WO2014046223A1

WO2014046223A1 - Method for producing organic silyl amine compound

Info

Publication number: WO2014046223A1
Application number: PCT/JP2013/075412
Authority: WO
Inventors: 亮灘野; 優子多比良
Original assignee: セントラル硝子株式会社
Priority date: 2012-09-20
Filing date: 2013-09-20
Publication date: 2014-03-27
Also published as: JPWO2014046223A1; JP6304033B2

Abstract

This method for producing an organic silyl amine compound (3) represented by general formula (3) is characterized in that ammonia is removed by reactive distillation when an organic disilazane compound (1) represented by general formula (1) is reacted with an alkyl amine represented by general formula (2). An organic silyl amine compound can be obtained by this production method with high productivity without producing a salt. (In the formulae, each of R¹, R² and R³ independently represents a linear or branched alkyl group having 1-7 carbon atoms, a cyclic alkyl group having 3-5 carbon atoms or a phenyl group; and each of R⁴ and R⁵ independently represents a hydrogen atom, a linear or branched alkyl group having 1-5 carbon atoms or a cyclic alkyl group having 3-5 carbon atoms, provided that R⁴ and R⁵ are not hydrogen atoms at the same time.)

Description

Method for producing organic silylamine compound

The present invention relates to a method for producing an organic silylamine compound.

Trialkylsilylalkylamine is widely used as a synthesis unit, and can be used as a synthesis element having a protecting group by replacing a hydrogen atom of an alkylamine with a trialkylsilyl group. In addition, the silicon-nitrogen bond of trialkylsilylalkylamine is weaker than that of silicon-oxygen bond, and silicon-oxygen bond is formed when applied on the surface of glass with hydroxyl group such as silanol. Since it is covered with a base and its surface state changes, it is also used as a surface treatment agent.

As a method for synthesizing a trialkylsilylalkylamine, a method is known in which 1 equivalent of an alkylamine and 1 equivalent of an inorganic base are reacted with an industrially inexpensive trialkylsilylchloride to obtain a trialkylsilylalkylamine. (See Non-Patent Document 1).

On the other hand, a method of obtaining a trialkylsilylamine by reacting an organic disilazane compound such as hexaalkyldisilazane with an amine is also known. For example, Patent Document 1 discloses a method for obtaining a corresponding trialkylsilylamine compound using morpholine, allylamine, aniline, or triazole as an amine. Non-Patent Document 2 discloses a method for obtaining a corresponding trialkylsilylamine compound using imidazole, pyrazole or the like as an amine.

However, for silylalkylamine compounds such as trialkylsilylalkylamines, only methods using trialkylsilyl chloride, alkylamine and inorganic base as raw materials are known, and synthetic methods using organic disilazane compounds as raw materials have been established. Not.

German Patent Application No. 4041645

In the method of Non-Patent Document 1, since a salt of a base and hydrogen chloride is generated as the reaction proceeds, the reaction mixture becomes a slurry. In order to obtain the desired product, it is necessary to remove this salt, but it is known that the product trialkylsilylalkylamine is easily hydrolyzed by the presence of water, and simple operations such as washing with water can be performed. In addition, a complicated process of filtration operation is required. Further, when an inorganic base such as sodium hydroxide, sodium carbonate or sodium hydrogen carbonate is used as the base, there is a problem that water is generated and the product is decomposed. Even when an organic base is selected instead of an inorganic base, the hydrochloride of the organic base is bulky, and therefore, in industrial production, an operation of sufficiently diluting with a solvent is required to ensure the uniformity of the reaction. Furthermore, the greater the amount of solvent used for dilution, the lower the production volume per reactor size used for production. As described above, due to the difficulty of handling due to the physical properties of the product, it is difficult to improve the productivity and there is a problem that the equipment per production amount becomes large.

As described above, the conventional method for producing an organic silylamine compound cannot yet be said to have sufficient production efficiency.

Therefore, an object of the present invention is to provide a method for producing an organic silylamine compound represented by the general formula (3) useful as a building block and a surface treatment agent with high productivity by a simple operation.

Wherein R ¹ , R ² and R ³ are each independently a linear or branched alkyl group having 1 to 7 carbon atoms, a cyclic alkyl group having 3 to 5 carbon atoms, or a phenyl group. R ⁴ and R ⁵ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a cyclic alkyl group having 3 to 5 carbon atoms, and R ⁴ and R ⁵ are It is not a hydrogen atom at the same time.)

In order to solve the above problems, the present inventors have conducted intensive studies. As a result, when organic disilazane compound and alkylamine are used as raw materials, the by-product is ammonia, so salt is not generated and the reaction solution is not slurried. The present invention was completed by obtaining the knowledge that an organic silylamine compound can be easily obtained without requiring an operation of diluting with a solvent by separating it from the alkylamine by distillation and then discharging it out of the system (Scheme). 1).

That is, the present invention includes the following inventions 1 to 12.

