Method for producing silyl amicate compounds and silyl amicate compounds

Abstract

To provide a method for producing silyl ester compounds of amidic acid without generating by-products. [Solution] A method for producing a silyl ester compound of an amide acid, comprising the step of reacting a compound having a predetermined bissilylamino group with a predetermined amine compound and a predetermined acid anhydride, for example, as shown in the scheme below. TIFF2026089321000034.tif27161

Description

[Technical Field]

[0001] This invention relates to a method for producing silyl ester compounds of amidic acid and to silyl ester compounds of amidic acid. [Background technology]

[0002] Silyl ester compounds of polyamic acids are precursors of imide compounds and can be converted to imide compounds by heating. Compared to their corresponding polyamic acids, silyl ester compounds of polyamic acids have lower polarity, resulting in good solubility in various organic solvents, low viscosity, and ease of handling.

[0003] One reported method for producing such silyl amide ester compounds involves reacting an amine compound with an acid anhydride to produce an amide acid, followed by silylation of the free carboxylic acid using trimethylsilyl chloride in the presence of triethylamine (Patent Document 1). In addition, a method has been reported in which an amine compound is reacted with N,O-bistrimethylsilyltrifluoroacetamide to produce N-trimethylsilylamine, which is then reacted with an acid anhydride (Non-Patent Literature 1). Furthermore, a method has been reported in which an N,N-bis(trimethylsilyl)amine compound is reacted with a dicarboxylic acid anhydride in the presence of a protic compound or water (Patent Document 2). [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] Journal of Photopolymer Science and Technology, 2001,14,37-40 [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2001-072690 [Patent Document 2] Japanese Patent Publication No. 2007-332091 [Overview of the project] [Problems that the invention aims to solve]

[0006] In the method described in Patent Document 1, solid triethylamine hydrochloride is produced as the reaction progresses, requiring separation by filtration or other means. Furthermore, not only is the process complex, but washing of the residue is also necessary to obtain the target product in good yield.

[0007] In the method described in Non-Patent Document 1, an amine compound is reacted with N,O-bistrimethylsilyltrifluoroacetamide, and the resulting N-silylamine compound is reacted with an acid anhydride without purification to obtain a silyl amide ester compound. Therefore, to obtain a high-purity silyl amide ester compound, it is necessary to remove the desilylated trifluoroacetamide and N-trimethylsilyltrifluoroacetamide. However, removing these compounds by heating strips may convert the silyl amide ester compound into an imide compound.

[0008] While the method described in Patent Document 2 can produce silyl ester compounds of amidic acid with high purity, it also produces protic compounds or compounds in which water has been silylated. Therefore, it has the same problems as described in Non-Patent Document 1.

[0009] The present invention has been made in view of the above matters, and aims to provide a method for producing silyl ester compounds of amic acid without generating by-products, and a silyl ester compound of amic acid. [Means for solving the problem]

[0010] As a result of intensive studies to solve the above problems, the present inventors have found that an amido acid silyl ester compound of interest can be obtained without generating by-products by a production method including a reaction of a compound having a bissilylamino group, an amine compound, and an acid anhydride, and have completed the present invention.

[0011] That is, the present invention provides 1. The following general formula (1-A), (1-B), (1-C) or (1-D) [Chemical formula] [(In the formula, R 1 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms which may have an oxygen, nitrogen, silicon or sulfur atom intervening therebetween, R 2 represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms which may have an oxygen, nitrogen, silicon, sulfur atom or siloxane bond intervening therebetween, X represents a bissilylamino group represented by the following general formula (2), R 3 each independently represents a monovalent hydrocarbon group having 1 to 6 carbon atoms having a bissilylamino group represented by the following general formula (2) at the terminal or an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, but at least one of R 3 is a monovalent hydrocarbon group having 1 to 6 carbon atoms having the bissilylamino group at the terminal. In general formula (1-C), when the number of the monovalent hydrocarbon groups having 1 to 6 carbon atoms having the bissilylamino group at the terminal in R 3 is p 1 , p 1 is a number satisfying 0 < p 1 / 2n + 6 ≤ 0.8. In general formula (1-D), when the number of the monovalent hydrocarbon groups having 1 to 6 carbon atoms having the bissilylamino group at the terminal in R 3 is q 1 , q 1 is a number satisfying 0 < q 1 / 2m + 6 ≤ 0.8. n represents an integer of 0 to 1000, and m represents 0, 1, 2 or 3. [Chemical formula] (In the formula, R4 Each of the symbols independently represents an unsubstituted monovalent hydrocarbon group with 1 to 10 carbon atoms, and *- represents a bond. A compound having a bissilylamino group represented by, The following general formulas (3-A), (3-B), (3-C), or (3-D) [ka] (In the formula, R 1 , R 2 ,n and m have the same meanings as above, R 5 Each of these independently represents a monovalent hydrocarbon group having 1 to 6 carbon atoms with a primary amino group at its terminus, or an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, but R 5 At least one of them is a monovalent hydrocarbon group having 1 to 6 carbon atoms and having a primary amino group at its terminus, and in general formula (3-C), R 5 The number of C1-C6 monovalent hydrocarbon groups having the primary amino group at the terminal is p 2 Therefore, p 2 is 0 <p 2 It is a number that satisfies / 2n+6≦0.8, and in the general formula (3-D), R 5 The number of monovalent hydrocarbon groups with 1 to 6 carbon atoms having a primary amino group at the end is q. 2 Therefore, q 2 is 0 2 (This is a number that satisfies the condition / 2m + 6 ≤ 0.8.) An amine compound represented by, The following general formula (4) or general formula (5) [ka] (In the formula, R 6 and R 7 Each of these independently represents a hydrogen atom, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a methylene group formed with the carbon atoms on the ring to which they are bonded, or an SiO-containing C1-C10 alkyl group, R 6 and R 7 ​These may bond with each other to form an aliphatic cyclic structure, a heterocyclic structure, or an aromatic cyclic structure with the carbon atoms to which they are bonded, but in that case, R 6 and R 7 The substituents of the substituted alkyl group in R do not include carboxyl groups or hydroxyl groups. 8 (This represents a single bond or a double bond.) The process includes reacting an acid anhydride having 1 to 4 structures represented by the following general formula (6-A), (6-B), (6-C), or (6-D). [ka] (In the formula, R 1 , R 2 ,n and m have the same meanings as above, R 9 Each of these independently represents a monovalent hydrocarbon group having 1 to 6 carbon atoms having a silyl amide ester structure represented by the following general formula (7) at its terminal, or an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, but R 9 At least one of them is a monovalent hydrocarbon group having 1 to 6 carbon atoms and having the silyl ester structure of the amidate at its terminus, and in the general formula (6-C), R 9 The number of monovalent hydrocarbon groups having 1 to 6 carbon atoms and having the silyl ester structure of the amidate at the terminal is p 3 Therefore, p 3 is 0 <p 3 It is a number that satisfies / 2n+6≦0.8, and in the general formula (3-D), R 9 The number of monovalent hydrocarbon groups having the silyl ester structure of the amidate at the terminal, with carbon atoms 1 to 6, is q. 3 Therefore, q 3 is 0 3 Y is a number that satisfies / 2m+6≦0.8, and Y represents the base represented by the following general formula (7). [ka] (In the formula, R 4 , R 5 and R 7 ~R 9 (This has the same meaning as above, and *- represents a coupling.) ​A method for producing a silyl ester compound represented by the amidoic acid, 2. Silyl ester compounds of amidoates represented by the following general formula (8) [ka] (In the formula, R 4 Each of these independently represents an unsubstituted monovalent hydrocarbon group with 1 to 10 carbon atoms, and R 6 and R 7 Each of these independently represents a hydrogen atom, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a methylene group formed with the carbon atoms on the ring to which they are bonded, or an SiO-containing C1-C10 alkyl group, R 6 and R 7 These may bond with each other to form an aliphatic cyclic structure, a heterocyclic structure, or an aromatic cyclic structure with the carbon atoms to which they are bonded, but in that case, R 6 and R 7 The substituents of the substituted alkyl group in R do not include carboxyl groups or hydroxyl groups. 8 R represents a single bond or a double bond. 10 and R 11 Each of these independently represents an unsubstituted monovalent hydrocarbon group with 1 to 6 carbon atoms, and R 12 (where r represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, which may contain an oxygen, nitrogen, silicon, sulfur atom, or siloxane bond, and r represents 1 or 2.) To provide. [Effects of the Invention]

