JP6390583B2 - IMINE COMPOUND HAVING BISSILYLAMINO GROUP AND METHOD FOR PRODUCING THE SAME - Google Patents

Description

  The present invention relates to an imine compound having a bissilylamino group and a method for producing the same.

  The imino group is a functional group formed by a primary amino group and a carbonyl compound, and has no active hydrogen on nitrogen. From this, the compound having an imino group can be mixed with a compound having a functional group that reacts with an amino group, such as an epoxy group or an isocyanurate group.

  On the other hand, since the imino group is an equivalent of a carbonyl group, it has electrophilicity and can easily react with a nucleophile. By utilizing this property and reacting with an active metal terminal such as an anionic polymerization terminal, it is possible to form a covalent bond and introduce an amino group into the polymerization terminal (Patent Document 1). By this reaction, a secondary amino group as an amino group derived from an imino group is introduced into the polymerization terminal at the polymerization terminal, and a modified polymer having an amino group is obtained. In addition, it is generally known that the performance of a modified polymer is improved by introducing a plurality of amino groups in order to increase the effect of amino groups.

JP-A-9-151275

  Examples of the compound used for introducing a large number of amino groups at the polymerization terminal include N-benzylidene (diethylaminoethyl) amine having an imino group and an amino group in the same molecule. However, the amino group allowed for a compound having an imino group and an amino group in the same molecule is limited to a tertiary amino group. This is because the anionic polymerization terminal reacts with active hydrogen on nitrogen rich in the reactivity of the primary or secondary amino group and deactivates the polymerization terminal.

  On the other hand, if a primary amino group can be introduced into the polymerization terminal, not only can the interaction derived from the active hydrogen of the primary amino group be improved, but further functional group conversion is possible. For these reasons, there has been a demand for a compound capable of allowing a primary amino group to coexist at the polymerization terminal while having a functional group capable of reacting with the active metal terminal.

  As a result of intensive studies to achieve the above object, the present inventors have found that the above-mentioned problems can be solved by using an imine compound having a bissilylamino group in which one amino group is protected by a silyl group. I found it. In other words, the imine compound having a bissilylamino group has both an imino group and an amino group, but since there is no reactive hydrogen active on these nitrogen atoms, the imino group does not deactivate the active metal terminal. Since the primary amino group can be constructed by removing the silyl group of the bissilylamino group after the reaction, a highly active primary amino group can be introduced into the polymerization terminal.

Accordingly, the present invention provides an imine compound having a bissilylamino group shown below and a method for producing the same.
[1]
The following general formula (1)
(Wherein R ^{1 to} R ⁶ are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R ³ and R ⁴ are bonded to each other to form a ring together with the nitrogen atom and silicon atom to which they are bonded. R ⁷ is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ⁸ and R ⁹ are hydrogen atoms, or substituted or unsubstituted monovalent hydrocarbon having 1 to 20 carbon atoms. Except that R ⁸ and R ⁹ are both hydrogen atoms, and R ⁸ and R ⁹ may be bonded to each other to form a ring together with the carbon atom to which they are bonded.)
An imine compound having a bissilylamino group represented by
[2]
The following general formula (2)
(Wherein R ^{1 to} R ⁷ are the same as described above.)
An amine compound having a bissilylamino group represented by the following general formula (3):
(In the formula, R ⁸ and R ⁹ are the same as described above.)
The method for producing an imine compound having a bissilylamino group according to [1], wherein the carbonyl compound represented by formula (1) is reacted.

  The imine compound having a bissilylamino group provided by the present invention can be reacted with an imino group without deactivating the active metal terminal, particularly when used as an anionic polymerization terminal modifier, and after the reaction, By removing the group, a highly reactive primary amino group can be constructed, which is useful as an anionic polymerization terminal modifier.

2 is an IR chart of N-benzylidene (bis (trimethylsilyl) aminoethyl) amine obtained in Example 1. FIG. 2 is a ¹ H-NMR chart of N-benzylidene (bis (trimethylsilyl) aminoethyl) amine obtained in Example 1. FIG. 2 is an IR chart of N-cinnamylidene (bis (trimethylsilyl) aminoethyl) amine obtained in Example 2. FIG. 2 is a ¹ H-NMR chart of N-cinnamylidene (bis (trimethylsilyl) aminoethyl) amine obtained in Example 2. FIG. 4 is an IR chart of N-benzylidene (bis (trimethylsilyl) aminopropyl) amine obtained in Example 3. FIG. 2 is a ¹ H-NMR chart of N-benzylidene (bis (trimethylsilyl) aminopropyl) amine obtained in Example 3. FIG.