[Invention 1]
Reacting the organic disilazane compound represented by the general formula (1) with the alkylamine represented by the general formula (2) in the presence of an acid catalyst while removing the produced ammonia by reactive distillation.
The manufacturing method of the organic silylamine compound represented by General formula (3).

Wherein R ¹ , R ² and R ³ are each independently a linear or branched alkyl group having 1 to 7 carbon atoms, a cyclic alkyl group having 3 to 5 carbon atoms, or a phenyl group. .)

(Wherein the R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group or the number 3 to 5 cyclic alkyl group having a carbon linear or branched chain having 1 to 5 carbon atoms, R ⁴ and R ⁵ is not a hydrogen atom at the same time.)

(Wherein, each R ^1, R ² and R ³ has the same meaning as R ^1, R ² and R ³ in the general formula (1), respectively R ⁴ and R ^5, R ⁴ in the general formula (2) And synonymous with R ^5. )

[Invention 2]
The production method according to invention 1, wherein R ¹ , R ² and R ³ are all methyl groups.

[Invention 3]
The production method according to invention 1 or 2, wherein R ⁴ and R ⁵ are each independently a methyl group or an ethyl group.

[Invention 4]
The production method according to any one of Inventions 1 to 3, wherein the number of theoretical plates of the reactive distillation is 2 or more and 100 or less.

[Invention 5]
The production method according to any one of Inventions 1 to 4, wherein the reactive distillation is performed at a pressure of −0.09 MPaG or more and +1 MPaG or less.

[Invention 6]
The production method according to any one of inventions 1 to 5, wherein the acid catalyst is an amine salt of “Bronsted acid having a pKa of −13 or more and +1 or less”.

[Invention 7]
The group in which the Bronsted acid consists only of sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, trifluoroacetic acid, and perchloric acid The production method according to invention 6, wherein the production method is at least one Bronsted acid selected from the above.

[Invention 8]
The acid catalyst is at least one acid catalyst selected from the group consisting of triethylamine hydrochloride, dimethylamine hydrochloride, pyridine hydrochloride, ammonium hydrochloride, ammonium oxalate, triethylamine sulfate, dimethylamine sulfate, pyridine sulfate, ammonium sulfate, and ammonium nitrate. The manufacturing method in any one of invention 1 thru | or 6.

[Invention 9]
In the reaction system, the acid catalyst is brought into contact with the “alkylamine represented by the general formula (2)” present in the reaction system with “Bronsted acid having a pKa of −13 or more and +1 or less”. The production method according to any one of Inventions 1 to 6, wherein the production method is obtained by the method described above.

[Invention 10]
“Bronsted acid having a pKa of −13 or more and +1 or less” is contacted with an amine to prepare an amine salt of “Bronsted acid having a pKa of −13 or more and +1 or less”, and then the amine salt The manufacturing method in any one of invention 1 thru | or 6 including the process thrown into the said reaction system as an "acid catalyst".

[Invention 11]
The production method according to claim 7, wherein the Bronsted acid is sulfuric acid.

[Invention 12]
The manufacturing method in any one of invention 1 thru | or 6 whose reaction temperature is 30 degreeC or more and 150 degrees C or less.

When the present inventors calculated each energy by the quantum chemistry calculation about the virtual reaction of the organic silylamine compound which uses the organic disilazane compound and the alkylamine as raw materials, it was shown that the equilibrium of the reaction was greatly biased toward the raw material side ( (See Scheme 2). On the other hand, when the reaction between the organic disilazane compound and imidazole as in Non-Patent Document 2 was calculated in the same manner, it was shown that the equilibrium was biased toward the product side, which reproduced the experimental facts described in the literature. there were. Imidazole has a carbon-carbon double bond or a carbon-nitrogen double bond, and in the product, the π electron of the double bond is coordinated to the vacant orbit of the silyl substituent of the organic silylamine compound to stabilize the compound. In contrast, the reaction is considered to proceed spontaneously, and conversely, amines that do not have the effect of stabilizing the product, such as the raw material of the present invention, for example, aliphatic groups that do not have a double bond It has been suggested that amines having an alkyl group as a substituent do not spontaneously proceed because the equilibrium is biased toward the raw material system. That is, the reaction of the present invention cannot easily occur in the conventional method, and it can be said that the use of the form of the present invention is very important for solving the problem.

By using the production method of the present invention, the target organic silylamine compound can be efficiently obtained, and no salt is generated in the reaction, so there is no need for complicated operations such as a filtration step, and there is no solvent. Reaction is also possible, and operability and productivity can be improved.

Hereinafter, the organic disilazane compound represented by the general formula (1) used in the production method of the present invention, the alkylamine represented by the general formula (2), and the organic silylamine compound represented by the general formula (3) as a product. The acid catalyst and production conditions will be described. However, the production method of the present invention is not construed as being limited to the description of the embodiments and examples shown below.

<1. Organic Disilazane Compound>
The organic disilazane compound represented by the general formula (1) used in the production method of the present invention is represented by the general formula (1).