[0012] According to the present invention, since no by-products are generated, silyl ester compounds of amidic acid can be produced without removing by-products by filtration or heated strips. In particular, the desired silyl ester compound of amidic acid can be obtained without causing an imidation reaction by heated strips. [Brief explanation of the drawing]

[0013] [Figure 1]This figure shows the 1H-NMR spectrum of the compound obtained in Example 1. [Figure 2] This figure shows the 1H-NMR spectrum of the compound obtained in Example 2. [Figure 3] This figure shows the 1H-NMR spectrum of the compound obtained in Example 3. [Figure 4] This figure shows the 1H-NMR spectrum of the compound obtained in Example 4. [Figure 5] This figure shows the 1H-NMR spectrum of the compound obtained in Example 5. [Figure 6] This figure shows the 1H-NMR spectrum of the compound obtained in Example 6. [Figure 7] This figure shows the 1H-NMR spectrum of the compound obtained in Example 7. [Figure 8] This figure shows the 1H-NMR spectrum of the compound obtained in Example 8. [Figure 9] This figure shows the 1H-NMR spectrum of the compound obtained in Example 9. [Modes for carrying out the invention]

[0014] The present invention will be described in detail below. The present invention provides a method for producing a silyl amide ester compound, comprising a compound having a bissilylamino group represented by the following general formulas (1-A), (1-B), (1-C), or (1-D) (hereinafter referred to as "compound (1-A)", "compound (1-B)", "compound (1-C)", and "compound (1-D)", respectively, and collectively referred to as "compound (1)") and an amine compound represented by the following general formulas (3-A), (3-B), (3-C), or (3-D) (hereinafter referred to as "compound (3-A)", "compound (3-B)", "compound (3-C)", and Compound (3-D) is called "compound (3-D)" and is collectively referred to as "compound (3)." This is done by reacting a silyl amide ester compound represented by the following general formulas (6-A), (6-B), (6-C), or (6-D) with an acid anhydride having 1 to 4 structures represented by the following general formulas (4) or (5) (hereinafter referred to as "compound (4)" or "compound (5)" respectively) to obtain a silyl amide ester compound represented by the following general formulas (6-A), (6-B), (6-C), or (6-D) (hereinafter referred to as "compound (6)" respectively and collectively referred to as "compound (6)").

[0015] [1] About compound (1) [ka]

[0016] In general formula (1-A), R 1 This represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, which may be interposed by oxygen, nitrogen, silicon, sulfur atoms, or siloxane bonds. R 1The monovalent hydrocarbon group can be linear, branched, or cyclic. Specific examples include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl groups; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, texyl, and 2-ethylhexyl groups; cyclic alkyl groups such as cyclopentyl and cyclohexyl groups; alkenyl groups such as vinyl, allyl, propenyl, butenyl, and pentenyl groups; aryl groups such as phenyl, tolyl, and naphthyl groups; and aralkyl groups such as benzyl, phenethyl, and naphthylmethyl groups. Among these, R 1 Preferably, the alkyl groups are substituted or unsubstituted linear C1-C10 alkyl groups and unsubstituted linear C1-C10 alkenyl groups. From the viewpoint of ease of raw material procurement, substituted or unsubstituted linear C1-C5 alkyl groups and unsubstituted linear C1-C5 alkenyl groups are more preferred, and substituted propyl groups and allyl groups having substituents, as described later, are even more preferred.

[0017] Also, R 1 However, examples of monovalent hydrocarbon groups that involve oxygen, nitrogen, silicon, sulfur atoms or siloxane bonds include alkyloxyalkyl groups, alkylaminoalkyl groups, alkylenedialkylsilylalkyl groups, alkylenedialkylsilylaryl groups, alkylthioalkyl groups, alkyldimethylsiloxanylalkyl groups, alkylpolydimethylpolysiloxanylalkyl groups, and the like.

[0018] Note, R 1The monovalent hydrocarbon group may have some or all of its hydrogen atoms substituted with substituents, such substituents include, for example, alkoxy groups having 1 to 3 carbon atoms; halogen atoms such as chlorine, bromine, and iodine atoms; aryl groups having 6 to 10 carbon atoms; aralkyl groups having 7 to 10 carbon atoms; cyano groups, amino groups, acyl groups, carboxyl groups, alkoxyalkyl groups having 1 to 6 carbon atoms, alkoxycarbonyl groups having 1 to 3 carbon atoms, trialkoxysilyl groups having 3 to 9 carbon atoms, alkyldialkoxysilyl groups having 3 to 12 carbon atoms, dialkylalkoxysilyl groups having 3 to 15 carbon atoms, and trialkylsilyl groups having 3 to 18 carbon atoms.

[0019] In general formula (1-B), R 2 This represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 2 to 18 carbon atoms, and more preferably 2 to 8 carbon atoms, which may be interposed by oxygen, nitrogen, silicon, or sulfur atoms. R 2 The divalent hydrocarbon group can be linear, branched, or cyclic. Specific examples include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, hexamethylene, octamethylene, decylene, dodecylene, tetradecylene, hexadecylene, and octadecylene; branched alkylene groups such as methyltrimethylene and methyltetramethylene; cyclic alkylene groups such as cyclohexylene and methylenecyclohexylenemethylene; linear alkenylene groups such as butenylene, hexenylene, and octenylene; branched alkenylene groups such as isobutenylene; arylene groups such as phenylene; and aralkylene groups such as methylenephenylene and methylenephenylmethylenemethylene. Among these, R 2Preferably, the groups are substituted or unsubstituted linear alkylene groups having 2 to 10 carbon atoms, substituted or unsubstituted arylene groups having 6 to 15 carbon atoms, and substituted or unsubstituted aralkylene groups having 7 to 15 carbon atoms. From the viewpoint of ease of raw material procurement, unsubstituted linear alkylene groups having 2 to 8 carbon atoms, unsubstituted arylene groups having 6 to 12 carbon atoms, and unsubstituted aralkylene groups having 7 to 12 carbon atoms are more preferred, and ethylene groups, propylene groups, phenylene groups, and methylenephenylmethylene groups are even more preferred.

[0020] Also, R 2 However, examples of divalent hydrocarbon groups that involve oxygen, nitrogen, silicon, or sulfur atoms include alkyleneoxyalkylene groups, alkyleneaminoalkylene groups, alkylenedialkylsilylalkylene groups, alkylenedialkylsilylarylene groups, alkylentioalkylene groups, and others. Note, R 2 Some or all of the hydrogen atoms in the divalent hydrocarbon group may be substituted with substituents, such as R 1 Similar examples include the above.

[0021] In general formulas (1-A) and (1-B), X represents a bissilylamino group represented by the following general formula (2).

[0022] [ka] (In the formula, *- represents a bond.)