The imine compound having a bissilylamino group of the present invention is a compound represented by the following general formula (1).

Here, R < ¹ > -R < ⁶ > is a C1-C20, Preferably it is 1-10, More preferably, it is a 1-6 substituted or unsubstituted monovalent hydrocarbon group. Specifically, straight chain such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, etc. Branched alkyl group such as isopropyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, texyl group, 2-ethylhexyl group, cyclic alkyl group such as cyclopentyl group, cyclohexyl group, vinyl group, Examples include alkenyl groups such as allyl group, propenyl group, aryl groups such as phenyl group and tolyl group, aralkyl groups such as benzyl group, and the like, particularly methyl group, ethyl group, isopropyl group, sec-butyl group, tert-butyl group Is preferred. In addition, some or all of the hydrogen atoms of the hydrocarbon group may be substituted. Specific examples of the substituent include alkoxy groups such as a methoxy group, an ethoxy group, and an (iso) propoxy group. Group: halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; cyano group; amino group; aryl group having 6 to 18 carbon atoms such as phenyl group and tolyl group; acyl group having 2 to 10 carbon atoms; Examples are each alkyl group, trialkylsilyl group, trialkoxysilyl group, dialkylmonoalkoxysilyl group or monoalkyldialkoxysilyl group each having 1 to 5 carbon atoms, and further ester group (—COO—), An ether group (—O—), a sulfide group (—S—) or the like may be interposed, and these may be used in combination.

Examples of the —R ³ —R ⁴ — group when R ³ and R ⁴ are bonded include a methylene group, an ethylene group, a methylethylene group, a propylene group, and a methylpropylene group.

R ⁷ is a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. Specific examples of the divalent hydrocarbon group having 1 to 10 carbon atoms include a methylene group, an ethylene group, Alkylene groups such as methylethylene group, propylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, decamethylene group, isobutylene group, arylene group such as phenylene group, methylenephenylene group, methylenephenylenemethylene group, etc. Aralkylene groups and the like are exemplified, and a methylene group, a propylene group, and a hexamethylene group are desirable from the viewpoint of easy procurement of raw materials.

R ⁸ and R ⁹ are each a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. In the case of a monovalent hydrocarbon group, the same hydrocarbon groups as R ^{1 to} R ⁶ are exemplified, and the product From the viewpoint of usefulness, a phenyl group is preferable.