Wherein R ¹ , R ² and R ³ are each independently a linear or branched alkyl group having 1 to 7 carbon atoms, a cyclic alkyl group having 3 to 5 carbon atoms, or a phenyl group. is there.)

Specific preferred organic disilazane compounds include R ¹ , R ² and R ^{3 which} are each independently a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group from the viewpoint of availability. Those which are groups, t-butyl groups or phenyl groups are preferred. Examples of the cyclic alkyl group include a cyclohexyl group. Specific examples of these organic disilazane compounds include hexamethyldisilazane, hexaethyldisilazane, hexa-n-propyldisilazane, hexaiso-propyldisilazane, hexan-butyldisilazane, hexat-butyldisilazane, Examples include hexaphenyldisilazane, 1,1,2,2-tetramethyl-3,3-diethyldisilazane, and the like. Of these, hexamethyldisilazane is particularly preferable.

<2. Alkylamine>
The alkylamine used in the production method of the present invention is represented by the general formula (2).

The alkylamine needs to be separated from the ammonia produced as the reaction proceeds, but it is not easy to separate the alkylamine having a boiling point close to that of ammonia, so it is effective to separate the ammonia by reactive distillation. Therefore, the closer the alkylamine has a boiling point to that of ammonia, the more useful the method of the present invention is, and it is particularly effective for those having a boiling point of 150 ° C. or less at atmospheric pressure. Even when an alkylamine having a boiling point different from that of ammonia is used, by carrying out the present invention, it can be separated from ammonia more precisely.

Specific suitable alkylamines include methylamine, ethylamine, n-propylamine, iso-propylamine, cyclopropylamine, n-butylamine, sec-butylamine, iso-butylamine, t-butylamine, cyclobutylamine, n- Pentylamine, cyclopentylamine, dimethylamine, diethylamine, n-dipropylamine, iso-dipropylamine, dicyclopropylamine, n-dibutylamine, sec-dibutylamine, iso-dibutylamine, t-dibutylamine, dicyclo Mention may be made of butylamine, methylethylamine, methyl-n-propylamine, methyl-iso-propylamine, methyl-cyclopropylamine. Of these, methylamine, ethylamine, n-propylamine, iso-propylamine, cyclopropylamine, dimethylamine, diethylamine, di-n-propylamine, di-iso-propylamine, dicyclopropylamine, and methylethylamine are particularly preferable. .

<3. Product Organic Silylamine Compound>
The organosilylamine compound that is the object of the present invention is represented by the general formula (3).

<4. Manufacturing conditions>
Details of the production conditions of the production method of the present invention will be described below.

4-1. Equivalent relation of reaction raw materials The amount ratio of the organic disilazane compound of the general formula (1) and the alkylamine (2) of the general formula (2), which are usually raw materials, is not limited. The equivalent of the alkylamine is preferably 0.4 to 10 molar equivalents, more preferably 1 to 5 molar equivalents, more preferably 1.5 to 3 molar equivalents relative to 1 molar equivalent of the starting organic disilazane compound. The equivalent or less is particularly preferable. If the equivalent amount of alkylamine to 1 molar equivalent of the organic disilazane compound is less than 0.4 molar equivalent, there are many organic disilazane compounds that do not participate in the reaction, which is economically undesirable. Moreover, when the equivalent of the alkylamine with respect to 1 molar equivalent of the organic disilazane compound exceeds 10 molar equivalents, many alkylamines are not involved in the reaction, which is economically undesirable.

As described above, in a preferable equivalent relationship, the alkylamine of the general formula (2) is excessively present. In this case, as described later, if “Bronsted acid” such as sulfuric acid or methanesulfonic acid is directly charged into the reaction system, an alkylamine salt of the “Bronsted acid” is generated in the system. “Salt” preferably functions as an “acid catalyst”.

4-2. Reactive Distillation In the present invention, ammonia is extracted out of the reaction system continuously and selectively using the boiling point difference between ammonia and a substance other than ammonia among the raw materials and products contained in the reaction system. As a means for performing such an operation, reactive distillation is particularly suitable.

As exemplified in “Comparative Example 1” described later, if this “reactive distillation” operation is not performed, the target reaction does not occur sufficiently even if other conditions are met. In this sense, “reactive distillation” is a very important operation in the present invention.

The operating conditions for reactive distillation in the present invention are adjusted according to the boiling point of the raw material and the boiling point of the product, and comprehensive conditions are described below.

As the reactive distillation apparatus used in the present invention, any apparatus suitable for discharging generated ammonia as a gas from the reaction system can be used. For example, a so-called reactive distillation column can be used. The form of the reactive distillation column is not particularly limited. For example, a packed distillation column or a shelf distillation column can be used. Moreover, the theoretical plate number of the reactive distillation column should just be 2 or more and 100 or less. Especially, 3 or more and 50 or less are preferable and 5 or more and 20 or less are more preferable. If the number of theoretical plates is less than 2, the separation and removal of ammonia becomes incomplete, and accompanying the ammonia, the raw material alkylamine, organic disilazane compound, or product organic silylamine compound is released out of the system, resulting in a decrease in yield. Therefore, it is not preferable. If the number exceeds 100, the equipment becomes expensive, which is not preferable as an industrial method.