[0023] In general formula (2), R 4 Each of these independently represents an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 carbon atom. R 4The monovalent hydrocarbon group can be linear or cyclic, and specific examples include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and decyl groups; cyclic alkyl groups such as cyclopentyl and cyclohexyl groups; alkenyl groups such as vinyl and allyl groups; and aryl groups such as phenyl groups. Among these, R 4 As such, unsubstituted linear alkyl groups having 1 to 5 carbon atoms are preferred, and from the viewpoint of ease of raw material procurement and reactivity, unsubstituted linear alkyl groups having 1 to 3 carbon atoms are more preferred, and methyl groups are even more preferred.

[0024] In general formulas (1-C) and (1-D), R 3 Each of these independently represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, or an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, having a bissilylamino group represented by general formula (2) at its terminus, but R 3 At least one of these is a monovalent hydrocarbon group having the bissilylamino group described above at its terminal end.

[0025] R 3 Specific examples of monovalent hydrocarbon groups having a bissilylamino group at its terminus are preferably linear, and specific examples include bissilylaminomethyl group, bissilylaminopropyl group, bissilylaminobutyl group, bissilylaminopentyl group, and bissilylaminohexyl group. Among these, R 3 Preferably, a linear monovalent hydrocarbon group having 1 to 4 carbon atoms and a bissilylamino group is preferred, and from the viewpoint of ease of raw material procurement, a linear monovalent hydrocarbon group having 1 to 3 carbon atoms and a bissilylamino group is more preferred.

[0026] R 3The non-substituted monovalent hydrocarbon group may be linear or cyclic. Specific examples thereof include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-group, etc.; cyclic alkyl groups such as cyclopentyl, cyclohexyl groups, etc.; alkenyl groups such as vinyl, allyl groups, etc.; aryl groups such as phenyl group, etc. Among these, R 3 is preferably a non-substituted linear alkyl group having 1 to 4 carbon atoms, a non-substituted linear alkenyl group having 1 to 3 carbon atoms, or an aryl group. From the perspective of easy availability of raw materials, a non-substituted linear alkyl group having 1 to 3 carbon atoms, a linear alkenyl group having 1 to 3 carbon atoms, or an aryl group is more preferable, and methyl, vinyl, or phenyl group is even more preferable.

[0027] In general formula (1-C), the number of the monovalent hydrocarbon groups having 1 to 6 carbon atoms and having a bissilylamino group at the above-mentioned terminal in R 3 is represented by p 1 Then, p 1 is a number satisfying 0 < p 1 / 2n + 6 ≤ 0.8, preferably 0.05 < p 1 / 2n + 6 ≤ 0.6, more preferably 0.1 < p 1 / 2n + 6 ≤ 0.5. n represents an integer of 0 to 1000, preferably 0 to 500, more preferably 0 to 200.

[0028] In general formula (1-D), the number of the monovalent hydrocarbon groups having 1 to 6 carbon atoms and having a bissilylamino group at the above-mentioned terminal in R 3 is represented by q 1 Then, q 1 is a number satisfying 0 < q 1 / 2m + 6 ≤ 0.8, preferably 0.05 < q 1 / 2m + 6 ≤ 0.6, more preferably 0.1 < q 1 / 2m + 6 ≤ 0.5. m is 0, 1, 2 or 3, preferably representing 1.

[0029] Specific examples of compound (1-A) include N,N-bis(trimethylsilyl)methylamine, N,N-bis(trimethylsilyl)ethylamine, N,N-bis(trimethylsilyl)propylamine, N,N-bis(trimethylsilyl)hexylamine, N,N-bis(trimethylsilyl)octylamine, N,N-bis(trimethylsilyl)methoxyethylamine, N,N-bis(trimethylsilyl)methoxypropylamine, N,N-bis(trimethylsilyl)ethoxypropylamine, N,N-bis(trimethylsilyl) N,N-bis(trimethylsilyl) alkylamines such as s(trimethylsilyl)-N',N'-dimethylethylenediamine, N,N-bis(trimethylsilyl)-N',N'-diethylethylenediamine, and N,N-bis(trimethylsilyl)methylsulfanylethylamine; N,N-bis(trimethylsilyl) alkenylamines such as N,N-bis(trimethylsilyl)allylamine, N,N-bis(trimethylsilyl)hexenylamine, and N,N-bis(trimethylsilyl)octenylamine;N,N-bis(trimethylsilyl)trimethoxysilylpropylamine, N,N-bis(trimethylsilyl)methyldimethoxysilylpropylamine, N,N-bis(trimethylsilyl)dimethylmethoxysilylpropylamine, N,N-bis(trimethylsilyl)triethoxysilylpropylamine, N,N-bis(trimethylsilyl)methyldiethoxysilylpropylamine, N,N-bis(trimethylsilyl)dimethylethoxysilylpropylamine, N,N-bis(trimethylsilyl)trimethoxysilyloctylamine, N,N-bis(trimethylsilyl)methyldimethoxysilyloctylamine, N,N-bis(trimethylsilyl Examples include N,N-bis(trimethylsilyl)alkylamines having an alkoxysilyl group, such as dimethylmethoxysilyloctylamine, N,N-bis(trimethylsilyl)-(trimethoxysilylethyldimethylsiloxydimethylsilyl)propylamine, N,N-bis(trimethylsilyl)-(triethoxysilylethyldimethylsiloxydimethylsilyl)propylamine, and N,N-bis(trimethylsilyl)-(trimethoxysilylethyldimethylsilylphenylenedimethylsilyl)propylamine. Compound (1-A) may be a commercially available product or may be manufactured. If manufactured, conventionally known methods may be followed, for example, by reacting an amine compound with a trialkylsilyl chloride.

[0030] Specific examples of compound (1-B) include bis(N,N-bis(trimethylsilyl)amino)alkanes such as 1,2-bis(N,N-bis(trimethylsilyl)amino)ethane, 1,3-bis(N,N-bis(trimethylsilyl)amino)propane, 1,4-bis(N,N-bis(trimethylsilyl)amino)butane, 1,6-bis(N,N-bis(trimethylsilyl)amino)hexane, and 1,8-bis(N,N-bis(trimethylsilyl)amino)octane; 1,2-bis(N,N-bis(trimethylsilyl)amino)benzene, 1,3-bis(N,N-bis(trimethylsilyl)amino)benzene, 1,4-bis(N,N-bis(trimethylsilyl)amino)benzene, 1,2-bis(N,N-bis(trimethylsilyl)aminomethyl)benzene, 1,3-bis(N,N-bis(trimethylsilyl)aminomethyl)benzene, 1,4-bis(N,N-bis(trimethylsilyl)aminomethyl)benzene, etc. Examples of bis(N,N-bis(trimethylsilyl)aminopropyl)benzenes include N,N-bis(trimethylsilyl)aminopropyl) ether, bis(N,N-bis(trimethylsilyl)aminopropyl) sulfide, bis(N,N-bis(trimethylsilyl)aminopropyl) sulfide, bis(N,N-bis(trimethylsilyl)aminopropyl) dimethylsilane, bis(N,N-bis(trimethylsilyl)aminopropyl) diethylsilane, bis(N,N-bis(trimethylsilyl)aminopropyl) diphenylsilane, and other oxygen, sulfur, and silicon-mediated bis(N,N-bis(trimethylsilyl)amino) alkanes; and bis(N,N-bis(trimethylsilyl)aminopropyl) dimethylsilyl) benzenes such as 1,2-bis(N,N-bis(trimethylsilyl)aminopropyl)dimethylsilyl)benzene, 1,3-bis(N,N-bis(trimethylsilyl)aminopropyl)dimethylsilyl)benzene, and 1,4-bis(N,N-bis(trimethylsilyl)aminopropyl)dimethylsilyl)benzene. Compound (1-B) may be a commercially available product or may be manufactured. If manufactured, conventionally known methods may be followed, for example, by reacting an amine compound with a trialkylsilyl chloride.

