JP7015451B2 - Method for producing peroxycarbamate compound - Google Patents

Description

The present invention relates to a method for producing a peroxycarbamate compound.

Conventionally, a peroxycarbamate compound represented by the following formula (4) having one alcoholic silyl group and one peroxide bond in the molecule has been known.

In the peroxycarbamate compound represented by the above formula (4), the peroxide bond is cleaved by heat, and a t-butoxy radical and an aminyl radical having an alkoxysilyl group are generated. The aminyl radical having an alkoxysilyl group can have a radical site at the growth end of the polymer chain or can be bonded to the polymer chain, while the alkoxysilyl group can react with glass or inorganic fine particles. Since it is possible, it is known to be useful as a radical generator capable of synthesizing an organic-inorganic hybrid polymer.

Further, the use of the peroxycarbamate compound represented by the formula (4) is expected to be effective as a polymerization catalyst for polymer-modifying the surface of glass or inorganic fine particles. Therefore, for the purpose of promoting the silane coupling reaction, those containing phenol have been desired.

Patent Document 1 discloses a method for synthesizing a peroxycarbamate compound represented by the formula (1) by reacting t-butyl hydroxy peroxide with 3- (trimethoxysilyl) propyl isocyanate.

In addition, Non-Patent Document 1 also discloses a method for synthesizing a peroxycarbamate compound represented by the formula (1). Further, Patent Document 2 discloses a reaction between a carbonate compound and a primary amine.

Bioorganic & Medical Chemistry 14 (2006) 6213-6222

JP-A-48-40726 WO2014 / 092161

In the reaction described in Non-Patent Document 1, nitrophenol is produced as a by-product, but since nitrophenol exhibits strong acidity, the decomposition of the obtained peroxycarbamate compound is promoted, and the yield is not only lowered. , There is a safety issue. Therefore, a production method that does not generate nitrophenol is desired.

In the method described in Patent Document 1, since t-butyl hydroxyperoxide is an aqueous solution, there is a problem that if water is present, isocyanate reacts with water and is inactivated, and the target compound cannot be efficiently obtained. Moreover, since phenol is not produced, it was necessary to add phenol separately to the reaction system.

In the reaction described in Patent Document 2, the reaction between the carbonate compound and the primary amine is disclosed, but this reaction condition is because the reaction uses a sodium methoxide / methanol solution as a reaction catalyst at a temperature of 50 ° C. When the organic peroxide is synthesized in the above, not only the product is decomposed and the yield is lowered, but also there is a safety problem.

An object of the present invention is to provide a production method for synthesizing a specific peroxycarbamate compound safely and easily in a high yield.

（式（１）において、Ｒ^１は、炭素数１～４の炭化水素基である）

次いで、前記ヒドロキシペルオキシドの前記炭化水素溶液とフェニルクロロホルメートとを混合し、前記ヒドロキシペルオキシドとフェニルクロロホルメートとを－１０℃以上、２０℃以下の反応温度で反応させることによって、ペルオキシフェニルモノカーボネートを得る工程（Ｂ）；および
次いで、前記ペルオキシフェニルモノカーボネートと、式（２）で表されるシリル基含有アミンとを、炭素数５～１２の炭化水素中で－１０℃以上、２０℃以下の反応温度で反応させることによって、式（３）で表される化合物を得る工程（Ｃ）

（式（２）において、Ｒ^２、Ｒ^３、Ｒ^４は、それぞれ独立して、水素原子または炭素数１～４の炭化水素基である）

（式（３）において、Ｒ^１は炭素数１～４の炭化水素基であり、Ｒ^２、Ｒ^３、Ｒ^４は、それぞれ独立して、水素原子または炭素数１～４の炭化水素基である）
をこの順で実施することを特徴とする、ペルオキシカーバメート化合物の製造方法。 That is, the present invention is as follows.
(1) A step of obtaining a hydrocarbon solution of hydroxyperoxide having a water content of 1% or less by substituting the solvent of the aqueous solution of hydroxyperoxide represented by the formula (1) from water with a hydrocarbon having 5 to 12 carbon atoms. (A);

(In the formula (1), R ¹ is a hydrocarbon group having 1 to 4 carbon atoms).

Next, the hydrocarbon solution of the hydroxy peroxide and phenylchloroformate are mixed, and the hydroxyperoxide and phenylchloroformate are reacted at a reaction temperature of −10 ° C. or higher and 20 ° C. or lower to peroxyphenyl mono. Step (B) of obtaining a carbonate; and then, the peroxyphenyl monocarbonate and the silyl group-containing amine represented by the formula (2) are placed at −10 ° C. or higher and 20 ° C. in a hydrocarbon having 5 to 12 carbon atoms. Step (C) to obtain the compound represented by the formula (3) by reacting at the following reaction temperature.

(In the formula (2), R ² , R ³ , and R ⁴ are independently hydrogen atoms or hydrocarbon groups having 1 to 4 carbon atoms).