As the packing packed in the distillation column of the reactive distillation in the present invention, either regular packing or irregular packing can be used. The regular packing may be those usually used, and examples thereof include melapack, gempack, technopack, flexipack, sulzer packing, glitch grid, and good roll packing. The irregular packing may be a commonly used one, such as Raschig ring, Lessing ring, Pole ring, Berle saddle, Interlocks saddle, Dixon packing, McMahon packing, Helipak, Cascade Mini ring (registered trademark), etc. .

Examples of the tray (tray) provided in the distillation column for reactive distillation in the present invention include a bubble bell tray, a uniflat tray, a perforated plate tray, a jet tray, a bubble tray, a venturi tray, a turbo grid tray, a dual flow tray, and a ripple. Examples include trays, kittel trays, slit trays, and sieve trays. Moreover, you may use combining a shelf and a filler.

In the reactive distillation in the present invention, a method of achieving distillation separation through a thin film such as a spinning band can also be used.

In the reactive distillation in the present invention, extractive distillation can be used in order to improve the separation of ammonia from any one of the starting organic disilazane compound, alkylamine, and target organic silylamine compound. That is, by adding a solvent at a constant rate from the top of the distillation column, the vapor pressure characteristics of the two compounds can be changed to improve the separation efficiency. As a solvent in this case, <6. Solvents described later in “Solvent> can be used.

The temperature of the reaction solution during the reactive distillation in the present invention is usually from 30 ° C. to 150 ° C., preferably from 50 ° C. to 100 ° C. If it is less than 30 ° C., the speed at which the equilibrium of the reaction is shifted is slow, so that it cannot be a practical method. If it exceeds 150 ° C., it is not preferable because the fractionation operation of ammonia and the raw material system in the reactive distillation becomes difficult.

The pressure during reactive distillation in the present invention may be −0.09 MPaG (“G” represents gauge pressure, the same shall apply hereinafter) or more and +5 MPaG or less on the basis of gauge pressure. Among them, −0.02 MPaG or more and +2 MPaG or less is preferable, and 0.00 MPaG or more and +1 MPaG or less is particularly preferable. If it is lower than −0.09 MPaG, it is not preferable because the separation ability of distillation is lowered, and if it exceeds +5 MPaG, the equipment that can withstand the pressure becomes expensive, which is not industrially preferable.

The reaction time is adjusted according to the temperature, pressure, type and amount of acid catalyst used, etc., and the reaction may be terminated by arbitrarily determining the end point of the reaction.

The end point of the reaction may be determined, for example, by quantifying the amount of ammonia discharged by reactive distillation. This amount of ammonia can be determined by, for example, introducing a gas discharged by reactive distillation into a container containing an arbitrary amount of water to form an aqueous solution, and performing acid-base titration, coulometric titration, ion chromatographic analysis, etc. from a sampling solution of this aqueous solution. It can be quantified. As another example, the reaction solution may be sampled from the reaction system, gas chromatographic analysis or the like of the sample solution may be performed, and the conversion rate may be obtained from the amount of the remaining raw material, the amount of the generated target product, or the like.

After completion of the reaction, the target organic silylamine compound can be purified from the reaction system by the following post-treatment process.

4-3. Post-treatment step In addition to the target organic silylamine compound, unreacted raw materials, acid catalysts, and the like may remain in the reaction system after completion of the reaction. When an additive such as a solvent described later is added, the additive may remain. The target organic silylamine compound can be purified from the reaction solution by employing a general procedure commonly used by those skilled in the art. For example, simple distillation (flash distillation), thin film distillation and the like are preferable. The purification method is not limited to these.

<5. Acid catalyst>
In the production method of the present invention, the reaction is carried out in the presence of an acid catalyst in order to accelerate the reaction. The acid catalyst is preferably an amine salt having a “pKa (referring to pKa in an aqueous solution; the same applies to other parts of the present specification) of −13 or more and +1 or less of Bronsted acid”. Such “amine salts formed between strong acids and amines” are generally moderate to weak acids, but such “amine salts that are relatively weak acids” are used as “acid catalysts” in the reaction system. The present inventors have found that the silylamine-forming reaction of the present invention proceeds particularly preferably when present in (see Examples).

The acid catalyst may be obtained in the reaction system by bringing the Bronsted acid into contact with the “alkylamine represented by the general formula (2)” present in the reaction system. In the reaction system, it can be considered that the Bronsted acid sufficiently exhibits the ability as an acid catalyst after forming an amine salt with the alkylamine represented by the general formula (2).