[0031] Specific examples of compound (1-C) include siloxane compounds having an N,N-bis(trimethylsilyl)amino group at one end, such as 3-N,N-bis(trimethylsilyl)aminopropyl-1,1,1,3,3-pentamethyldisiloxane, 9-N,N-bis(trimethylsilyl)aminopropyl-1,1,3,5,5,7,7,9,9-undecamethylpentasiloxane, and ω-N,N-bis(trimethylsilyl)aminopropyl-polydimethylpolysiloxane; 1,3-bis(N,N-bis(trimethylsilyl)aminopropyl)-1,1,3, Siloxanes having N,N-bis(trimethylsilyl)amino groups at both ends, such as 3-tetramethyldisiloxane, 1,9-bis(N,N-bis(trimethylsilyl)aminopropyl)-1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane, 1,15-bis(N,N-bis(trimethylsilyl)aminopropyl)-1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15-hexadecamethyloctasiloxane, α,ω-bis(N,N-bis(trimethylsilyl)aminopropyl)-polydimethylpolysiloxane, etc. San compounds; siloxanes having an N,N-bis(trimethylsilyl)amino group in the side chain, such as 3-N,N-bis(trimethylsilyl)aminopropyl)-1,1,1,3,5,5,7,7,9,11,11,13,13,15,15,17,17,17-nonadecamethylnonasiloxane, 3,5-bis(N,N-bis(trimethylsilyl)aminopropyl)-1,1,1,3,5,7,7,7-octamethyltetrasiloxane Examples include siloxane compounds having N,N-bis(trimethylsilyl)amino groups at both ends and in the side chain, such as 1,3,5-tris(N,N-bis(trimethylsilyl)aminopropyl)-1,1,3,5,5-pentamethyltrisiloxane, 1,9,17-tris(N,N-bis(trimethylsilyl)aminopropyl)-1,1,3,3,5,5,7,7,9,11,11,13,13,15,15,17,17-heptadecamethylnonasiloxane, and poly(N,N-bis(trimethylsilyl)aminopropyl)-polydimethylpolysiloxane. Compound (1-C) may be a commercially available product or may be manufactured. If manufactured, conventionally known methods can be followed, for example, by reacting a hydrosiloxane compound with an N,N-bis(trimethylsilyl)alkenylamine using a transition metal catalyst.

[0032] Specific examples of compound (1-D) include cyclic trisiloxane compounds such as 1-bis(bis(trimethylsilyl)aminopropyl)-1,3,3,5,5-pentamethylcyclotrisiloxane and 1,3,5-tris(bis(trimethylsilyl)aminopropyl)-1,3,5-trimethylcyclotrisiloxane; 1-bis(trimethylsilyl)aminopropyl-1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane, 1,3-bis(bis(trimethylsilyl)aminopropyl)-1,3,5,5,7,7-hexamethylcyclotetrasiloxane, 1,5-bis(bis(trimethylsilyl)aminopropyl)-1,3,3,5,7,7-hexamethylcyclotetrasiloxane, and 1,3-bis(bis(trimethylsilyl)aminopropyl)-5,7-dipropyl Examples include cyclic tetrasiloxane compounds such as ropyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-bis(bis(trimethylsilyl)aminopropyl)-3,7-dipropyl-1,3,5,7-tetramethylcyclotetrasiloxane, and 1,3,5,7-tetrakiss(bis(trimethylsilyl)aminopropyl)-1,3,5,7-tetramethylcyclotetrasiloxane; cyclic pentasiloxane compounds such as 1,3,5,7,9-pentakis(bis(trimethylsilyl)aminopropyl)-1,3,5,7,9-pentamethylcyclopentasiloxane; and cyclic hexasiloxane compounds such as 1,3,5,7,9,11-hexakis(bis(trimethylsilyl)aminopropyl)-1,3,5,7,9,11-hexamethylcyclohexasiloxane. Regarding the compound (1-D), commercially available products may be used, or it may be produced. When producing it, it may be produced according to a conventionally known method. For example, it can be obtained by reacting a cyclic hydrosiloxane compound with N,N-bis(trimethylsilyl)alkenylamine using a transition metal catalyst or the like.

[0033] [2] Regarding the compound (3)

Chemical formula

[0034] In the general formulas (3-C) and (3-D), R 5 each independently represents a monovalent hydrocarbon group having a primary amino group at the terminal, having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, or an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. However, at least one of R 5 is a monovalent hydrocarbon group having a primary amino group at the terminal.

[0035] As the monovalent hydrocarbon group having a primary amino group at the terminal of R 5 , a linear group is preferable. Specific examples thereof include linear aminoalkyl groups such as aminomethyl, aminopropyl, aminobutyl, aminopentyl, and aminohexyl groups. Among these, as R 5 , a linear aminoalkyl group having 1 to 5 carbon atoms is preferable. From the viewpoint of easy availability of raw materials, a linear aminoalkyl group having 1 to 4 carbon atoms is more preferable, and an aminopropyl group is even more preferable. As the unsubstituted monovalent hydrocarbon group of R 5 , the same groups as the unsubstituted monovalent hydrocarbon group of R 3 can be mentioned.

[0036] In the general formula (3-C), the number of the monovalent hydrocarbon groups having 1 to 6 carbon atoms with a primary amino group at the terminal in R 5 is p2 Therefore, p 2 is, 0 <p 2 / 2n+6≦0.8, preferably 0.05 <p 2 / 2n+6≦0.6, more preferably 0.1 <p 2 It is a number that satisfies the condition / (2n+6) ≤ 0.5. In general formula (3-D), R 5 The number of monovalent hydrocarbon groups with 1 to 6 carbon atoms having a primary amino group at the end of the above-mentioned group is q. 2 Therefore, q 2 is, 0 2 / 2m+6≦0.8, preferably 0.05 2 / 2m+6≦0.6, more comfortable 0.1 2 It is a number that satisfies the condition / 2m+6≦0.5.

[0037] Specific examples of compound (3-A) include alkylamines such as methylamine, ethylamine, propylamine, hexylamine, octylamine, methoxyethylamine, methoxypropylamine, ethoxypropylamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, and methylsulfanylethylamine; alkenylamines such as allylamine, hexenylamine, and octenylamine; and trimethoxysilylpropylamine, methyldimethoxysilylpropylamine, dimethylmethoxysilylpropylamine, triethoxysilylpropylamine, and methyldiethoxysilylpropylamine. Examples include trimethylsilyl alkylamines having an alkoxysilyl group, such as propylamine, dimethylethoxysilylpropylamine trimethoxysilyloctylamine, methyldimethoxysilyloctylamine, dimethylmethoxysilyloctylamine, (trimethoxysilylethyldimethylsiloxydimethylsilyl)propylamine, (methyldimethoxysilylethyldimethylsiloxydimethylsilyl)propylamine, (triethoxysilylethyldimethylsiloxydimethylsilyl)propylamine, and (trimethoxysilylethyldimethylsilylphenylenedimethylsilyl)propylamine. ​​​Compound (3-A) may be a commercially available product or may be manufactured. If manufactured, conventionally known methods may be followed, for example, by reacting an alkyl halide with ammonia or its equivalent.

