JP4344936B2 - Method for producing organosilicon compound containing amino groups at both ends - Google Patents

Description

  The present invention relates to a method for producing an organosilicon compound containing amino groups at both ends, which is useful as a modifier for polyimide used in semiconductor insulating films, liquid crystal alignment films, and the like, and as a modifier for polyurethane and polyamide.

  As a method for producing an organosilicon compound containing both terminal amino groups, a method is known in which allylamine and a Si-H group-containing silane compound are hydrosilylated in the presence of a platinum catalyst (Non-patent Document 1: Izv.Acad.Nauk SSSR Ser.Khim., 2249 (1969)). However, in this method, the reaction is very slow, and it takes a very long time for production. Also, since it involves many side reactions, the yield is low and a high-purity target product cannot be obtained. There is a problem.

  As a method for improving the above problems, N-trimethylsilylallylamine and a Si-H group-containing silane compound at both ends are hydrosilylated and then deprotected (Non-Patent Document 2: J. Org. Chem., 24, 119, (1959), Non-Patent Document 3: Dokl. A method of performing deprotection after hydrosilylation reaction of the containing silane compound (Patent Document 1: Japanese Patent Publication No. 7-55953), N, N-bistrimethylsilylallylamine and Si-H group-containing silane compound at both ends A method of deprotecting after hydrosilylation reaction (Patent Document 2: JP-A-11-3227) 6 JP) there is.

  However, in the method using N-trimethylsilylallylamine as a raw material, there is a problem in that many isomers added inside rather than at the end are formed during the hydrosilylation reaction, and the purity is lowered. In addition, when a siloxane compound such as tetramethyldisiloxane is used as the Si-H group-containing silane compound at both ends, when deprotecting with water or alcohol, trimethylalkoxysilane and trimethylsilanol produced by the deprotection are intended. Due to the equilibration reaction with siloxane, there is a problem that 3-aminopropylpentamethyldisiloxane is by-produced and the yield is reduced.

In the method using N-benzylideneallylamine, in addition to hydrosilylation to an allyl group, a hydrosilylation reaction to an imino group also occurs, resulting in a decrease in yield.
In addition, in the method using N, N-bistrimethylsilylallylamine as a raw material, since the raw material N, N-bistrimethylsilylallylamine must introduce two silyl groups into allylamine, it is difficult to produce and very expensive. There is a problem that it is.

Japanese Patent Publication No. 7-55953 JP-A-11-322766 Izv. Acad. Nauk SSSR Ser. Khim. , 2249 (1969) J. et al. Org. Chem. , 24, 119, (1959) Dokl. Akad. Nauk SSSR, 179,600 (1968)

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an industrially effective production method for a high-quality, both-terminal amino group-containing organosilicon compound with few isomers.

  As a result of intensive studies to achieve the above object, the present inventor, as a raw material, uses an allylamine obtained by protecting one NH group of allylamine with a silyl group bulky than a trimethylsilyl group as a starting material. By carrying out a hydrosilylation reaction with a silicon compound and then deprotecting it, a high-quality organosilicon compound containing both end amino groups with few isomers can be obtained. In the case of a compound, since the alkoxysilane and silanol compound produced during deprotection have a bulky silyl group, the equilibration reaction between the target both-terminal amino group-containing organosilicon compound does not occur and It has been found that the rate does not decrease, and the present invention has been completed.

（式中、Ｒ¹、Ｒ²は炭素数１〜１０の１価炭化水素基、Ｒ³は炭素数２〜１０の１価炭化水素基である。）
で示されるシリル基で保護されたアリルアミンと、下記一般式（２）

［式中、Ａは下記一般式（３）

（式中、ｎは０〜１００の整数である。）
で示される結合、又は炭素数１〜１０の２価炭化水素基である。］
で示されるＳｉ−Ｈ基含有有機ケイ素化合物とを白金触媒存在下で反応させ、下記一般式（４）

（式中、Ｒ¹、Ｒ²、Ｒ³、Ａは上記と同様である。）
で示される化合物を得、その後脱保護することを特徴とする下記一般式（５）

（式中、Ａは上記と同様である。）
で示される両末端アミノ基含有有機ケイ素化合物の製造方法を提供する。 Accordingly, the present invention provides the following general formula (1)