  Specific examples of the imine compound having the bissilylamino group represented by the general formula (1) include N-benzylidene (bis (trimethylsilyl) aminoethyl) amine, N-benzylidene (bis (trimethylsilyl) aminopropyl) amine, N -Benzylidene (bis (trimethylsilyl) aminobutyl) amine, N-benzylidene (bis (trimethylsilyl) aminohexyl) amine, N-benzylidene (bis (triethylsilyl) aminoethyl) amine, N-benzylidene (bis (triethylsilyl) aminopropyl ) Amine, N-benzylidene (bis (triethylsilyl) aminobutyl) amine, N-benzylidene (bis (triethylsilyl) aminohexyl) amine, N-benzylidene (bis (triisopropylsilyl) aminoethyl) a N-benzylidene (bis (triisopropylsilyl) aminopropyl) amine, N-benzylidene (bis (triisopropylsilyl) aminobutyl) amine, N-benzylidene (bis (triisopropylsilyl) aminohexyl) amine, N-benzylidene (2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane-1-ethyl) amine, N-benzylidene (2,2,5,5-tetramethyl-1-aza- 2,5-disilacyclopentan-1-propyl) amine, N-benzylidene (2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane-1-butyl) amine, N -Benzylidene (2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane-1-hexyl) amine, N- (1, -Dimethyl-butylidene)-(bis (trimethylsilyl) aminoethyl) amine, N- (1,3-dimethyl-butylidene)-(bis (trimethylsilyl) aminopropyl) amine, N- (1,3-dimethyl-butylidene)- (Bis (trimethylsilyl) aminobutyl) amine, N- (1,3-dimethyl-butylidene)-(bis (trimethylsilyl) aminohexyl) amine, N- (1,3-dimethyl-butylidene)-(bis (triethylsilyl) Aminoethyl) amine, N- (1,3-dimethyl-butylidene)-(bis (triethylsilyl) aminopropyl) amine, N- (1,3-dimethyl-butylidene)-(bis (triethylsilyl) aminobutyl) amine N- (1,3-Dimethyl-butylidene)-(bis (triethylsilyl) amino (Hexyl) amine, N- (1,3-dimethyl-butylidene)-(bis (triisopropylsilyl) aminoethyl) amine, N- (1,3-dimethyl-butylidene)-(bis (triisopropylsilyl) aminopropyl) Amines, N- (1,3-dimethyl-butylidene)-(bis (triisopropylsilyl) aminobutyl) amine, N- (1,3-dimethyl-butylidene)-(bis (triisopropylsilyl) aminohexyl) amine, N- (1,3-dimethyl-butylidene)-(2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane-1-ethyl) amine, N- (1,3- Dimethyl-butylidene)-(2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane-1-propyl) amine, N- (1,3- Methyl-butylidene)-(2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane-1-butyl) amine, N- (1,3-dimethyl-butylidene)-(2 , 2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane-1-hexyl) amine, N-cinnamylidene (bis (trimethylsilyl) aminoethyl) amine, N-cinnamylidene (bis (trimethylsilyl)) Aminopropyl) amine, N-cinnamylidene (bis (trimethylsilyl) aminobutyl) amine, N-cinnamylidene (bis (trimethylsilyl) aminohexyl) amine, N-cinnamylidene (bis (triethylsilyl) aminoethyl) amine, N-cinnamylidene (bis) (Triethylsilyl) aminopropyl) amine, N-cinnamylide (Bis (triethylsilyl) aminobutyl) amine, N-cinnamylidene (bis (triethylsilyl) aminohexyl) amine, N-cinnamylidene (bis (triisopropylsilyl) aminoethyl) amine, N-cinnamylidene (bis (triisopropylsilyl)) Aminopropyl) amine, N-cinnamylidene (bis (triisopropylsilyl) aminobutyl) amine, N-cinnamylidene (bis (triisopropylsilyl) aminohexyl) amine, N-cinnamylidene (2,2,5,5-tetramethyl- 1-aza-2,5-disilacyclopentane-1-ethyl) amine, N-cinnamylidene (2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane-1-propyl ) Amine, N-cinnamylidene (2,2,5,5- Tetramethyl-1-aza-2,5-disilacyclopentane-1-butyl) amine, N-cinnamylidene (2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane- 1-hexyl) amine and the like are exemplified.

The method for producing an imine compound having a bissilylamino group represented by the above general formula (1) in the present invention is represented by the following general formula (2).
(Wherein R ^{1 to} R ⁷ are the same as described above.)
An amine compound having a bissilylamino group represented by the following general formula (3):
(In the formula, R ⁸ and R ⁹ are the same as described above.)
The method of making the carbonyl compound shown by react is illustrated.

  Specific examples of the amine compound having a bissilylamino group represented by the general formula (2) include bis (trimethylsilyl) aminoethylamine, bis (trimethylsilyl) aminopropylamine, bis (trimethylsilyl) aminobutylamine, and bis (trimethylsilyl). ) Aminohexylamine, bis (triethylsilyl) aminoethylamine, bis (triethylsilyl) aminopropylamine, bis (triethylsilyl) aminobutylamine, bis (triethylsilyl) aminohexylamine, bis (triisopropylsilyl) aminoethylamine, bis ( Triisopropylsilyl) aminopropylamine, bis (triisopropylsilyl) aminobutylamine, bis (triisopropylsilyl) aminohexylamine, (2,2,5,5) Tetramethyl-1-aza-2,5-disilacyclopentane-1-ethyl) amine, (2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane-1-propyl) ) Amine, (2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane-1-butyl) amine, (2,2,5,5-tetramethyl-1-aza-) 2,5-disilacyclopentane-1-hexyl) amine and the like are exemplified.