[0038] Specific examples of compound (3-B) include diaminoalkanes such as 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, and 1,8-diaminooctane; diaminobenzenes such as 1,2-diaminobenzene, 1,3-diaminobenzene, 1,4-diaminobenzene, 1,2-bis(aminomethyl)benzene, 1,3-bis(aminomethyl)benzene, and 1,4-bis(aminomethyl)benzene; diaminoalkanes mediated by oxygen, sulfur, and silicon atoms such as bis(aminopropyl) ether, bis(aminopropyl) sulfide, bis(aminopropyl)dimethylsilane, bis(aminopropyl)diethylsilane, and bis(aminopropyl)diphenylsilane; and bis(aminopropyldimethylsilyl)benzenes such as 1,2-bis(aminopropyldimethylsilyl)benzene, 1,3-bis(aminopropyldimethylsilyl)benzene, and 1,4-bis(aminopropyldimethylsilyl)benzene. The amine compound represented by compound (3-B) can be a commercially available product.

[0039] Specific examples of compound (3-C) include siloxane compounds having an amino group at one end, such as 3-aminopropyl-1,1,1,3,3-pentamethyldisiloxane, 9-aminopropyl-1,1,1,3,3,5,5,7,7,9,9-undecamethylpentasiloxane, and ω-aminopropyl-polydimethylpolysiloxane; 1,3-bis(aminopropyl)-1,1,3,3-tetramethyldisiloxane Siloxane compounds having amino groups at both ends, such as 1,9-bis(aminopropyl)-1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane, 1,15-bis(aminopropyl)-1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15-hexadecamethyloctasiloxane, and α,ω-bis(aminopropyl)-polydimethylpolysiloxane; 3- Siloxane compounds having amino groups in their side chains, such as aminopropyl-1,1,1,3,5,5,5-heptamethyltrisiloxane, 9-aminopropyl-1,1,1,3,3,5,5,7,7,9,11,11,13,13,15,15,17,17,17-nonadecamethylnonasiloxane, and 3,5-bis(aminopropyl)-1,1,1,3,5,7,7,7-octamethyltetrasiloxane; 1, Examples include siloxane compounds having amino groups at both ends and in the side chain, such as 3,5-tris(aminopropyl)-1,1,3,5,5-pentamethyltrisiloxane, 1,9,17-tris(aminopropyl)-1,1,3,3,5,5,7,7,9,11,11,13,13,15,15,17,17-heptadecamethylnonasiloxane, and poly(aminopropyl)-polydimethylpolysiloxane. Furthermore, commercially available compounds can be used for compound (3-C).

[0040] Specific examples of compound (3-D) include 1-aminopropyl-1,3,3,5,5-pentamethylcyclotrisiloxane, 1,3,5-tris(aminopropyl)-1,3,5-trimethylcyclotrisiloxane, 1-aminopropyl-1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane, 1,3-bis(aminopropyl)-1,3,5,5,7,7-hexamethylcyclotetrasiloxane, 1,5-bis(aminopropyl)-1,3,3,5,7,7-hexamethylcyclotetrasiloxane, and 1,3-bis(aminopropyl)-5,7-dipropyl-1,3,5 Examples include cyclic siloxane compounds having amino groups, such as ,7-tetramethylcyclotetrasiloxane, 1,5-bis(aminopropyl)-3,7-dipropyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis(aminopropyl)-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentakis(aminopropyl)-1,3,5,7,9-pentamethylcyclopentasiloxane, and 1,3,5,7,9,11-hexakis(aminopropyl)-1,3,5,7,9,11-hexamethylcyclohexasiloxane. Compound (3-D) may be a commercially available product or it may be manufactured. If manufactured, conventionally known methods can be followed, for example, by reacting a cyclic hydrosiloxane compound with an alkenylamine in the presence of a transition metal catalyst.

[0041] [3] Regarding compounds (4) and (5) [ka] (In the formula, R 8 (This represents a single bond or a double bond.)

[0042] In general formulas (4) and (5), R 6 and R 7Each of these independently represents a hydrogen atom, a substituted or unsubstituted C1-C10 alkyl group, preferably C1-C6, more preferably C1-C3, a substituted or unsubstituted C2-C10 alkenyl group, a methylene group (C=CH2 group, hereinafter simply referred to as "methylene group") formed with the carbon atoms on the ring to which they are bonded, or an SiO-containing C1-C10 alkyl group, preferably C1-C6, more preferably C1-C3.

[0043] R 6 and R 7 The alkyl group can be linear, branched, or cyclic. Specific examples include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and decyl groups; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, texyl, and 2-ethylhexyl groups; and cyclic alkyl groups such as cyclopentyl and cyclohexyl groups. R 6 and R 7 The alkenyl group can be linear, branched, or cyclic, and specific examples include vinyl, allyl, propenyl, butenyl, and pentenyl alkenyl groups. Among these, R 6 and R 7 Preferably, the group consists of a hydrogen atom, a substituted or unsubstituted linear alkyl group having 1 to 6 carbon atoms, a linear alkenyl group having 2 to 6 carbon atoms, or a methylene group. From the viewpoint of ease of raw material procurement, a substituted or unsubstituted linear alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted linear alkenyl group having 2 to 3 carbon atoms, or a methylene group is more preferred, and a hydrogen atom, a methylene group, a methyl group, or an allyl group is even more preferred.

[0044] Also, R 6 , R 7Some or all of the hydrogen atoms in the alkyl or alkenyl group may be substituted with substituents, and examples of such substituents include trialkoxysilyl groups having 3 to 9 carbon atoms, such as trimethoxysilyl group and triethoxysilyl group; alkyldialkoxysilyl groups having 3 to 12 carbon atoms, such as methyldimethoxysilyl group, methyldiethoxysilyl group, phenyldimethoxysilyl group, and phenyldiethoxysilyl group; dialkylalkoxysilyl groups having 3 to 15 carbon atoms, such as dimethylmethoxysilyl group, dimethylethoxysilyl group, diisopropylmethoxysilyl group, diisopropylethoxysilyl group, diphenylmethoxysilyl group, and diphenylethoxysilyl group; and trialkylsilyl groups having 3 to 18 carbon atoms, such as trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, and tert-butyldiphenylsilyl group.

[0045] Furthermore, R 6 and R 7 These may bond with each other to form aliphatic cyclic structures, heterocyclic structures, or aromatic cyclic structures with the carbon atoms to which they are bonded. Specific examples of these structures include the following. In this case, R 6 and R 7 In this case, the substituents of the substituted alkyl group are limited to carboxyl and hydroxyl groups.

[0046] [ka]

[0047] Specific examples of compound (4) include maleic anhydride, succinic anhydride, allyl succinic anhydride, butyl succinic anhydride, hexenyl succinic anhydride, decyl succinic anhydride, dodecenyl succinic anhydride, dodecyl succinic anhydride, hexadecyl succinic anhydride, trimethoxysilylpropyl succinic anhydride, triethoxysilylpropyl succinic anhydride, citraconic anhydride, itaconic anhydride, 2,3-dimethylmaleic anhydride, 2,2-dimethylmaleic anhydride, phthalic anhydride, cyclohexene-1,2-dicarboxylic acid anhydride, and cyclohexane. Dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic acid anhydride, 4-methylcyclohexane-1,2-dicarboxylic acid anhydride, bicyclo[2,2,2]octo-5-ene-2,3-dicarboxylic acid anhydride, glutaric acid anhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-butanetetracarboxylic acid 1,2:3,4-dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, pyromellitic acid dianhydride, 3-(carboxymethyl) -1,2,4-cyclopentanetricarboxylic acid 1,4:2,3-dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, bicyclo[2,2,2]octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, ethylenediaminetetracarboxylic acid dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarbon Acid anhydrides, naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid 2,3:6,7-dianhydride, 4,4'-biphthalic anhydride, 3,4'-biphthalic anhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic acid dianhydride, 4,4'-oxydiphthalic anhydride, 3,4'-oxydiphthalic anhydride, 4,4'-(ethyn-1,2-diyl)diphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 5,5'-sulfonylbis(isobenzofuran-1,3-dione), norbornane-2-spiro-α-cyclopentanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, ethane-1,2-diylbis(1,3-dihydro-1,3-dioxobenzofuran-5-carboxylate), 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 1,4-phenylenebis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate), 9,9-bis(3,4- Examples include dicarboxyphenyl)fluorene dianhydride, 1,3-bis(propyl succinate anhydride)-1,1,3,3-tetramethyldisiloxane, 1,9-bis(propyl succinate anhydride)-1,1,3,3,5,5,7,7,9,9-decamethylpentaloxane, 1,15-bis(propyl succinate anhydride)-1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15-hexadecamethyloctasiloxane, 1,3,5-tris(propyl succinate anhydride)-1,3,5-trimethylcyclotrisiloxane, and 1,3,5,7-tetrakis(propyl succinate anhydride)-1,3,5,7-tetramethylcyclotetrasiloxane. Specific examples of compound (5) include glutaric anhydride, homophthalic anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, and 3,4,9,10-perylenetetracarboxylic dianhydride.