(In the formula, R ¹ and R ² are monovalent hydrocarbon groups having 1 to 10 carbon atoms, and R ³ is a monovalent hydrocarbon group having 2 to 10 carbon atoms.)
An allylamine protected with a silyl group represented by the following general formula (2):

[In the formula, A represents the following general formula (3)

(In the formula, n is an integer of 0 to 100.)
Or a divalent hydrocarbon group having 1 to 10 carbon atoms. ]
Is reacted with an Si-H group-containing organosilicon compound represented by the following general formula (4):

(Wherein R ¹ , R ² , R ³ and A are the same as above)
A compound represented by the following general formula (5):

(In the formula, A is the same as above.)
The manufacturing method of the both-terminal amino group containing organosilicon compound shown by these is provided.

  According to the present invention, by using allylamine obtained by protecting one NH group of allylamine with a bulky silyl group as compared with a trimethylsilyl group as a raw material, a high-purity amino group-containing organosilicon compound containing no isomers Can be produced in high yield.

  The method for producing an organosilicon compound containing amino groups at both ends of the present invention comprises the following two reaction steps.

Here, R ¹ and R ² are monovalent hydrocarbon groups having 1 to 10 carbon atoms, preferably linear, branched or cyclic alkyl groups, aryl groups such as phenyl groups, and aralkyl groups such as benzyl groups. . R ³ is a monovalent hydrocarbon group having 2 to 10 carbon atoms, preferably a linear, branched or cyclic alkyl group, an aryl group such as a phenyl group, or an aralkyl group such as a benzyl group.

Examples of the alkyl group for R ¹ and R ² include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, texyl group, An octyl group and the like are exemplified, and examples of the alkyl group for R ³ include the same groups as described above except for a methyl group.

（式中、ｎは０〜１００、好ましくは０〜１０の整数である。）
で示される結合、又は炭素数１〜１０の２価炭化水素基である。この場合、２価の炭化水素基としては、直鎖状、分岐状又は環状のアルキレン基、フェニレン基等のアリーレン基、アルキレン基とアリーレン基とが結合した基等が挙げられる。なお、環状アルキレン基は、ノルボルニレン基等の橋かけを有するものであってもよい。 A represents the following general formula (3)

(In the formula, n is an integer of 0 to 100, preferably 0 to 10.)
Or a divalent hydrocarbon group having 1 to 10 carbon atoms. In this case, examples of the divalent hydrocarbon group include a linear, branched or cyclic alkylene group, an arylene group such as a phenylene group, a group in which an alkylene group and an arylene group are bonded, and the like. The cyclic alkylene group may have a bridge such as a norbornylene group.

（式中、Ｒ¹、Ｒ²は炭素数１〜１０の１価炭化水素基、Ｒ³は炭素数２〜１０の１価炭化水素基である。）
で示されるシリル基で保護されたアリルアミンと、下記一般式（２）

［式中、Ａは下記一般式（３）

（式中、ｎは０〜１００の整数である。）
で示される結合、又は炭素数１〜１０の２価炭化水素基である。］
で示される両末端Ｓｉ−Ｈ基含有有機ケイ素化合物とを白金触媒存在下で反応させ、下記一般式（４）

（式中、Ｒ¹、Ｒ²、Ｒ³、Ａは上記と同様である。）
で示される化合物とするものである。 The hydrosilylation step is represented by the following general formula (1)

(In the formula, R ¹ and R ² are monovalent hydrocarbon groups having 1 to 10 carbon atoms, and R ³ is a monovalent hydrocarbon group having 2 to 10 carbon atoms.)
An allylamine protected with a silyl group represented by the following general formula (2):

[In the formula, A represents the following general formula (3)

(In the formula, n is an integer of 0 to 100.)
Or a divalent hydrocarbon group having 1 to 10 carbon atoms. ]
Is reacted with an Si-H group-containing organosilicon compound represented by formula (4) in the presence of a platinum catalyst.

(Wherein R ¹ , R ² , R ³ and A are the same as above)
It is set as the compound shown by these.