  Specific examples of the carbonyl compound represented by the general formula (3) include aliphatic saturation such as acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, pentanal, 3-methylbutanal, hexanal, octanal, decanal, and dodecanal. Aldehyde unsaturated aldehydes such as aldehyde, acrolein, 2-butenal, 3-methyl-2-butenal, 3-butenal, 3-octenal, aldehyde compounds such as benzaldehyde, cinnamaldehyde, jasmine aldehyde, etc., and acetone, Aliphatic saturated ketones such as methyl ethyl ketone and methyl isobutyl ketone, aliphatic unsaturated ketones such as methyl vinyl ketone, cycloaliphatic ketones such as cyclobutanone, cyclopentanone and cyclohexanone, aceto Enon, propiophenone, valerophenone, ketone compounds such as aromatic ketones such as dibenzyl ketone are exemplified.

The compounding ratio of the amine compound having a bissilylamino group represented by the general formula (2) and the carbonyl compound represented by the general formula (3) is not particularly limited, but from the viewpoint of reactivity and productivity, the general formula ( The range of 0.1 to 4 mol, particularly 0.2 to 2 mol, of the compound represented by the general formula (3) is preferable with respect to 1 mol of the compound represented by 2).
In this case, the reaction temperature is preferably 0 to 200 ° C., particularly 20 to 120 ° C., and the reaction time is usually 1 to 30 hours, particularly 1 to 20 hours.
The above reaction proceeds even without solvent, but a solvent can also be used. Solvents used include hydrocarbon solvents such as hexane, cyclohexane, isooctane, benzene, toluene and xylene, ether solvents such as tetrahydrofuran and dioxane, ester solvents such as ethyl acetate, propyl acetate and butyl acetate, acetonitrile, N , N-dimethylformamide, N-methylpyrrolidone and other aprotic polar solvents, dichloroethane and other chlorinated hydrocarbon solvents, and the like. These solvents may be used alone or in combination of two or more.
The above reaction proceeds even without catalyst, but a catalyst can also be used. Examples of the catalyst used include acidic catalysts such as hydrogen chloride, hydrogen bromide, sulfuric acid, methanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, and trifluoroacetic acid.

  The reaction rate can be improved by extracting the water produced in the above reaction together with the solvent. Examples of the solvent used include the same solvents as used in the above reaction.

  The reaction rate can be improved by capturing water generated in the above reaction with a dehydrating agent. Examples of dehydrating agents used include chemical desiccants such as calcium oxide, calcium chloride, sodium hydroxide, potassium hydroxide, anhydrous sodium sulfate, anhydrous magnesium sulfate, and anhydrous copper sulfate, silica gel, aluminum oxide, molecular sieve, Examples include physical desiccants such as allophane and zeolite, and silazane compounds such as hexamethyldisilazane. In particular, hexamethyldisilazane is preferable because water can be chemically converted.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a reference example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

Synthesis Example 1 Synthesis of bis (trimethylsilyl) aminoethylamine In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 126.5 g (2.105 mol) of ethylenediamine and 7.3 g of dodecylbenzenesulfonic acid (0 0.021 mol) was charged and heated to 80 ° C. After the internal temperature was stabilized, 373.5 g (2.314 mol) of hexamethyldisilazane was added dropwise over 1.5 hours, followed by stirring at 140 ° C. for 4 hours.
The obtained reaction solution was decompressed to 10 kPa and heated to reflux, and then ethylenediamine and trimethylsilylethylenediamine produced over 32 hours were distilled off. To this reaction solution, 4.2 g (0.022 mol) of 28% sodium methoxide methanol solution was added. Next, 40.1 g (1.25 mol) of methanol was added at room temperature, and the mixture was stirred at room temperature for 30 minutes. 97.0g of bis (trimethylsilyl) aminoethylamine was obtained by fractionating a 78 degreeC / 1.0kPa fraction from the obtained reaction liquid by distillation under reduced pressure.

[Example 1] Synthesis of N-benzylidene (bis (trimethylsilyl) aminoethyl) amine In a flask equipped with a stirrer, a refluxer, a dropping funnel and a thermometer, 25.5 g (0.240 mol) of benzaldehyde and hexamethyldiethyl were added. 6.5 g (0.040 mol) of silazane and 40 mL of toluene were charged, and a mixed solution consisting of 40.9 g (0.200 mol) of bis (trimethylsilyl) aminoethylamine and 40 mL of toluene was added at 40 ° C. to room temperature. It was dripped over 3 hours, keeping the following. The reaction mixture was transferred to a separatory funnel and the produced water was separated, and then concentrated with an evaporator. The obtained residue was distilled to obtain 45.9 g of a fraction at 143 ° C./0.2 kPa.