[0048] In the production method of the present invention, the mixing ratio of compound (1), compound (3), and compound (4) or compound (5) is not particularly limited, but it is preferable that the number of moles of bissilylamino groups in compound (1) is equal to the number of moles of amino groups in compound (3), and that the total number of moles of these is equal to the number of moles of acid anhydride structures in compound (4) or compound (5). Furthermore, the method of mixing compound (1) with compound (3) and compound (4) or compound (5) is not particularly limited, but from the viewpoint of controlling reactivity, a method of adding compound (3) to a mixture of compound (1) and compound (4) or compound (5) is preferred.

[0049] The reaction temperature is not particularly limited, but is preferably 0 to 50°C, more preferably 10 to 40°C, and even more preferably 15 to 30°C. Since the silyl ester structure of compound (6) can be converted to an imide group by heating, it is not preferable to expose it to high temperatures of 50°C or higher for a long period of time. The reaction time is not particularly limited, but is preferably 0.5 to 10 hours, and more preferably 1 to 4 hours.

[0050] This reaction can proceed without a solvent, but a solvent may also be used. Suitable solvents include (iso)paraffin compounds such as hexane, octane, isooctane, decane, dodecane, and isododecane; aromatic hydrocarbon compounds such as toluene and xylene; ether compounds such as tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyltetrahydropyran, cyclopentyl methyl ether, dioxane, ethylene glycol dimethyl ether, and propylene glycol dimethyl ether; nitrile compounds such as acetonitrile, propionitrile, and butyronitrile; ketone compounds such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and ester compounds such as ethyl acetate and butyl acetate. These may be used individually or in combination of two or more.

[0051] [4] Regarding compound (6) [ka] (In the formula, R 1 , R 2 ,n and m have the same meaning as above.

[0052] In general formulas (6-A) and (6-B), Y represents a silyl ester structure of amidic acid represented by the following general formula (7). [ka] (In the formula, R 4 , R 5 and R 7 ~R 9 The above has the same meaning, and *- represents a combination.

[0053] In general formulas (6-C) and (6-D), R 9 Each of these independently represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, or an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, having a silyl ester structure at its terminal end. 9 At least one of these is a monovalent hydrocarbon group having a silyl ester structure at its terminal end.

[0054] R 9 Specific examples of monovalent hydrocarbon groups having an amidic acid silyl ester structure at their terminus include linear groups, and specific examples of such linear aminoalkyl groups such as aminomethyl, aminopropyl, aminobutyl, aminopentyl, and aminohexyl groups. Among these, R 9 As such, linear aminoalkyl groups having 1 to 5 carbon atoms are preferred, linear aminoalkyl groups having 1 to 4 carbon atoms are more preferred from the viewpoint of ease of raw material procurement, and linear aminoalkyl groups having 1 to 3 carbon atoms are even more preferred. R 9 As for the unsubstituted monovalent hydrocarbon group, R 3 Examples include groups similar to the unsubstituted monovalent hydrocarbon groups.

[0055] In general formula (6-C), R 9 The number of monovalent hydrocarbon groups with 1 to 6 carbon atoms having an amidoic acid silyl ester structure at the end of the above-mentioned structure is p 3 Therefore, p 3 is, 0 <p 3 / 2n+6≦0.8, preferably 0.05 <p 3 / 2n+6≦0.6, more preferably 0.1 <p 3It is a number that satisfies the condition / (2n+6) ≤ 0.5. In general formula (6-D), R 9 The number of C1-C6 monovalent hydrocarbon groups having an amidoic acid silyl ester structure at the end of the above is q 3 Therefore, q 3 is, 0 3 / 2m+6≦0.8, preferably 0.05 3 / 2m+6≦0.6, more comfortable 0.1 3 It is a number that satisfies the condition / 2m+6≦0.5.

[0056] Since the manufacturing method of the present invention does not produce by-products, in most cases only the target compound (6) is obtained, so there is no problem in using the reaction solution as is or further converting it. In other words, the reaction solution can be used as is, or simply by removing the solvent, without performing by-product removal steps such as vacuum stripping, various chromatography methods, or treatment with adsorbents, which are usually carried out to isolate the target compound (6) from the reaction solution.

[0057] [4] Method for producing silyl amicate ester compounds contained in compound (6-A) Furthermore, among the compounds containing a silyl ester structure of amic acid included in compound (6-A), the silyl ester compound of amic acid represented by the following general formula (8) is a compound that can be used as a silane coupling agent because it has a hydrolyzable alkoxysilyl group. In particular, the hydrolyzable alkoxy group (OR 10 The number of R 12 Because it has one or two atoms bonded to each silicon atom, it is a compound with excellent storage stability.

[0058] [ka] (In the formula, R 4 , R 6 ~R 8 (This has the same meaning as above, and r represents 1 or 2.)

[0059] ​​​In general formula (8), R 10 and R 11 Each of these independently represents an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, and this monovalent hydrocarbon group is R 3 Examples include groups similar to the unsubstituted monovalent hydrocarbon groups.

[0060] R 12 This is a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 3 to 6 carbon atoms, which may be interposed by oxygen, nitrogen, silicon, sulfur atoms, or siloxane bonds. R 12 The divalent hydrocarbon group can be linear, branched, or cyclic. Specific examples include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, hexamethylene, octamethylene, and decylene; branched alkylene groups such as methyltrimethylene and methyltetramethylene; cyclic alkylene groups such as cyclohexylene and methylenecyclohexylenemethylene; linear alkenylene groups such as butenylene, hexenylene, and octenylene; branched alkenylene groups such as isobutenylene; arylene groups such as phenylene; and aralkylene groups such as methylenephenylene and methylenephenylmethylenemethylene. Among these, R 12 Preferably, the group is a substituted or unsubstituted linear alkylene group having 2 to 8 carbon atoms, or a substituted or unsubstituted aralkylene group having 7 to 10 carbon atoms. From the perspective of ease of raw material procurement, an unsubstituted linear alkylene group having 3 to 6 carbon atoms or an unsubstituted aralkylene group having 7 to 9 carbon atoms is even more preferred, and a propylene group, a phenylene group, or a methylenephenylenemethylene group is even more preferred.

[0061] Also, R 12However, examples of divalent hydrocarbon groups that involve oxygen, nitrogen, silicon, sulfur atoms or siloxane bonds include alkylene oxyalkylene groups, alkylene aminoalkylene groups, alkylenedialkylsilylalkylene groups, alkylenedialkylsilylarylene groups, alkylentioalkylene groups, alkylene dimethylsiloxanylalkylene groups, and alkylene polydimethylpolysiloxanylalkylene groups. [Examples]

[0062] The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0063] [Example 1] [ka] (In the formula, Me represents a methyl group, Et represents an ethyl group, and TMS represents a trimethylsilyl group. The same applies hereafter.)