  Specific examples of the allylamine protected by the silyl group represented by the general formula (1) used in the above reaction include ethyldimethylsilylallylamine, diethylmethylsilylallylamine, triethylsilylallylamine, t-butyldimethylsilylallylamine, Examples include sildimethylsilylallylamine, triisopropylsilylallylamine, triisobutylsilylallylamine, t-butyldiphenylsilylallylamine, triphenylsilylallylamine, cyclohexyldimethylsilylallylamine, cyclohexyldiethylsilylallylamine, and the like. Of these, triethylsilylallylamine, t-butyldimethylsilylallylamine, texyldimethylsilylallylamine, triisopropylsilylallylamine, and triisobutylsilylallylamine are preferable.

The allylamine protected by the silyl group represented by the general formula (1) is, for example, allylamine and the following general formula (6):
R ¹ R ² R ³ SiCl (6)
(In the formula, R ¹ , R ² and R ³ are the same as above.)
It can manufacture by making the chlorosilane compound shown by react.

  Specific examples of the Si-H group-containing organosilicon compound represented by the general formula (2) include 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5. -Hexamethyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1,4-bis (dimethylsilyl) benzene, 1,4-bis (dimethylsilyl) cyclohexane, 2 , 5-bis (dimethylsilyl) norbornane and the like.

  The compounding ratio of the allylamine protected with a silyl group and the Si-H group-containing organosilicon compound used in the above reaction is not particularly limited, but from the viewpoint of reactivity and productivity, 1 mol of allylamine protected with a silyl group is used. On the other hand, the Si—H group-containing organosilicon compound is preferably in the range of 0.2 to 1 mol, particularly 0.3 to 0.6 mol.

  Specific examples of the platinum catalyst used in the above reaction include chloroplatinic acid, an alcohol solution of chloroplatinic acid, and toluene of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex. Alternatively, xylene solution, tetrakistriphenylphosphine platinum, dichlorobistriphenylphosphine platinum, dichlorobisacetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadiene platinum and the like are exemplified.

  The amount of platinum catalyst used is not particularly limited, but from the viewpoint of reactivity and productivity, 0.000001 to 0.01 mol, particularly 0.00001 to 0.001 mol, relative to 1 mol of allylamine protected with a silyl group. The range of is preferable.

  In the deprotection step, the silyl group on the nitrogen atom of the both-terminal silyl-protected amino group-containing organosilicon compound is eliminated to obtain a both-terminal amino group-containing organosilicon compound.

  The deprotection reaction can be carried out by hydrolysis with water, alcoholysis with alcohol, or simultaneous hydrolysis and alcoholysis in a water-alcohol system. Specific examples of the alcohol used for the alcoholysis decomposition reaction include methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, and glycerin.

  The amount of water and / or alcohol used in the deprotection reaction is not particularly limited. However, from the viewpoint of reactivity and productivity, 0.5 to 100 mol, particularly 0. A range of 8 to 10 mol is preferred.

  The deprotection reaction proceeds even without a catalyst, but it may be carried out by adding a catalyst such as hydrochloric acid, sulfuric acid, methanesulfonic acid, ammonium sulfate, or ammonium chloride.

  The hydrosilylation reaction and deprotection reaction proceed even without solvent, but a solvent can also be used. Solvents used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene and xylene, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, and ester solvents such as ethyl acetate and butyl acetate. And aprotic polar solvents such as acetonitrile and N, N-dimethylformamide, and chlorinated hydrocarbon solvents such as dichloromethane and chloroform. These solvents may be used alone or in combination of two or more.

  The reaction temperature for the hydrosilylation reaction and deprotection reaction is not particularly limited, but is preferably 0 to 150 ° C, particularly preferably 10 to 120 ° C. Although the reaction time is not particularly limited, it is preferably 1 to 20 hours, particularly 1 to 15 hours. The reaction atmosphere is preferably an inert gas atmosphere such as nitrogen or argon.

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

[Synthesis Example 1] Synthesis of N-triethylsilylallylamine 314.1 g (5.5 mol) of allylamine and 375 ml of toluene were charged into a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. 376.8 g (2.5 mol) of triethylchlorosilane was added dropwise at 20 to 40 ° C. over 2 hours, followed by stirring at room temperature for 1 hour. 560 g of a 20% aqueous sodium hydroxide solution was added to dissolve the resulting salt, the aqueous layer was removed, and the organic layer was distilled. 341.6 g of N-triethylsilylallylamine was obtained as a fraction having a boiling point of 85 to 86 ° C./3 kPa (yield 80%).

