazine, 1-[8-(trimethoxysilyl)octyl]-4-[2-(azepanyl)ethyl]piperazine 1-[8-(trimethoxysilyl)octyl]-4-[2-(morpholinyl)ethyl]piperazine, 1-[8-(trimethoxysilyl)octyl]-4-[2-(4-methyl-1-piperazinyl)ethyl]piperazine, 1-[8-(trimethoxysilyl)octyl]-4-[2-(4-ethyl-1-piperazinyl)ethyl]piperazine, 1-[8-(triethoxysilyl)octyl]-4-[2-(pyrrolidinyl)ethyl]piperazine, 1-[8-(triethoxysilyl)octyl]-4-[2-(piperidinyl)ethyl]piperazine alkoxysilane compounds having a plurality of heterocyclic ring structures, such as 1-[8-(triethoxysilyl)octyl]-4-[2-(azepanyl)ethyl]piperazine, 1-[3-(triethoxysilyl)octyl]-4-[2-(morpholinyl)ethyl]piperazine, 1-[8-(triethoxysilyl)octyl]-4-[2-(4-methyl-1-piperazinyl)ethyl]piperazine, and 1-[8-(triethoxysilyl)octyl]-4-[2-(4-ethyl-1-piperazinyl)ethyl]piperazine.

[0023] Next, a method for producing a nitrogen-containing organoxysilane compound will be described. The nitrogen-containing organoxysilane compound according to the present invention can be produced by reacting a haloalkylalkoxysilane compound represented by the following general formula (2) (hereinafter referred to as "compound (2)") with 1,4-diazabicyclo[2.2.2]octane represented by the following general formula (3) (hereinafter referred to as "compound (3)") in the presence of an organic solvent, which is used as needed, and then reacting the resulting compound with a secondary amine compound represented by the following general formula (4) (hereinafter referred to as "compound (4)").

[0024] (In the formula, R 1 ~R 3 , X and n have the same meanings as above.)

[0025]

[0026] (In the formula, R 4 and R 5 has the same meaning as above.)

[0027] Specific examples of compound (2) include (chloroalkyl)trialkoxysilanes such as (chloromethyl)trimethoxysilane, (3-chloropropyl)trimethoxysilane, (8-chlorooctyl)trimethoxysilane, (chloromethyl)triethoxysilane, (3-chloropropyl)triethoxysilane, and (8-chlorooctyl)triethoxysilane; (chloromethyl)dimethoxymethylsilane, (3-chloropropyl)dimethoxymethylsilane, (8-chlorooctyl)dimethoxymethylsilane, and (chloromethyl)diethoxymethylsilane; (chloroalkyl)dialkoxyalkylsilanes such as (chloromethyl)methoxydimethylsilane, (3-chloropropyl)methoxydimethylsilane, (8-chlorooctyl)methoxydimethylsilane, (chloromethyl)ethoxydimethylsilane, (3-chloropropyl)ethoxydimethylsilane, and (8-chlorooctyl)ethoxydimethylsilane; and (chloroalkyl)alkoxydialkylsilanes such as (chloromethyl)methoxydimethylsilane, (3-chloropropyl)methoxydimethylsilane, (8-chlorooctyl)ethoxydimethylsilane.

[0028] Among these, from the viewpoint of easy availability of raw materials, (3-chloropropyl)alkoxysilane is preferred, and (3-chloropropyl)trimethoxysilane, (3-chloropropyl)triethoxysilane, (3-chloropropyl)dimethoxymethylsilane, (3-chloropropyl)diethoxymethylsilane, (3-chloropropyl)methoxydimethylsilane, and (3-chloropropyl)ethoxydimethylsilane are more preferred. Compound (2) may be commercially available or may be produced. When produced, it may be produced according to a conventionally known method, for example, by a method of subjecting a halogenated alkenyl compound and a hydrosilane compound to a hydrosilylation reaction.

[0029] In the above reaction, the amount of compound (2) used is not particularly limited, but is preferably in the range of 0.9 to 1.1 moles, more preferably 0.95 to 1.05 moles, per mole of compound (3).