[0064] A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 17.0 g (0.0505 mol) of N,N-bistrimethylsilylaminopropylmethyldiethoxysilane and 9.8 g (0.100 mol) of maleic anhydride were charged and cooled to 10°C. 9.6 g (0.050 mol) of 3-aminopropylmethyldiethoxysilane was added dropwise for 1 hour, ensuring the temperature did not exceed 30°C. The mixture was then stirred at room temperature for 1 hour to obtain 36.2 g of the reaction solution. The reaction solution was analyzed by GC and confirmed that the three raw materials listed above had disappeared. In addition, the reaction solution was analyzed by IR and 1 1H-NMR was measured. The results are shown in Figure 1. IR analysis revealed that 1780 cm⁻¹ -1 Since no peaks were observed in the vicinity, it was confirmed that the imidation reaction was not proceeding. 1 The formation of the target product was confirmed by 1H-NMR.

[0065] [Example 2] [ka]

[0066] The procedure was carried out in the same manner as in Example 1, except that the maleic anhydride was replaced with 11.4 g (0.100 mol) of glutaric anhydride, to obtain 38 g of reaction solution. The reaction solution was analyzed by GC and confirmed that the three raw materials had disappeared. Furthermore, the reaction solution was analyzed by IR and... 1 1H-NMR was measured. The results are shown in Figure 2. IR analysis revealed that 1780 cm⁻¹ -1 Since no peaks were observed in the vicinity, it was confirmed that the imidation reaction was not proceeding. 1 The formation of the target product was confirmed by 1H-NMR.

[0067] [Example 3] [ka]

[0068] Replace the maleic anhydride in Example 1 with 11.2 g (0.100 mol) of citraconic anhydride. The procedure was carried out in the same manner as in Example 1, except for the modification, to obtain 37.5 g of the reaction solution. The reaction solution was analyzed by GC and confirmed that the three raw materials had disappeared. Furthermore, the reaction solution was analyzed by IR and... 1 1H-NMR was measured. The results are shown in Figure 3. IR analysis revealed that 1780 cm⁻¹ -1 Since no peaks were observed in the vicinity, it was confirmed that the imidation reaction was not proceeding. 1 ¹H-NMR confirmed that the target product was formed as a mixture of isomers.

[0069] [Example 4] [ka]

[0070] The procedure was carried out in the same manner as in Example 1, except that the maleic anhydride in Example 1 was replaced with 11.2 g (0.100 mol) of itaconic anhydride, and 37.5 g of the reaction solution was obtained. The reaction solution was analyzed by GC and confirmed that the three raw materials had disappeared. Furthermore, the reaction solution was analyzed by IR and... 1 1H-NMR was measured. The results are shown in Figure 4. IR analysis revealed that 1780 cm⁻¹ -1 Since no peaks were observed in the vicinity, it was confirmed that the imidation reaction was not proceeding. 1 ¹H-NMR confirmed that the target product was formed as an isomer mixture.

[0071] [Example 5] [ka]

[0072] The procedure was carried out in the same manner as in Example 1, except that the maleic anhydride in Example 1 was replaced with 16.8 g (0.100 mol) of methylcyclohexanedicarboxylic acid anhydride, and 43.2 g of the reaction solution was obtained. The reaction solution was analyzed by GC and confirmed that the three raw materials had disappeared. Furthermore, the reaction solution was analyzed by IR and... 1 1H-NMR was measured. The results are shown in Figure 5. IR analysis revealed that 1780 cm⁻¹ -1 Since no peaks were observed in the vicinity, it was confirmed that the imidation reaction was not proceeding. 1 ¹H-NMR confirmed that the target product was formed as an isomer mixture.

[0073] [Example 6] [ka]

[0074] A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 17.0 g (0.0505 mol) of N,N-bistrimethylsilylaminopropylmethyldiethoxysilane, 10.9 g (0.0500 mol) of pyromellitic anhydride, and 37.3 g of dipropylene glycol dimethyl ether (hereinafter referred to as "DPGDME") were charged into it and cooled to 10°C. 9.6 g (0.050 mol) of 3-aminopropylmethyldiethoxysilane was added dropwise for 1 hour, keeping the temperature below 30°C. The mixture was then stirred at room temperature for 4 hours to obtain 74.6 g of the reaction solution. The reaction solution was analyzed by GC and confirmed that the three raw materials had disappeared. Furthermore, the reaction solution was analyzed by IR and... 1 1H-NMR was measured. The results are shown in Figure 6. IR analysis revealed that 1780 cm⁻¹ -1 Since no peaks were observed in the vicinity, it was confirmed that the imidation reaction was not proceeding. 1 ¹H-NMR confirmed that the target product was formed as an isomer mixture.

[0075] [Example 7] [ka]

[0076] A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 16.5 g (0.0510 mol) of N,N-bistrimethylsilylaminopropyltrimethoxysilane and 11.5 g (0.101 mol) of glutaric acid anhydride were charged in, and the mixture was cooled to 10°C. 9.0 g (0.050 mol) of 3-aminopropyltrimethoxysilane was then added dropwise for 1 hour, ensuring the temperature did not exceed 30°C. The mixture was then stirred at room temperature for 1 hour to obtain 36.8 g of the reaction solution. The reaction solution was analyzed by GC and confirmed that the three raw materials listed above had disappeared. In addition, the reaction solution was analyzed by IR and 1 1H-NMR was measured. The results are shown in Figure 7. IR analysis revealed that 1780 cm⁻¹ -1 Since no peaks were observed in the vicinity, it was confirmed that the imidation reaction was not proceeding. 1The formation of the target product was confirmed by 1H-NMR.

[0077] [Example 8] [ka]

[0078] The procedure was carried out in the same manner as in Example 7, except that the glutaric acid anhydride was replaced with 21.0 g (0.0800 mol) of trimethoxysilylpropyl succinic acid anhydride, to obtain 46.5 g of the reaction solution. The reaction solution was analyzed by GC and confirmed that the three raw materials listed above had disappeared. In addition, the reaction solution was analyzed by IR and 1 1H-NMR was measured. The results are shown in Figure 8. IR analysis revealed that 1780 cm⁻¹ -1 Since no peaks were observed in the vicinity, it was confirmed that the imidation reaction was not proceeding. 1 ¹H-NMR confirmed that the target product was formed as an isomer mixture.

[0079] [Example 9] [ka]

[0080] A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 7.00 g (0.0130 mol) of 1,3-bis(N,N-bistrimethylsilylaminopropyl)-1,1,3,3-tetramethyldisiloxane, 13.1 g (0.0500 mol) of trimethoxysilylpropyl succinic anhydride, and 10 g of DPGDME were charged in, and the mixture was cooled to 10°C. 3.10 g (0.0125 mol) of 1,3-bis(aminopropyl)-1,1,3,3-tetramethyldisiloxane was added dropwise for 1 hour, ensuring the temperature did not exceed 30°C. The mixture was then stirred at room temperature for 1 hour to obtain 33.0 g of the reaction solution. The reaction solution was analyzed by GC and confirmed that the three raw materials listed above had disappeared. In addition, the reaction solution was analyzed by IR and 1 1H-NMR was measured. The results are shown in Figure 9. IR analysis revealed that 1780 cm⁻¹ -1Since no peaks were observed in the vicinity, it was confirmed that the imidation reaction was not proceeding. 1 The formation of the target product was confirmed by 1H-NMR.