[Example 1]
In a flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 34.3 g (0.2 mol) of N-triethylsilylallylamine, 0.02 mmol of a toluene solution of a platinum-divinyltetramethyldisiloxane complex (in terms of platinum atom) ) And heated to 50 ° C. After the internal temperature was stabilized, 13.4 g (0.1 mol) of 1,1,3,3-tetramethyldisiloxane was added dropwise over 2 hours and stirred at that temperature for 1 hour. Thereafter, 9.6 g (0.3 mol) of methanol was added at 25 ° C., and the mixture was stirred at 25 ° C. as it was. After 1 hour, gas chromatographic analysis revealed that all triethylsilyl groups were deprotected and converted to 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and triethylmethoxysilane. It was converted. Further, 1- (3-aminopropyl) -1,1-dimethyl-3,3,3-triethyldisiloxane, which is considered to be produced by a siloxane equilibration reaction, was not produced at all. The reaction solution was distilled to obtain 21.9 g of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane as a fraction having a boiling point of 81-82 ° C./0.13 kPa ( Yield 89%). As a result of analyzing the obtained compound by gas chromatography, isomer 1- (2-aminopropyl) -3- (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane was produced. It was confirmed that they did not.

[Example 2]
In a flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 17.1 g (0.1 mol) of N-triethylsilylallylamine, 0.01 mmol of a toluene solution of a platinum-divinyltetramethyldisiloxane complex (in terms of platinum atom) ) And heated to 50 ° C. After the internal temperature was stabilized, 10.1 g (0.05 mol) of 1,1,3,3,5,5-hexamethyltrisiloxane was added dropwise over 2 hours and stirred at that temperature for 1 hour. Thereafter, 4.8 g (0.15 mol) of methanol was added at 25 ° C., and the mixture was stirred at 25 ° C. as it was. One hour later, when analyzed by gas chromatography, all triethylsilyl groups were deprotected, and 1,5-bis (3-aminopropyl) -1,1,3,3,5,5-hexamethyltrisiloxane and It was converted to triethylmethoxysilane. Further, 1- (3-aminopropyl) -1,1-dimethyl-3,3,3-triethyldisiloxane and the like, which are considered to be produced by a siloxane equilibration reaction, were not produced at all. 13. The reaction solution is distilled to obtain 1,5-bis (3-aminopropyl) -1,1,3,3,5,5-hexamethyltrisiloxane as a fraction having a boiling point of 108-110 ° C./0.067 kPa. 7 g was obtained (yield 85%).

[Example 3]
In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 51.4 g (0.3 mol) of N-triethylsilylallylamine, 0.03 mmol of a toluene solution of a platinum-divinyltetramethyldisiloxane complex (in terms of platinum atom) ) And heated to 50 ° C. After the internal temperature was stabilized, 29.2 g (0.15 mol) of 1,4-bis (dimethylsilyl) benzene was added dropwise over 4 hours and stirred at that temperature for 1 hour. Thereafter, 14.4 g (0.45 mol) of methanol was added at 25 ° C., and the mixture was stirred at 25 ° C. as it was. One hour later, when analyzed by gas chromatography, all triethylsilyl groups were deprotected and converted to 1,4-bis (3-aminopropyldimethylsilyl) benzene and triethylmethoxysilane. The reaction solution was distilled to obtain 37.0 g of 1,4-bis (3-aminopropyldimethylsilyl) benzene as a fraction having a boiling point of 150-158 ° C./0.024 kPa (yield 80%). As a result of analyzing the obtained compound by gas chromatography, it was confirmed that an isomer of 1,4-bis (3-aminopropyldimethylsilyl) benzene was not produced.

[Synthesis Example 2] Synthesis of N-triisopropylsilylallylamine 376.9 g (6.6 mol) of allylamine and 450 ml of toluene were charged into a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. 578.4 g (3.0 mol) of triisopropylchlorosilane was added dropwise at 20 to 40 ° C. over 2 hours, followed by stirring at 70 ° C. for 6 hours. After cooling to room temperature, 650 g of a 20% aqueous sodium hydroxide solution was added, the resulting salt was dissolved, the aqueous layer was removed, and the organic layer was distilled. As a fraction having a boiling point of 74 to 75 ° C./0.2 kPa, 557.2 g of N-triisopropylsilylallylamine was obtained (yield 87%).