(In the formula (3), R ¹ is a hydrocarbon group having 1 to 4 carbon atoms, and R ² , R ³ and R ⁴ are independently hydrogen atoms or hydrocarbon groups having 1 to 4 carbon atoms. be)
A method for producing a peroxycarbamate compound, which comprises carrying out the above in this order.

According to the present invention, the raw material compound is dehydrated, and then the peroxycarbonate compound is reacted with the primary amine under the conditions of −10 ° C. to 20 ° C. to obtain the desired peroxy represented by the formula (3). The carbamate compound could be obtained safely and easily in high yield. Moreover, since phenol is contained as a by-product of the reaction, it is not necessary to add phenol separately.

(Step (A))
In the step (A), the solvent of the aqueous solution of hydroxyperoxide represented by the formula (1) is replaced with a hydrocarbon having 5 to 12 carbon atoms to obtain a hydroxyperoxide having a water content of 1.0% by mass or less. This is a step of obtaining a hydrocarbon solution.

The following can be exemplified as this solvent replacement method.
(A) The aqueous hydroxyperoxide solution is dehydrated, and then the obtained hydroxyperoxide is redissolved in a hydrocarbon solvent having 5 to 12 carbon atoms.
(B) A hydrocarbon solvent and an inorganic salt are added to and mixed with a hydroxyperoxide aqueous solution, the oil phase and the aqueous phase are separated, and the oil phase is used as a hydrocarbon solution in the step (B).

Here, the method (b) is more preferable. At this time, known inorganic salts can be used, for example, chlorides such as sodium chloride, potassium chloride and calcium chloride, sulfides such as sodium sulfate, potassium sulfate, magnesium sulfate and ammonium sulfate (sulfate), sodium nitrate and potassium nitrate. Nitrate and the like are used. Of these, potassium chloride, calcium chloride and ammonium sulfate are preferable. The reason for using the inorganic salt is to increase the specific gravity of the aqueous phase and improve the separability from the oil phase.

Further, by adding a dehydrating agent to the hydrocarbon solution, the water content can be further reduced. A known dehydrating agent can be used. Sodium sulfate decahydrate (Glauber's salt) and magnesium sulfate heptahydrate are preferred.

Since each reaction of steps (B) and (C) needs to be carried out in a water-free system, the water content of the hydrocarbon solution obtained in step (A) is 1.0% by mass or less, but 0.5% by mass. % Or less is more preferable.

The solvent used in the step (A) is a hydrocarbon having 5 to 12 carbon atoms. Specifically, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, isopentane, isohexane, isoheptane, isooctane, isononan, isodecane, and cyclohexane, benzene, toluene, ethylbenzene, o-xylene. , M-xylene, p-xylene, naphthalene and other aromatic hydrocarbons are used. Of these, toluene, ethylbenzene, m-xylene and p-xylene are preferable. Further, non-polar solvents are preferable to polar solvents such as alcohols, ethers, ketones, esters, carboxylic acids, amides, and sulfoxides. Further, the hydrocarbon solvent may be one kind or a mixture of a plurality of kinds.

(Step (B))
In step (B), the above-mentioned hydrocarbon solution of hydroxyperoxide and phenylchloroformate are mixed and reacted at a reaction temperature of −10 ° C. to 20 ° C. to obtain peroxyphenyl monocarbonate.

In the step (B), the reaction temperature is −10 ° C. to 20 ° C., preferably 0 ° C. to 10 ° C. When the reaction temperature is low, the progress of the reaction is slowed down and the yield is lowered. On the other hand, if the reaction temperature is high, the obtained peroxyphenyl monocarbonate is decomposed and the yield is lowered, and if the reaction temperature is too high, the peroxyphenyl monocarbonate is rapidly decomposed, which poses a safety problem.

The reaction time in the step (B) is preferably 30 minutes to 240 minutes, more preferably 60 minutes to 120 minutes. By setting the reaction time to 30 minutes or more, it is easy to sufficiently proceed with the reaction and the yield is improved. On the other hand, by setting the reaction time to 240 minutes or less, the decomposition of the obtained peroxyphenyl monocarbonate can be suppressed, thereby improving the yield.

(Process (C))
In the step (C), the peroxyphenyl monocarbonate and the silyl group-containing amine represented by the formula (2) are mixed in a hydrocarbon having 5 to 12 carbon atoms at a reaction temperature of −10 ° C. or higher and 20 ° C. or lower. By reacting, the compound represented by the formula (3) is obtained.

In the step (C), the reaction temperature is −10 ° C. to 20 ° C., preferably 0 ° C. to 10 ° C. When the reaction temperature is low, the progress of the reaction is slowed down and the yield is lowered. On the other hand, if the reaction temperature is high, the obtained peroxycarbamate compound is decomposed and the yield is lowered, and if the reaction temperature is too high, the peroxycarbamate compound is rapidly decomposed, which poses a safety problem.