Suitable Bronsted acids include sulfonic acids such as sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, trifluoroacetic acid, peroxysulfonic acid, Examples include chloric acid. However, as described above, if water is present in a large amount in the reaction system, the target product may be hydrolyzed, which may affect the yield and purity of the product. Therefore, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, and camphorsulfonic acid, which are acids that do not require the presence of water, are particularly preferable. Among these, sulfuric acid from which an anhydrous reagent can be obtained at low cost is more preferable because it does not require a subsequent dehydration operation, and good reactivity can be obtained with a simple operation. For example, “concentrated sulfuric acid of 98% or more” is one of particularly preferred Bronsted acids.

The acid catalyst may be one in which the Bronsted acid is converted to an amine salt in advance. Specifically, the Bronsted acid is brought into contact with an amine to prepare an amine salt of the Bronsted acid, and then the amine salt is used as the “acid catalyst” in the reaction system. If the said amine salt is what is marketed, the said preparation process can be skipped and it can use for a reaction system as it is. The amine in this case is not particularly limited as long as it is an amine having a basicity close to that of the alkylamine represented by the general formula (2) which is a raw material of the production method of the present invention. Specific examples include ammonia or tertiary amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, pyridine, 2,4-dimethylpyridine, 2,6-dimethylpyridine, and N, N-dimethylaminopyridine. .

Suitable amine salts of the Bronsted acid include ammonium methanesulfonate, ammonium p-toluenesulfonate, ammonium camphorsulfonate, ammonium iodide, triethylamine hydrochloride, dimethylamine hydrochloride, pyridine hydrochloride, ammonium hydrochloride, ammonium bromoacid, Examples thereof include triethylamine sulfate, dimethylamine sulfate, pyridine sulfate, ammonium sulfate, and ammonium nitrate. Among them, triethylamine hydrochloride, dimethylamine hydrochloride, pyridine hydrochloride, ammonium hydrochloride, ammonium oxalate, triethylamine sulfate, dimethylamine sulfate, pyridine sulfate, ammonium sulfate, and ammonium nitrate are more preferable, and ammonium sulfate is particularly preferable.

These acid catalysts (amine salts) can be synthesized by bringing the Bronsted acid into contact with the amine. The amine salt can be synthesized outside the system in advance and then introduced into the reaction system of the present invention.

On the other hand, as described above, when the alkylamine represented by the general formula [2] is in an excessive condition, the excess alkylamine also serves as the “amine”, and this is used as the Bronsted. It is also possible to generate an “acid catalyst (alkylamine salt)” in the reaction system by reacting with an acid. In this case, it is particularly preferable because it eliminates the trouble of separately synthesizing an “amine salt” outside the system, and a highly active “acid catalyst” can be generated in the system simply by adding, for example, sulfuric anhydride into the reaction system. .

In the case of an amine salt using “Bronsted acid having a pKa of more than +1” as the Bronsted acid, the ability as a catalyst for mediating the reaction is low, which may not be a practical production method (described later “ See Reference Examples). Examples of the Bronsted acid having a pKa exceeding +1 include phosphoric acid (pKa: about 2), acetic acid (pKa: about 4.8), and the like.

In addition, when a Bronsted acid having a pKa of less than -13 is used, various side reactions may be induced. An example of a Bronsted acid having a pKa of less than −13 is trifluoromethanesulfonic acid (pKa: about −14). In particular, when such a super strong acid is directly added to the reaction system, care must be taken because the super strong acid comes into direct contact with the raw material compound before the conversion to the amine salt.

The acid catalyst can be diluted with a solvent. However, as described later, since it is not essential to use a solvent in the reaction of the present invention, it is not necessary to dilute and use an acid catalyst with a solvent. If diluted with a solvent, it will be described in <6. Solvents listed in <Solvent> can be preferably employed.

The amount of the acid catalyst used may be 0.0001 g or more and 0.8 g or less, preferably 0.1 g or less, and more preferably 0.02 g or less, with respect to 1 g of the raw organic disilazane compound. Even if added in excess of 0.8 g, there is no effect of improving the moving speed to equilibrium, which is not industrially preferable. When the amount is less than 0.0001 g, the effect as a catalyst is not sufficient.

