JP4717479B2 - Method for producing aminotriazine dithiol compound - Google Patents

Description

  The present invention relates to a method for producing aminotriazine dithiol compounds used as a crosslinking agent, an adhesion promoter, a surface treating agent, a heavy metal treating agent, a rust preventive agent and the like.

JP 59-9661 Japanese Patent Laid-Open No. 10-237047 Japanese Patent Laid-Open No. 11-71357 JP 2002-47345 A The Chemical Society of Japan pp.1655 (1991) The Chemical Society of Japan pp. 952 (1993) Z.anorg.all.chem., 504, pp201 (1983) Indian.J.Chem, 12, pp490 (1974) The Chemistry of cyclic compounds, Vol.XIII, pp297 (1959)

  Triazine thiol compounds are used as crosslinking agents, adhesion promoters, surface treatment agents, heavy metal treatment agents, rust prevention agents, and the like. For example, Non-Patent Documents 1 to 5 and Patent Documents 1 to 4 describe methods for synthesizing various triazine thiol compounds.

  Non-Patent Documents 1 to 4 describe a method for producing a triazine thiol compound from a guanidine derivative. However, these methods are difficult to handle because they use a large excess of low-boiling carbon disulfide as a raw material, and there are also reactions at high temperatures.

  Patent Documents 1 to 4 describe a method for producing a triazine thiol compound in which an intermediate triazine dichloride is once synthesized and then isolated and then thiolated. However, the isolated triazine dichloride has a problem that the hygroscopic decomposition is likely to proceed, and it is difficult to adjust the reaction temperature due to a rapid exotherm generated during thiolation.

  An object of this invention is to provide the manufacturing method which can synthesize | combine amino triazine dithiol compounds by a simple method with high yield, without performing complicated operation.

（式中、R¹、R²は水素である。）で示されるアミノトリアジンジクロリドを合成し、反応混合物からアミノトリアジンジクロリドを単離することなく、アルカリ金属の水硫化物又はアルカリ金属の硫化物を加えてアミノトリアジンジクロリドと反応させて、一般式(4)

（式中、R¹、R²は上記と同じである。）で表されるアミノトリアジンジチオール化合物を合成し、次いでアミノトリアジンジチオール化合物を単離するアミノトリアジンジチオール化合物の製造方法に関する。
In the present invention, cyanuric chloride and ammonia are reacted until the consumption of cyanuric chloride is completed.

(Wherein R ¹ and R ² are hydrogen ), an alkali metal hydrosulfide or an alkali metal sulfide is synthesized without isolating the aminotriazine dichloride from the reaction mixture. And reacting with aminotriazine dichloride to give a general formula (4)

(Wherein R ¹ and R ² are the same as above). The present invention relates to a method for producing an aminotriazine dithiol compound in which an aminotriazine dithiol compound is synthesized and then the aminotriazine dithiol compound is isolated .

In the present invention, the reaction between cyanuric chloride and ammonia is carried out in an aqueous solvent using 1.5 to 3.0 times moles of ammonia with respect to cyanuric chloride until the cyanuric chloride disappears at 3 to 20 ° C. ) And a polar organic solvent compatible with water in the resulting reaction mixture, and 2.0 to 4.0 times molar alkali metal hydrosulfide based on the cyanuric chloride used as a raw material , or In the method for producing an aminotriazine dithiol compound represented by the general formula (4), an aqueous solution of an alkali metal sulfide is added and the reaction is carried out at 3 to 20 ° C. until the aminotriazine dichloride disappears.

The production method of the aminotriazine dithiol compound of the present invention includes a reaction (first reaction) of cyanuric chloride with an amine or ammonia (hereinafter also referred to as amines) represented by R ¹ R ² NH, and a first reaction. Aminotriazine obtained by the first reaction through the reaction (second reaction) of the aminotriazine dichloride and the alkali metal hydrosulfide or alkali metal sulfide (hereinafter also referred to as alkali metal sulfides). Dichloride is not isolated from the reaction mixture.

The raw material cyanuric chloride is represented by the following formula (1).

The amine used in the first reaction is represented by R ¹ R ² NH. Here, R ¹ and R ² independently represent H or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. The substituent is not particularly limited as long as it does not inhibit the reaction, and examples thereof include halogen, alkoxy, acyl, and acyloxy. Preferred examples of R ¹ and R ² include H, a methyl group, an n-butyl group, and an allyl group. Specific examples include ammonia, methylamine, ethylamine, allylamine, aniline, dimethylamine, diethylamine, and perfluoromethylamine.

  Examples of the alkali metal sulfide used include sodium hydrosulfide, potassium hydrosulfide, sodium sulfide, potassium sulfide and the like.

  The amount of amines used in the first reaction is preferably 1.5 to 4.0 times mol, more preferably 1.8 to 3.0 times mol based on the raw material cyanuric chloride. If the amount of amine used is too small, the reaction may not occur sufficiently, and if too much, the yield of the target product may decrease due to excessive reaction.

  The amount of alkali metal sulfides used in the second reaction is preferably 2.0 to 4.0 times mol, preferably 2.5 to 3.5 times mol based on the raw material cyanuric chloride used in the first reaction. More preferred.

  The first reaction is an amination reaction, and is preferably performed in water and in a suspended state. The amount of water used is preferably 800 to 3000 mL, more preferably 1000 to 2000 mL, per 1 mol of cyanuric chloride.