[0030] Compound (3) may be commercially available.

[0031] Specific examples of compound (4) include linear dialkylamines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, and didecylamine; diisopropylamine, diisobutylamine, di(sec-butyl)amine, di(tert-butyl)amine, diisopentylamine, dineopentylamine, diisohexylamine, diisoheptylamine, diisooctylamine, and di(2-ethylhexyl)amine; branched dialkylamines such as dicyclopentylamine and dicyclohexylamine; cyclic dialkylamines such as diallylamine, dibutenylamine, dimethallylamine, dihexenylamine and dioctenylamine; diarylamines such as diphenylamine and ditolylamine; diaralkylamines such as dibenzylamine and diphenethylamine; and heterocyclic amines such as pyrrolidine, piperidine, azepane, morpholine and 1-methylpiperazine.

[0032] Among these, from the viewpoints of easy availability of raw materials and high reactivity, linear dialkylamines and heterocyclic amines are preferred, and diethylamine, dibutylamine, dihexylamine, azepane, morpholine, and 1-methylpiperazine are more preferred. Compound (4) may be commercially available or may be produced. When produced, it may be produced according to a conventionally known method, for example, by a method of subjecting a primary amine compound to a substitution reaction with an alkyl halide compound.

[0033] In the above reaction, the amount of compound (4) used is not particularly limited, but is preferably in the range of 0.9 to 3.0 moles, more preferably 0.95 to 2.0 moles, per mole of compound (3).

[0034] In the above reaction, from the viewpoint of suppressing side reactions, it is preferable to react compound (2) with compound (3), confirm the consumption of compound (2) by an analytical method such as gas chromatography or NMR, and then add compound (4) to the reaction mixture and react them.

[0035] The reaction can be carried out in the presence or absence of an organic solvent. Specific examples of usable organic solvents include hydrocarbon solvents such as benzene, toluene, and xylene; ether solvents such as diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyltetrahydropyran, and dioxane; ester solvents such as ethyl acetate and butyl acetate; aprotic polar solvents such as acetonitrile, N,N-dimethylformamide, and N-methylpyrrolidone; and alcohol solvents such as methanol and ethanol. These solvents may be used alone or in combination of two or more. When a solvent is used, the amount thereof is not particularly limited, but is preferably in the range of 0.01 to 1.0 liter, more preferably 0.02 to 0.50 liter, per mole of compound (3).

[0036] There is no limitation on the pressure during the reaction, but normal pressure is preferred. The reaction temperature is not particularly limited, but is preferably 20 to 200°C, more preferably 50 to 150°C. The reaction time is also not particularly limited, but is preferably 1 to 40 hours, more preferably 1 to 24 hours. The reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon.

[0037] In the above reaction, a catalyst may be used to shorten the reaction time. The catalyst is preferably a quaternary onium salt, and specific examples thereof include tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylphosphonium bromide, and tributylmethylphosphonium iodide.

[0038] In the above reaction, the by-product amine hydrohalide can be removed by filtration after the reaction is complete. Alternatively, the by-product amine hydrohalide can be regenerated into the amine by adding ethylenediamine, 1,8-diazabicyclo[5.4.0]-7-undecene, or the like after the reaction is complete.

[0039] The nitrogen-containing organoxysilane compound represented by the general formula (1) obtained by the production method of the present invention can be further purified before use by various purification methods such as distillation, filtration, washing, column separation, etc., depending on the desired quality. Purification by distillation is particularly preferred to achieve high purity.