<6. Solvent>
The production method of the present invention can be carried out without using a solvent, but a solvent may be used for the purpose of adjusting the pressure conditions of the reaction. There is no restriction | limiting in particular in the kind of solvent to be used. Specific examples include nitriles, amides, sulfoxides, ethers, hydrofluorocarbons, hydrofluoroethers, hydrocarbons or aromatic hydrocarbons. More specifically, examples of the nitrile include acetonitrile and benzonitrile. Examples of the ketone include acetone, methyl ethyl ketone, diethyl ketone, methyl-n-propyl ketone, methyl-iso-propyl ketone, methyl-n-butyl ketone, and methyl-iso-butyl ketone. Examples of the amide include N, N-dimethylformamide, N, N-dimethylacetamide, and N, N-dimethylimidazolidinone. Examples of the sulfoxide include dimethyl sulfoxide. Examples of the ether include diethyl ether, methyl t-butyl ether, diisopropyl ether, dibutyl ether, and tetrahydrofuran. Hydrofluorocarbons include trifluoromethane, difluoromethane, 1,1,1,2-tetrafluoroethane, 1,1,1-tetrafluoroethane, 1,1-difluoroethane, 1,1,1,2,3,3, 3-heptafluoropropane, 1,1,1,3,3,3-hexafluoropropane, 1,1,1,3,3-heptafluoropropane, 1,1,1,3,3-pentafluorobutane, Examples include 1,1,1,2,2,3,4,5,5,5-decafluoropentane and 1,1,2,2,3,3,4-heptafluorocyclopentane. Hydrofluoroethers are methyl 1,1,2,2,2-pentafluoroethyl ether, methyl trifluoromethyl ether, methyl 1,1,2,2-tetrafluoroethyl ether, 1,1,2,2-tetra Fluoro-1- (2,2,2-trifluoroethoxy) ethane, (2,2,3,3-tetrafluoropropyl) (1,1,2,3,3,3-hexafluoropropyl) ether, (Methyl) (nonafluorobutyl) ether, (methyl) (nonafluoroisobutyl) ether, (ethyl) (nonafluorobutyl) ether, (ethyl) (nonafluoroisobutyl) ether, 1,1,1,2,2, 3,4,5,5,5-decafluoro-3-methoxy-4- (trifluoromethyl) pentane, 2-trifluoromethyl-3-ethoxy Dodecafluoro hexane, 1,1,1,2,3-hexafluoro-4- (1,1,2,3,3,3-hexafluoro-propoxy), and pentane. Aromatic hydrocarbons include benzene, toluene, xylene, mesitylene, and perfluorobenzene. Examples of the hydrocarbon include butane, pentane, hexane, heptane, octane, nonane, and decane. These solvents may be used alone as a raw material solvent or an extractant for extractive distillation, or may be used in combination of a plurality of types.

The optimum amount of solvent when a solvent is used in the raw material system is adjusted according to the type of raw material, but may be 5 g or less with respect to 1 g of the organic disilazane compound of the raw material, preferably 2 g or less, and 0.5 g or less. More preferred. If the solvent is added in excess of 5 g, the amount of raw materials charged to the reactor is reduced, that is, productivity is lowered, which is not preferable.

As described above, the object of the present invention may be decomposed when it comes into contact with a large amount of water. For this reason, it is not preferable to use water as a solvent. When the acid such as hydrochloric acid as described above is directly introduced into the reaction system as a Bronsted acid, water is inevitably introduced into the system. It can wake itself up. However, it is not desirable that water be actively present in the reaction system, and the mass of water relative to the total mass of the solution should normally be 10% or less, preferably 5% or less, more preferably 1% or less. is there.

<7. Reaction operation>
The production method of the present invention can take any of batch, semi-batch and continuous reaction modes depending on the raw material introduction method. The reaction operation will be described below for the case where a batch system is used.

In a reaction vessel equipped with a condenser or a distillation column provided with a condensing part at the top, an organic disilazane compound of the general formula (1), an alkylamine of the general formula (2), an acid catalyst or an acid catalyst precursor, and A predetermined amount of each solvent is introduced as necessary. In this case, the acid catalyst means a pre-prepared amine salt of "Bronsted acid having a pKa of -13 or more and +1 or less", and the acid catalyst precursor means "brene having a pKa of -13 or more and +1 or less. “Sted acid” means the same. The reactor may be a pressure resistant reactor to adjust the type of raw material or the reaction temperature. The reactor may be equipped with a stirrer to enhance the stirring effect. The order of introducing the raw materials is not limited. The introduction of the raw material or the like may be in a liquid, gas, or solid state, and may be performed in a state dissolved in a solvent as necessary. Next, the reaction temperature and reaction pressure are brought close to the predetermined values while stirring as necessary, the reflux in the distillation column is confirmed, the generated ammonia is extracted from the upper part of the distillation column, and the reaction is continued for a predetermined time, and then the reaction is completed. To do.

After completion of the reaction, the reactor contents can be taken out with liquid or gas. The extracted reactor contents may contain unreacted substances or solvents such as acid compounds or salts thereof. By subjecting this to operations such as simple distillation (flash distillation) and rectification, the target organic silylamine compound of the general formula (3) can be obtained.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.