[0081] [Example 10] [ka]

[0082] A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 10.1 g (0.0501 mol) of N,N-bistrimethylsilylallylamine and 11.4 g (0.100 mol) of glutaric acid anhydride were charged in, and the mixture was cooled to 10°C. 2.9 g (0.051 mol) of allylamine was then added dropwise for 1 hour, ensuring the temperature did not exceed 30°C. The mixture was then stirred at room temperature for 1 hour to obtain 24.4 g of the reaction solution. The reaction solution was analyzed by GC and confirmed that the three raw materials listed above had disappeared. In addition, the reaction solution was analyzed by IR and 1 1H-NMR was measured. IR analysis revealed 1780 cm⁻¹. -1 Since no peaks were observed in the vicinity, it was confirmed that the imidation reaction was not proceeding. 1 The formation of the target product was confirmed by 1H-NMR.

[0083] [Comparative Example 1] [ka]

[0084] A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 20.1 g (0.100 mol) of N,N-bistrimethylsilylallylamine and 11.5 g (0.101 mol) of glutaric acid anhydride were charged in, and the mixture was cooled to 10°C. 3.2 g (0.100 mol) of methanol was added dropwise for 1 hour, ensuring the temperature did not exceed 30°C. The mixture was then stirred at room temperature for 1 hour to obtain 34.2 g of reaction solution. The reaction solution was analyzed by GC and confirmed that the two raw materials mentioned above had disappeared and that trimethylmethoxysilane had been formed. The reaction solution was analyzed by IR and 1 1H-NMR was measured. IR analysis revealed 1780 cm⁻¹. -1 Since no peaks were observed in the vicinity, it was confirmed that the imidation reaction was not proceeding at this point. 1 The formation of the target product was confirmed by 1H-NMR. Next, the unwanted trimethylmethoxysilane was removed from the resulting reaction solution by stripping it under reduced pressure, ensuring the temperature did not exceed 60°C, to obtain a strip solution. The IR of this strip solution was measured at 1780 cm⁻¹. -1 A peak was observed in the vicinity, confirming that the imidation reaction had proceeded.

[0085] The results from the examples show that the manufacturing method of the present invention produces no by-products and can produce the target silyl ester compound of amidate without undergoing an imidation reaction. On the other hand, the results of the comparative example show that while the conventional manufacturing method can obtain silyl ester compounds of amidic acid without causing an imidation reaction, it contains by-products. When the by-products are removed by heating and distillation, the imidation reaction proceeds, making it impossible to obtain the desired silyl ester compound of amidic acid in high purity.

Claims

1. The following general formulas (1-A), (1-B), (1-C), or (1-D) 【Chemistry 1】 [(wherein, R 1 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms which may have an oxygen, nitrogen, silicon or sulfur atom intervening therebetween, R 2 represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms which may have an oxygen, nitrogen, silicon, sulfur atom or siloxane bond intervening therebetween, X represents a bissilylamino group represented by the following general formula (2), R 3 each independently represents a monovalent hydrocarbon group having 1 to 6 carbon atoms having a bissilylamino group represented by the following general formula (2) at the terminal or an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, but at least one of R 3 is a monovalent hydrocarbon group having 1 to 6 carbon atoms having the bissilylamino group at the terminal, in general formula (1-C), the number of the monovalent hydrocarbon groups having 1 to 6 carbon atoms having the bissilylamino group at the terminal in R 3 is p 1 when defined as such, p 1 is a number satisfying 0 < p 1 / 2n + 6 ≦ 0.8, in general formula (1-D), the number of the monovalent hydrocarbon groups having 1 to 6 carbon atoms having the bissilylamino group at the terminal in R 3 is q 1 when defined as such, q 1 is a number satisfying 0 < q 1 / 2m + 6 ≦ 0.8, n represents an integer of 0 to 1000, and m represents 0, 1, 2 or 3.) 【Chemistry 2】 (In the formula, R 4 Each of these independently represents an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and *- represents a bond. A compound having a bissilylamino group represented by, The following general formulas (3-A), (3-B), (3-C), or (3-D) 【Transformation 3】 (In the formula, R 1 , R 2 ,n and m have the same meaning as above, R 5 Each of these independently represents a monovalent hydrocarbon group having 1 to 6 carbon atoms with a primary amino group at its terminus, or an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, but R 5 At least one of them is a monovalent hydrocarbon group having 1 to 6 carbon atoms and having a primary amino group at its terminus, and in the general formula (3-C), R 5 The number of monovalent hydrocarbon groups having 1 to 6 carbon atoms and having the primary amino group at the terminal is p 2 Therefore, p 2 0 < p 2 It is a number that satisfies / 2n + 6 ≤ 0.8, and in the general formula (3-D), R 5 The number of monovalent hydrocarbon groups with 1 to 6 carbon atoms having a primary amino group at the terminal is q. 2 Then, q 2 0 < q 2 (This is a number that satisfies the condition / 2m + 6 ≤ 0.8.) An amine compound represented by, The following general formula (4) or general formula (5) 【Chemistry 4】 (In the formula, R 6 and R 7 Each of these independently represents a hydrogen atom, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a methylene group formed together with the carbon atoms on the ring to which they are bonded, or an SiO-containing C1-C10 alkyl group, R 6 and R 7 These may bond with each other to form an aliphatic cyclic structure, a heterocyclic structure, or an aromatic cyclic structure with the carbon atoms to which they are bonded, but in that case, R 6 and R 7 The substituents of the substituted alkyl group in R do not include carboxyl groups or hydroxyl groups. 8 (This represents a single bond or a double bond.) The process includes reacting an acid anhydride having 1 to 4 structures represented by the following general formula (6-A), (6-B), (6-C), or (6-D). 【Transformation 5】 (In the formula, R 1 , R 2 ,n and m have the same meaning as above, R 9 Each of these independently represents a monovalent hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted monovalent hydrocarbon group having a silyl amide ester structure represented by the following general formula (7) at its terminal, R 9 At least one of them is a monovalent hydrocarbon group having 1 to 6 carbon atoms and having the silyl ester structure of the amidate at its terminus, and in the general formula (6-C), R 9 The number of monovalent hydrocarbon groups having 1 to 6 carbon atoms and having the silyl ester structure of the amidate at the terminal is p 3 Therefore, p 3 0 < p 3 It is a number that satisfies / 2n + 6 ≤ 0.8, and in the general formula (3-D), R 9 The number of monovalent hydrocarbon groups having the silyl ester structure of the amidate at the terminal, with 1 to 6 carbon atoms, is q. 3 Then, q 3 0 < q 3 Y is a number that satisfies / 2m + 6 ≤ 0.8, and Y represents the base expressed by the following general formula (7). 【Transformation 6】 (In the formula, R 4 , R 5 and R 7 ~R 9 (This has the same meaning as above, and *- represents a coupling.) A method for producing a silyl ester compound represented by the amicate.

2. A silyl ester compound of an amidoate represented by the following general formula (8). 【Transformation 7】 (In the formula, R 4 Each of these independently represents an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 6 and R 7 Each of these independently represents a hydrogen atom, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a methylene group formed together with the carbon atoms on the ring to which they are bonded, or an SiO-containing C1-C10 alkyl group, R 6 and R 7 These may bond with each other to form an aliphatic cyclic structure, a heterocyclic structure, or an aromatic cyclic structure with the carbon atoms to which they are bonded, but in that case, R 6 and R 7 The substituents of the substituted alkyl group in R do not include carboxyl groups or hydroxyl groups. 8 R represents a single bond or a double bond. 10 and R 11 Each of these independently represents an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, and R 12 (where r represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, which may contain an oxygen, nitrogen, silicon, sulfur atom, or siloxane bond, and r represents 1 or 2.)

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