[Example 4]
In a flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 42.7 g (0.2 mol) of N-triisopropylsilylallylamine, 0.02 mmol of a toluene solution of a platinum-divinyltetramethyldisiloxane complex (platinum atom) Conversion) and heated to 50 ° C. After the internal temperature was stabilized, 13.4 g (0.1 mol) of 1,1,3,3-tetramethyldisiloxane was added dropwise over 4 hours and stirred at that temperature for 1 hour. Thereafter, 0.01 g of methanesulfonic acid was added, 19.2 g (0.6 mol) of methanol was added at 60 ° C., and the mixture was stirred at 60 ° C. as it was. After 6 hours, gas chromatography analysis revealed that all triisopropylsilyl groups were deprotected, and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and triisopropylmethoxy It was converted to silane. Further, 1- (3-aminopropyl) -1,1-dimethyl-3,3,3-triisopropyldisiloxane, which is considered to be produced by a siloxane equilibration reaction, was not produced at all. The reaction solution was distilled to obtain 22.5 g of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane as a fraction having a boiling point of 81-82 ° C./0.13 kPa ( Yield 91%). As a result of analyzing the obtained compound by gas chromatography, isomer 1- (2-aminopropyl) -3- (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane was produced. It was confirmed that they did not.

[Comparative Example 1]
In a flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 25.9 g (0.2 mol) of N-trimethylsilylallylamine, 0.02 mmol of a platinum-divinyltetramethyldisiloxane complex toluene solution (in terms of platinum atom) And heated to 50 ° C. After the internal temperature was stabilized, 13.4 g (0.1 mol) of 1,1,3,3-tetramethyldisiloxane was added dropwise over 2 hours and stirred at that temperature for 1 hour. Thereafter, 9.6 g (0.3 mol) of methanol was added at 25 ° C., and the mixture was stirred at 25 ° C. as it was. After 1 hour, analysis by gas chromatography revealed that all trimethylsilyl groups were deprotected and the reaction was complete, but 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane In addition to trimethylmethoxysilane, a large amount of 3-aminopropylpentamethyldisiloxane was produced by a siloxane equilibration reaction. In addition, the isomer 1- (2-aminopropyl) -3- (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane is the target 1,3-bis (3-amino). Propyl) -1,1,3,3-tetramethyldisiloxane was confirmed to be contained at 7%.

[Comparative Example 2]
In a flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 25.9 g (0.2 mol) of N-trimethylsilylallylamine, 0.02 mmol of a platinum-divinyltetramethyldisiloxane complex toluene solution (in terms of platinum atom) Charged and heated to 50 ° C. After the internal temperature was stabilized, 19.4 g (0.1 mol) of 1,4-bis (dimethylsilyl) benzene was added dropwise over 4 hours and stirred at that temperature for 1 hour. Thereafter, 9.6 g (0.3 mol) of methanol was added at 25 ° C., and the mixture was stirred at 25 ° C. as it was. After 1 hour, gas chromatographic analysis revealed that the reaction was complete, but the isomer 1- (2-aminopropyldimethylsilyl) -4- (3-aminopropyldimethylsilyl) benzene was the target 1 , 4-bis (3-aminopropyldimethylsilyl) benzene was confirmed to be contained at 9%.

Claims (2)

The following general formula (1)

(In the formula, R ¹ and R ² are monovalent hydrocarbon groups having 1 to 10 carbon atoms, and R ³ is a monovalent hydrocarbon group having 2 to 10 carbon atoms.)
An allylamine protected with a silyl group represented by the following general formula (2):

[In the formula, A represents the following general formula (3)

(In the formula, n is an integer of 0 to 100.)
Or a divalent hydrocarbon group having 1 to 10 carbon atoms. ]
Is reacted with an Si-H group-containing organosilicon compound represented by the following general formula (4):

(Wherein R ¹ , R ² , R ³ and A are the same as above)
A compound represented by the following general formula (5):

(In the formula, A is the same as above.)
The manufacturing method of the both-terminal amino group containing organosilicon compound shown by these. The bifunctional amino group-containing organosilicon compound according to claim 1, wherein the allylamine protected with a silyl group is triethylsilylallylamine, t-butyldimethylsilylallylamine, texyldimethylsilylallylamine, triisopropylsilylallylamine or triisobutylsilylallylamine. Manufacturing method.