  In this amination reaction, cyanuric chloride and water are mixed in air at normal pressure and stirred in an ice bath, and the amines are added in 0.1 to 30 ° C., preferably 3 to 10 ° C. while maintaining 3 to 10 ° C. 45 minutes, preferably 10 to 25 minutes. After completion of the addition of amines, the reaction may be carried out with stirring at 3 to 20 ° C., preferably 3 to 10 ° C., for 75 to 180 minutes, preferably 90 to 150 minutes. If the reaction temperature is too high, the yield of the target product may decrease due to excessive reaction. The reaction is desirably carried out until cyanuric chloride disappears.

  After completion of the amination reaction of the first reaction, a thiolation reaction of the second reaction is performed. At this time, the reaction is preferably performed in a mixed solvent obtained by adding an organic solvent such as alcohol or N, N-dimethylformamide to the reaction mixture in which the amination reaction has been performed without isolating the intermediate reaction product. As the organic solvent, a polar solvent compatible with water used in the first reaction is suitable. A mixed solvent to which N, N-dimethylformamide is added is preferable.

  The amount of the organic solvent used is 600 to 3000 mL, preferably 1200 to 2400 mL, based on 1 mol of cyanuric chloride used in the first reaction.

  The thiolation reaction of the second reaction is carried out by adding the organic solvent to the reaction mixture obtained by the amination reaction at a pressure of 3 to 20 ° C., preferably 3 to 12 ° C. in air at normal pressure for 0.1 to 30 minutes. It is preferably added in 10 to 20 minutes, and after completion of addition, an aqueous solution of alkali metal sulfides is maintained in 3 to 20 ° C., preferably 3 to 10 ° C. for 5 to 60 minutes, preferably 10 to 20 minutes. The addition may be carried out by a method such as stirring for 0.1 to 360 minutes, preferably 15 to 90 minutes after completion of the addition.

  After completion of the second reaction, 1000 to 4000 mL, preferably 1500 to 2500 mL of water is poured into the reaction mixture. A method of removing the filtrate is preferred.

  Next, the obtained filtrate is stirred, 3.6% (1N) to 36% (11.65N) hydrochloric acid is added, the pH is adjusted to 1 or less, and the mixture is stirred for 0.1 to 24 hours, preferably 0.5 to 18 hours. Then, the aminotriazine dithiol compound that is the target product is preferably precipitated.

  Thereafter, for example, the precipitated aminotriazine dithiol compound is collected by filtration, washed twice with 2000 to 6000 mL, preferably 3000 to 4500 mL of water, and naturally dried for 18 to 66 hours. Is obtained.

  It is not necessary to isolate the intermediate aminotriazine dichloride, which is prone to hygroscopic decomposition, and there is no abrupt exotherm generated during thiolation of conventional aminotriazine dichloride. Is also expensive.

  The production method of the present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1
To a 500 mL three-necked round bottom flask equipped with a thermometer and a stirrer, 9.22 g (50 mmol) of cyanuric chloride and 62 mL of water were added and cooled to an internal temperature of 5 ° C. or lower while stirring. To this, 7.60 g (125 mmoL) of 28% ammonia aqueous solution was added dropwise over 12 minutes while maintaining the internal temperature at 10 ° C. or lower. After completion of dropping, the mixture was stirred for 105 minutes at an internal temperature of 5 ° C. or lower. After 105 minutes, cyanuric chloride was completely consumed.
The flask containing the reaction mixture was placed in an ice bath as it was, and 75 mL of N, N-dimethylformamide was added with stirring while maintaining the internal temperature at 20 ° C. or lower, and the mixture was stirred for 20 minutes under the same conditions to cool the internal temperature to 5 ° C. or lower. To this, 10.8 g (135 mmol) of 70% sodium hydrosulfide.n hydrate dissolved in 60 mL of water was added dropwise over 20 minutes while maintaining the internal temperature at 12 ° C. or lower. After completion of dropping, the mixture was stirred for 90 minutes at an internal temperature of 5 ° C. or lower. After 90 minutes, the intermediate 2-amino-1,3,5-triazine-4,6-dichloride was completely consumed.
To the obtained reaction mixture, 200 mL of water was poured and stirred for 60 minutes in an ice bath. After completion of the stirring, the insoluble matter of the reaction mixture in the flask was separated by filtration to obtain a filtrate. The filtrate was adjusted to pH 1 or less by adding 6 mL of 36% hydrochloric acid, and stirred for 30 minutes in an ice bath. After completion of the stirring, the precipitate was collected by filtration, washed twice with 160 mL of water, and air dried for 40 hours. As a result, 7.44 g (46.4 mmol) of 2-amino-1,3,5-triazine-4,6-dithiol as a target product was obtained with a yield of 93%.

Claims (1)

The reaction between cyanuric chloride and ammonia is carried out in an aqueous solvent using 1.5 to 3.0 moles of ammonia with respect to cyanuric chloride until the cyanuric chloride disappears at 3 to 20 ° C. to generate aminotriazine dichloride, then a polar organic solvent aminotriazine dichloride to the reaction mixture obtained, without isolation compatible with water, 2.0 to 4.0-fold molar alkali metal hydrosulfide the cyanuric chloride based A method for producing an aminotriazine dithiol compound represented by the general formula (4), wherein an aqueous solution of an acid or an alkali metal sulfide is added and the reaction is carried out at 3 to 20 ° C. until the aminotriazine dichloride disappears.

(In the formula, R ¹ and R ² are hydrogen.)