[0040] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples. The purity of the nitrogen-containing organoxysilane compound is a value measured under the following gas chromatography measurement conditions. [Gas chromatography measurement conditions] Gas chromatograph: GC-2014 (Shimadzu Corporation) Packed column: Silicone SE-30 (GL Sciences Inc.) Detector: TCD Detector temperature: 300°C Injection port temperature: 300°C Heating program: 70°C (0 min) → 10°C / min → 300°C (10 min) Carrier gas: Helium (50 ml / min) Injection amount: 1 μl

[0041] Example 1 The interior of a four-neck flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was replaced with nitrogen. Nitrogen gas was passed through the open end at the top of the reflux condenser to prevent the inclusion of outside air. 56.1 g (500 mmol) of 1,4-diazabicyclo[2.2.2]octane and 12.0 g of methanol were charged and stirred. Next, while adjusting the internal temperature to 80°C, 99.3 g (500 mmol) of (3-chloropropyl)trimethoxysilane was added dropwise over 1 hour, followed by stirring at 80-100°C for 2 hours. Next, while adjusting the internal temperature to 140°C, 75.1 g (750 mmol) of 1-methylpiperazine was added dropwise over 1 hour, followed by stirring at 135-145°C for 10 hours. The reaction mixture was cooled to 60°C, and 45.1 g (750 mmol) of ethylenediamine was added dropwise. The mixture was then stirred at 60°C for 30 minutes. The reaction mixture was separated into two layers, and the lower layer was removed by a separation operation to obtain 167.5 g of a crude product. 1.7 g of a 28 mass % sodium methoxide methanol solution was added to the crude product, and the mixture was distilled at 70 Pa to obtain 1-[3-(trimethoxysilyl)propyl]-4-[2-(4-methyl-1-piperazinyl)ethyl]piperazine in a yield of 60.1% and a purity of 99.6%.

[0042] Mass spectrum of the resulting product: 1 The H-NMR spectrum (deuterated chloroform solvent) and the IR spectrum were measured. 1 The results of the H-NMR spectrum analysis are shown in Figure 1, and the results of the IR spectrum analysis are shown in Figure 2. Mass spectrum: m / z 374, 261, 113, 91, 70, 42 1 H-NMR spectrum (deuterated chloroform solvent): 1 H-NMR (600MHz, CDCl3): δ (ppm) = 3.52 (s, 9H), 2.45 (brm, 16H), 2.48 (s, 4H), 2. 28 (t, J=7.8Hz, 2H), 2.23 (s, 3H), 1.55 (quin, J=8.2Hz, 2H), 0.59-0.56 (m, 2H) IR spectrum: IR (ATR): 2938, 2795, 1452, 1293, 1189, 1164, 1087, 1013, 815 cm -1From the above results, the obtained compound was identified as 1-[3-(trimethoxysilyl)propyl]-4-[2-(4-methyl-1-piperazinyl)ethyl]piperazine.

[0043] Example 2 The interior of a four-neck flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was replaced with nitrogen. Nitrogen gas was passed through the open end at the top of the reflux condenser to prevent the inclusion of outside air. 22.4 g (200 mmol) of 1,4-diazabicyclo[2.2.2]octane and 8.0 g of ethanol were charged and stirred. Next, while adjusting the internal temperature to 80°C, 48.2 g (200 mmol) of (3-chloropropyl)triethoxysilane was added dropwise over 1 hour, followed by stirring at 80-100°C for 2 hours. Next, while adjusting the internal temperature to 140°C, 26.1 g (300 mmol) of morpholine was added dropwise over 1 hour, followed by stirring at 135-145°C for 10 hours. The reaction mixture was cooled to 60°C, and 18.0 g (300 mmol) of ethylenediamine was added dropwise. The mixture was then stirred at 60°C for 30 minutes. The reaction mixture was separated into two layers, and the lower layer was removed by a separation operation to obtain 58.9 g of a crude product. 1.0 g of a 20% by mass sodium ethoxide ethanol solution was added to the crude product, and the mixture was distilled at 0.1 kPa to obtain 1-[3-(triethoxysilyl)propyl]-4-[2-(morpholino)ethyl]piperazine in a yield of 58.6% and a purity of 99.3%.