[Example 1]
A 500 mL autoclave equipped with a 1 cm diameter, 30 cm high distillation column (12 theoretical plates) and a stirrer packed with a 3 mm diameter stainless steel Raschig ring was charged with 161 g (1 mol) hexamethyldisilazane and 6.5 g (0.05 mol) ammonium sulfate. ), And after sealing, 99 g (2.2 mol) of dimethylamine was injected. The upper part of the packed tower was provided with an outlet equipped with a condenser and a gas flow valve. The condenser was cooled with a refrigerant at −5 ° C. (the process up to this point is referred to as “process condition 1”. The same applies hereinafter in Examples, Reference Examples and Comparative Examples). When mixing in the autoclave with an agitator attached to the autoclave and heating in an oil bath at 80 ° C, the pressure inside the reactor gradually rises, and when the pressure reaches 1 MPaG, the valve at the outlet is gradually opened and gas is discharged. Started extracting. The extracted gas was guided and absorbed in 500 mL of water stretched in a 1 L flask. The amount of base in the generated aqueous ammonia was appropriately measured by acid-base titration and monitored as the amount of ammonia. The amount of ammonia extracted after 8 hours was 0.90 mol, and the internal pressure decreased to 0.08 MPaG. Further, gas extraction was continued, but gas generation stopped after 30 minutes. The amount of ammonia in the extracted gas was 1.02 mol. The temperature of the oil bath was raised to 100 ° C. and flash distillation was performed at normal pressure, and a liquid having a boiling point of 84 to 87 ° C. was fractionated to obtain 197 g of trimethylsilyldimethylamine (yield 84%). When analyzed by gas chromatography, the purity was 98 area%.

[Example 2]
Reactive distillation was carried out under the same conditions as in process condition 1 except that 4.9 g (0.05 mol) of sulfuric acid was used instead of ammonium sulfate. When heated in an oil bath at 80 ° C while mixing the autoclave contents with a stirrer, the pressure inside the reactor gradually increases, and when the pressure reaches 1 MPaG, the valve at the outlet is gradually opened to start gas extraction. did. The reaction was continued while monitoring the extracted ammonia, and the reaction was completed after 7 hours. Thereafter, the contents were flash distilled to obtain 190 g of trimethylsilyldimethylamine (yield 81%). When analyzed by gas chromatography, the purity was 97 area%.

[Example 3]
Using a 1 cm diameter, 30 cm high distillation column (4 theoretical plates) packed with 3 mm diameter stainless steel Raschig rings, 180 g (4 mol) of dimethylamine was used under the same conditions as in process condition 1 except that reactive distillation was performed. Carried out. When heated in an oil bath at 80 ° C. while mixing the contents of the autoclave with a stirrer, the pressure gradually increased. When the pressure reached 1 MPaG, the valve at the outlet was gradually opened to start gas extraction. The reaction was continued while monitoring the extracted ammonia, and the reaction was terminated after 3 hours. Thereafter, the content was flash distilled to obtain 172 g of trimethylsilyldimethylamine (yield 73%). When analyzed by gas chromatography, the purity was 98 area%.

[Example 4]
Using a 1 cm diameter, 30 cm high distillation column (4 theoretical plates) packed with 3 mm diameter stainless steel Raschig rings, 180 g (4 mol) of dimethylamine was used under the same conditions as in process condition 1 except that reactive distillation was performed. Carried out. When the autoclave contents were heated with an oil bath at 80 ° C. while mixing the contents of the autoclave with a stirrer, the pressure gradually increased, the pressure reached 1 MPaG, and the reaction was continued for 2 hours. Then, when the autoclave was cooled and the internal temperature of the reactor became 40 ° C. or lower, the outlet valve was gradually opened to extract gas. Further, after heating for 2 hours after heating in an oil bath at 80 ° C., the operation of cooling the autoclave again and extracting ammonia gas was repeated 4 times, and the amount of ammonia extracted reached 1.1 equivalents. The contents were flash distilled to obtain 187 g of trimethylsilyldimethylamine (yield 80%). When analyzed by gas chromatography, the purity was 98 area%.

[Example 5]
Reactive distillation was carried out under the same conditions as in process condition 1 except that 7.5 g (0.05 mol) of trifluoromethanesulfonic acid was used instead of ammonium sulfate. When heated in an oil bath at 80 ° C. while mixing the contents of the autoclave with a stirrer, the pressure gradually increased. When the pressure reached 1 MPaG, the valve at the outlet was gradually opened to start gas extraction. The reaction was continued while monitoring the extracted ammonia, and the reaction was completed after 7 hours. Thereafter, the contents were flash distilled to obtain 128 g of trimethylsilyldimethylamine (yield 55%). When analyzed by gas chromatography, the purity was 96 area%.

[Example 6]
Process conditions other than using a 1 cm diameter, 30 cm high empty column (theoretical plate number 1) instead of a 1 cm diameter, 30 cm high distillation column (12 theoretical plate) packed with 3 mm stainless steel Raschig rings Reactive distillation was carried out under the same conditions as in 1. When heated in an oil bath at 80 ° C. while mixing the contents of the autoclave with a stirrer, the pressure gradually increased. When the pressure reached 1 MPaG, the valve at the outlet was gradually opened to start gas extraction. The reaction was continued while monitoring the extracted ammonia, and the reaction was completed after 7 hours. Thereafter, the contents were flash distilled to obtain 111 g of trimethylsilyldimethylamine (yield 47%). When analyzed by gas chromatography, the purity was 92 area% and contained 5% hexamethyldisilazane.