A mass spectrum, ¹ H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m / z 293 277 174 130 100 73
IR spectrum FIG. 1 is a chart.
¹ H-NMR spectrum FIG. 2 is a chart.
From the above results, it was confirmed that the obtained compound was N-benzylidene (bis (trimethylsilyl) aminoethyl) amine.

[Example 2] Synthesis of N-cinnamylidene (bis (trimethylsilyl) aminoethyl) amine In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 31.9 g (0.241 mol) of transcinnamaldehyde and hexa 6.5 g (0.041 mol) of methyldisilazane and 40 mL of toluene were charged, and a mixed solution composed of 40.9 g (0.200 mol) of bis (trimethylsilyl) aminoethylamine and 40 mL of toluene was added to the resulting reaction solution at room temperature. It was dripped over 3 hours, keeping 40 degrees C or less. The reaction mixture was transferred to a separatory funnel and the produced water was separated, and then concentrated with an evaporator. The obtained residue was distilled to obtain 38.1 g of a fraction of 166 ° C./0.2 kPa.

A mass spectrum, ¹ H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m / z 319 303 174 73
IR spectrum FIG. 3 is a chart.
¹ H-NMR spectrum FIG. 4 is a chart.
From the above results, it was confirmed that the obtained compound was N-cinnamylidene (bis (trimethylsilyl) aminoethyl) amine.

[Example 3] Synthesis of N-benzylidene (bis (trimethylsilyl) aminopropyl) amine In a flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 12.9 g (0.121 mol) of benzaldehyde and hexamethyldibenzene were added. Silazane (3.3 g, 0.020 mol) and toluene (20 mL) were charged. To the resultant reaction solution, a mixed solution of bis (trimethylsilyl) aminopropylamine (21.9 g, 0.100 mol) and toluene (20 mL) was added at room temperature. The solution was added dropwise over 3 hours while maintaining at or below. The reaction mixture was transferred to a separatory funnel and the produced water was separated, and then concentrated with an evaporator. The obtained residue was distilled to obtain 28.5 g of a fraction at 144 ° C./0.2 kPa.

A mass spectrum, ¹ H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m / z 307 291 188 119 73
IR spectrum FIG. 5 is a chart.
¹ H-NMR spectrum FIG. 6 is a chart.
From the above results, it was confirmed that the obtained compound was N-benzylidene (bis (trimethylsilyl) aminopropyl) amine.

[Reference Example] Reaction of N-benzylidene (bis (trimethylsilyl) aminoethyl) amine and butyllithium A flask equipped with a stirrer, a refluxer, a dropping funnel and a thermometer was combined with N-benzylidene (bis ( Trimethylsilyl) aminoethyl) amine (2.9 g, 0.0099 mol) and toluene (7.5 mL) were charged and immersed in a water bath. To the obtained reaction solution, 6.25 mL (0.0100 mol) of n-butyllithium (2.60 M hexane solution) was added dropwise over 5 minutes, and then stirred at room temperature. Methanol 5.0mL was added to the obtained reaction liquid, reaction was stopped, and GC / MS analysis was performed. As a result, 2-aminoethyl (1-phenylpentyl) amine and 2-bis (trimethylsilyl) aminoethyl (1-phenylpentyl) amine are produced, and disappearance of the raw material N-benzylidene (bis (trimethylsilyl) aminoethyl) amine Was confirmed. From this result, it was confirmed that the imine compound having a bissilylamino group of the present invention can react with the metal terminal without deactivating the anionic polymerization terminal.

Claims (2)

The following general formula (1)
(Wherein R ^{1 to} R ⁶ are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R ³ and R ⁴ are bonded to each other to form a ring together with the nitrogen atom and silicon atom to which they are bonded. R ⁷ is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ⁸ and R ⁹ are hydrogen atoms, or substituted or unsubstituted monovalent hydrocarbon having 1 to 20 carbon atoms. Except that R ⁸ and R ⁹ are both hydrogen atoms, and R ⁸ and R ⁹ may be bonded to each other to form a ring together with the carbon atom to which they are bonded.)
An imine compound having a bissilylamino group represented by The following general formula (2)
(Wherein R ^{1 to} R ⁷ are the same as described above.)
An amine compound having a bissilylamino group represented by the following general formula (3):
(In the formula, R ⁸ and R ⁹ are the same as described above.)
The method for producing an imine compound having a bissilylamino group according to claim 1, wherein the carbonyl compound represented by the formula is reacted.