The reaction time is preferably 15 minutes to 240 minutes, more preferably 30 minutes to 120 minutes. By setting the reaction time to 15 minutes or more, the reaction proceeds sufficiently and the yield is further improved. On the other hand, by setting the reaction time to 240 minutes or less, the decomposition of the obtained peroxyphenyl monocarbonate can be suppressed and the yield can be improved.

This step (C) does not require a catalyst and is a non-catalytic reaction.
Generally, a catalyst such as sodium hydroxide or sodium methoxide is used for the reaction between the monocarbonate and the primary amine, but even if such a catalyst is not used in this reaction, the reaction can be sufficiently carried out under the above reaction conditions. proceed. On the other hand, when a catalyst is used, the peroxycarbamate compound is decomposed by exposure to a strong base and the yield is lowered. Further, since washing with water is required to remove the catalyst, the peroxycarbamate compound is exposed to water and the alkoxysilyl group is hydrolyzed, which is not preferable.

Further, in this step (C), the above-mentioned hydrocarbon solvent having 5 to 12 carbon atoms can be further added. In this case, when the mass of t-butylperoxyphenyl monocarbonate is 100 parts by mass, the mass of the hydrocarbon solvent having 5 to 12 carbon atoms is preferably 10 to 1000 parts by mass.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples, but the present invention is not limited to the scope of these examples.

(Example 1)
(Step (A))
To a 200 ml flask, 106 g of a 69% pure t-butyl hydroxyperoxide aqueous solution, 32 g of toluene, and 12 g of ammonium sulfate were added, and the mixture was stirred at room temperature for 15 minutes, and then the oil phase / aqueous phase was separated by a separating funnel. Magnesium sulfate (5 g) was added to the oil phase, and the mixture was dehydrated and filtered to obtain 100 g of a toluene solution of t-butyl hydroxyperoxide having a purity of 68%.
The yield of the obtained t-butyl hydroxyperoxide toluene solution was 99%, and the water content was 0.1%.

(Step (B))
To a 1000 ml flask, 100 g of the t-butyl hydroxyperoxide toluene solution obtained in step (A) and 36 g of pyridine were added and mixed at 5 ° C. On the other hand, a toluene solution obtained by mixing 60 g of phenylchloroformate and 24 g of toluene was added dropwise, and then the mixture was reacted at the same temperature (5 ° C.) for 60 minutes. The obtained reaction product was washed with a 4% aqueous hydrochloric acid solution and then with water, dehydrated and filtered to obtain 150 g of t-butylperoxyphenyl monocarbonate.
The yield of the obtained (C) t-butylperoxyphenyl monocarbonate was 88%.

(Process (C))
To a 1000 ml flask, 150 g of t-butylperoxyphenyl monocarbonate obtained in step (B), 3- (triethoxysilyl) propylamine, and 10 g of toluene are added, mixed at 5 ° C., and reacted for 60 minutes. As a result, the desired peroxycarbamate compound was obtained.

As a result, the yield in step (C) was 96%. The total yield of the steps (A) to (C) was 84%. The purity of the obtained peroxycarbamate compound was 50%, and the phenol content was 15%.

(Comparative Example 1)
Step (A) and step (B) were carried out in the same manner as in Example 1. Then, in the final step (D), 0.5 g of a 28% sodium methoxide / methanol solution was added to the reaction system as a catalyst, and the reaction was carried out at a reaction temperature of 50 ° C. Other than that, the same operation as in step (C) of Example 1 was carried out to obtain the desired peroxycarbamate compound.

The yield in the final step (D) was 12%. In addition, the total yield of the steps (A), "(B) and (D) was 10%. The purity of the peroxycarbamate compound was 6% and the phenol content was 15%.

Claims (1)

A step of obtaining a hydrocarbon solution of hydroxyperoxide having a water content of 1.0% by mass or less by substituting the solvent of the aqueous solution of hydroxyperoxide represented by the formula (1) from water with a hydrocarbon having 5 to 12 carbon atoms. (A);

(In the formula (1), R ¹ is a hydrocarbon group having 1 to 4 carbon atoms).

Next, the hydrocarbon solution of the hydroxy peroxide and phenylchloroformate are mixed, and the hydroxyperoxide and phenylchloroformate are reacted at a reaction temperature of −10 ° C. or higher and 20 ° C. or lower to peroxyphenyl mono. Step (B) to obtain a carbonate; Then, the peroxyphenyl monocarbonate and the silyl group-containing amine represented by the formula (2) are reacted in a non-catalytic system at a reaction temperature of −10 ° C. or higher and 20 ° C. or lower. Thereby, the step (C) of obtaining the compound represented by the formula (3).

(In the formula (2), R ² , R ³ , and R ⁴ are independently hydrogen atoms or hydrocarbon groups having 1 to 4 carbon atoms).

(In the formula (3), R ¹ is a hydrocarbon group having 1 to 4 carbon atoms, and R ² , R ³ and R ⁴ are independently hydrogen atoms or hydrocarbon groups having 1 to 4 carbon atoms. be)

A method for producing a peroxycarbamate compound, which comprises carrying out the above in this order.