[Reference example]
Reactive distillation was carried out under the same conditions as in process condition 1 except that 4.9 g (0.05 mol) of phosphoric acid was used instead of ammonium sulfate. Even when heated in an oil bath at 80 ° C. while mixing the contents of the autoclave with a stirrer, the pressure increased only to 0.5 MPaG, and heating was continued for 10 hours without extracting gas. The autoclave was cooled to room temperature and the contents were sampled. Analysis by gas chromatography revealed that the ratio of trimethylsilyldimethylamine to hexamethyldisilazane was 4:96 and the reaction conversion rate was low.

[Comparative Example 1]
The reaction was carried out under the same conditions as process condition 1 without extracting ammonia. The mixture was heated in an oil bath at 80 ° C. while mixing the contents of the autoclave with a stirrer, and the pressure reached 1.5 MPaG after 10 hours. Thereafter, the autoclave was cooled to room temperature and the contents were sampled. Analysis by gas chromatography revealed that the ratio of trimethylsilyldimethylamine to hexamethyldisilazane was 25:75 and the reaction conversion rate was low.

[Comparative Example 2]
Reactive distillation was carried out under the same conditions as in process condition 1 except that ammonium sulfate was not added. When heated in an oil bath at 80 ° C. while mixing the contents of the autoclave with a stirrer, the pressure increased only to 0.5 MPaG, and heating was continued for 10 hours without removing the gas. The autoclave was cooled to room temperature and the contents were sampled. When analyzed by gas chromatography, the ratio of trimethylsilyldimethylamine to hexamethyldisilazane was 1:99, indicating that the reaction conversion rate was low.

Table 1 summarizes the simple implementation conditions and results of Examples 1 to 6, Reference Example, and Comparative Examples 1 and 2.

The present invention is a method for producing an organic silylamine compound useful as a building block or a surface treatment agent. This production method has a simple production operation and high productivity as compared with the conventional production method of an organic silylamine compound. Further, the by-product in the production method of the present invention is ammonia, and the by-product ammonia can be easily recovered by reactive distillation. Since ammonia is a useful substance for various uses such as fertilizer, the production method of the present invention has almost no unnecessary waste and a low environmental load.

Claims

In the general formula (3), the organic disilazane compound represented by the general formula (1) and the alkylamine represented by the general formula (2) are reacted in the presence of an acid catalyst while removing generated ammonia by reactive distillation. The manufacturing method of the organic silylamine compound represented.

Wherein R 1 , R 2 and R 3 are each independently a linear or branched alkyl group having 1 to 7 carbon atoms, a cyclic alkyl group having 3 to 5 carbon atoms, or a phenyl group. .)

(Wherein the R 4 and R 5 are each independently a hydrogen atom, an alkyl group or the number 3 to 5 cyclic alkyl group having a carbon linear or branched chain having 1 to 5 carbon atoms, R 4 and R 5 is not a hydrogen atom at the same time.)

(Wherein, each R 1, R 2 and R 3 has the same meaning as R 1, R 2 and R 3 in the general formula (1), respectively R 4 and R 5, R 4 in the general formula (2) And synonymous with R 5. )
The production method according to claim 1 , wherein R 1 , R 2 and R 3 are all methyl groups.
The production method according to claim 1 or 2, wherein R 4 and R 5 are each independently a methyl group or an ethyl group.
The manufacturing method in any one of Claims 1 thru | or 3 which makes the theoretical plate number of the said reactive distillation 2 or more and 100 or less.
5. The production method according to claim 1, wherein the reactive distillation is performed at a pressure of −0.09 MPaG or more and +1 MPaG or less.
6. The production method according to claim 1, wherein the acid catalyst is an amine salt of “Bronsted acid having a pKa of −13 or more and +1 or less”.
The group in which the Bronsted acid consists only of sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, trifluoroacetic acid, and perchloric acid The production method according to claim 6, wherein the production method is at least one Bronsted acid.
The acid catalyst is at least one acid catalyst selected from the group consisting of triethylamine hydrochloride, dimethylamine hydrochloride, pyridine hydrochloride, ammonium hydrochloride, ammonium oxalate, triethylamine sulfate, dimethylamine sulfate, pyridine sulfate, ammonium sulfate, and ammonium nitrate. The manufacturing method in any one of Claims 1 thru | or 6.
In the reaction system, the acid catalyst is brought into contact with the “alkylamine represented by the general formula (2)” present in the reaction system with “Bronsted acid having a pKa of −13 or more and +1 or less”. The production method according to any one of claims 1 to 6, wherein the production method is obtained.
“Bronsted acid having a pKa of −13 or more and +1 or less” is contacted with an amine to prepare an amine salt of “Bronsted acid having a pKa of −13 or more and +1 or less”, and then the amine salt The production method according to claim 1, comprising a step of introducing the acid catalyst into the reaction system.
The production method according to claim 7, wherein the Bronsted acid is sulfuric acid.
The production method according to any one of claims 1 to 6, wherein the reaction temperature is 30 ° C or higher and 150 ° C or lower.