[0044] Mass spectrum of the resulting product: 1 The H-NMR spectrum (deuterated chloroform solvent) and the IR spectrum were measured. 1 The results of the H-NMR spectrum analysis are shown in Figure 3, and the results of the IR spectrum analysis are shown in Figure 4. Mass spectrum: m / z 403, 303, 257, 202, 100, 70 1 H-NMR spectrum (deuterated chloroform solvent): 1H-NMR (600MHz, CDCl3): δ (ppm) = 3.77 (q, J = 7.4Hz, 6H), 3.66 (t, J = 4.6Hz, 4H), 2.48 (s, 4H), 2.43 (b rm, 12H), 2.39 (t, J=7.8Hz, 2H), 1.55 (quin, J=8.2Hz, 2H), 1.17 (t, J=6.9Hz, 9H), 0.57-0.55 (m, 2H) IR spectrum: IR (ATR): 2937, 2806, 1448, 1295, 1165, 1118, 1079, 1010, 956 cm -1 From the above results, the obtained compound was confirmed to be 1-[3-(triethoxysilyl)propyl]-4-[2-(morpholino)ethyl]piperazine.

[0045] Example 3: The interior of a four-neck flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was replaced with nitrogen. Nitrogen gas was passed through the open end at the top of the reflux condenser to prevent the inclusion of external air. 22.4 g (200 mmol) of 1,4-diazabicyclo[2.2.2]octane and 8.0 g of methanol were charged and stirred. Next, while adjusting the internal temperature to 80°C, 39.7 g (200 mmol) of (3-chloropropyl)trimethoxysilane was added dropwise over 1 hour, followed by stirring at 80-100°C for 2 hours. Next, while adjusting the internal temperature to 140°C, 29.8 g (300 mmol) of azepane was added dropwise over 1 hour, followed by stirring at 135-145°C for 10 hours. The reaction mixture was cooled to 60°C, and 18.0 g (300 mmol) of ethylenediamine was added dropwise. The mixture was then stirred at 60°C for 30 minutes. The reaction mixture was separated into two layers, and the lower layer was removed by a separation operation to obtain 59.4 g of a crude product. 1.5 g of a 28% by mass sodium methoxide methanol solution was added to the crude product, and the mixture was distilled at 0.1 kPa to obtain 1-[3-(trimethoxysilyl)propyl]-4-[2-(azepanyl)ethyl]piperazine in a yield of 51.1% and a purity of 97.2%.

[0046] Mass spectrum of the resulting product: 1 The H-NMR spectrum (deuterated chloroform solvent) and the IR spectrum were measured. 1The results of the H-NMR spectrum analysis are shown in Figure 3, and the results of the IR spectrum analysis are shown in Figure 4. Mass spectrum: m / z 373, 261, 192, 130, 112, 58 1 H-NMR spectrum (deuterated chloroform solvent): 1 H-NMR (600MHz, CDCl3): δ (ppm) = 3.51 (s, 9H), 2.61-2.59 (m, 6H), 2.45 (brm, 8H), 2.4 4 (t, J=7.7Hz, 2H), 2.28 (t, J=7.8Hz, 2H), 1.58-1.52 (m, 10H), 0.58 (t, J=8.7Hz, 2H) IR spectrum: IR (ATR): 2936, 2807, 1453, 1304, 1190, 1088, 1010, 817, 780 cm -1 From the above results, the compound obtained was identified as 1-[3-(trimethoxysilyl)propyl]-4-[2-(azepanyl)ethyl]piperazine.

Claims

1. A nitrogen-containing organoxysilane compound represented by the following general formula (1): (In the formula, R 1 and R 2 each independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms; R 3 represents an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, which may contain a heteroatom; R 4 and R 5 each independently represents a substituted (excluding silyl groups) or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms; R 4 and R 5 may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded, and n represents an integer of 0 to 2.

2. The following general formula (2): (In the formula, R 1 ~R 3 and n are as defined above, and X represents a chlorine atom, a bromine atom, or an iodine atom, and and then reacting the compound represented by the following general formula (4) with 1,4-diazabicyclo[2.2.2]octane: (In the formula, R 4 and R 5 2. The method for producing a nitrogen-containing organoxysilane compound according to claim 1, wherein a secondary amine compound represented by the formula:

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