The method of obtaining substituted amino-1,3,5-triazines

 

(57) Abstract:

Usage: as pharmaceutical drugs, herbicides and intermediates in the synthesis of herbicides. The inventive product - substituted amino-1,3,5-triazine f-ly 1, where R = C1-C4-alkyl, haloalkyl, phenyl, 4-nitrophenyl, heterocyclic aromatic five - or six-membered cycle, which contains an oxygen atom or nitrogen; R' = C1-C4-alkyl, methoxyethyl, allyl, cyclohexyl; R2= a hydrogen atom, methyl, ethyl, cyclopropyl, phenyl, benzyl. Reagent 1: languagein f-crystals of N2NC(OTHER2) NCN. Reagent 2: alcohol f-ly R OH. Reagent 3: allerease agent. Reaction conditions: the interaction of reagents 1 and 2 is carried out in the presence of zinc chloride at a ratio of languagein: zinc chloride 1:(1-2), and the acylation in the environment of acetonitrile in the presence of triethylamine. Connection structure f-ly I . 1 C. p. F.-ly, 1 table.

The invention relates to a method for previously known and new derivatives of amino-1,3,5-triazine of General formula (I):

,

where R1-C4-alkyl, haloalkyl, phenyl, 4-nitrophenyl, heterocyclic aromatic five - or six-membered cycle, which contains an oxygen atom or nitrogen; R1WITH1-C4 the categories are used as pharmaceutical preparations, herbicides and intermediates in the synthesis of herbicides number of arylsulfonamides.

A method of obtaining unsubstituted amino-1,3,5-triazines (Ia) in the interaction of dicyandiamide (II) salts of divalent copper (in the ratio of about 2: 1) in the presence of the corresponding alcohols, usually in a solvent (N,N-dimethylformamide, o,O'-dimethyl - or diacylglycerol) through the formation of copper bis-complexes (III), with their subsequent processing by the corresponding anhydrides of carboxylic acids [1]

,

where R' is unsubstituted or substituted WITH1-C4-alkyl, and R1= C1-C4-alkyl.

Closest to the technical solution (prototype) is a method of obtaining substituted amino-1,3,5-triazines (Ib) in the interaction of languageyou (IV) salts of divalent copper ( in the ratio of about 2:1) in the presence of the corresponding alcohols through the formation of copper bis-complexes (V), with their subsequent processing by the corresponding anhydrides of carboxylic acids in the presence of pyridine or without it [2]

,

where R" is methyl, unsubstituted or substituted phenyl, -alkyl,- alkyl, unsubstituted or substituted phenyl. The disadvantage of this method is the low output (from 18 to 59%) of the target product.

This task is solved by the interaction of languageyou (VI) with zinc chloride (in a ratio of from 1:1 to 1:2) in the presence of the corresponding alcohols through the formation of zinc mono-complexes (VII) with their subsequent processing various allerease agents in the presence of triethylamine in an environment of acetonitrile:

.

The method is illustrated by the following examples.

Example 1. 2.5 g (30 mmole) of dicyandiamide (II), 4.8 g (35 mmole) of zinc chloride and 8 ml (198 mmole) of methanol is boiled under stirring for 4 h, cooled, filtered, washed on the filter with 2x10 ml of methanol, air-dried and gain of 7.3 g (96.9 percent) of the complex 0-methylguanosine and zinc chloride (VII). So pl. 215oC (decomp.). Found, 14,12; 14,16; N 3,29; 3,21; N 21,58; 21,72; Cl 27,93; to 28.05; C3H8Cl2N4OZn. Calculated From 14.3; N 3,2; N 22,2; Cl 28,1.

To 5.0 g (to 19.8 mmole) mono-complex (VII) add 15 ml of triethylamine and 10 ml of acetonitrile. To the resulting suspension with stirring, poured 4 ml (42,4 mmole) of acetic anhydride. The reaction mixture is boiled for 2.5 h and filtered. The precipitate was washed with 2x10 ml of acetonitrile, dried in air and get 2,62 g (94,1% ) 6-amino-4-methyl-2-methoxy-1,3,5-triazine (I). So pl. 258-260oC. the resulting product did not give the temperature depression of the PR is 5 mmole) of zinc chloride, 6 ml (148 mmole) of methanol and 13 ml of acetonitrile is boiled under stirring 4 h and Then distilled off the residue with methanol, cooled, added to 13.5 ml (143 mmole) of acetic anhydride and stirring dropwise 20 ml of triethylamine so that the temperature of the reaction mass does not exceed 70oC. the Resulting mixture is boiled under stirring for 3 h, cooled, evaporated in vacuum to dryness, washed with water. The residue is recrystallized from methanol. Get 5.73 g (81,0%) 6-methyl-4-methylamino-2-methoxy-1,3,5-triazine. So pl. 160-162oC. the resulting product did not give temperature depression at the joint fusion with a known pattern.

Example 3. 7.2 g (29 mmole) mono-complex (VII) (see example 1), 13 ml of triethylamine and 75 ml of acetonitrile is cooled to -5oC. To the obtained mixture under stirring was added dropwise 5.5 ml (77 mmole) acetylchloride so that the temperature of the reaction mixture did not exceed 0oC. Upon completion of addition, the mixture was stirred at 0o1 h and left overnight at room temperature. The mixture is then boiled for 1.5 h and filtered. The precipitate was washed with 2x10 ml of acetonitrile. Get 2,40 g 60,0%) 6-amino-4-methyl-2-methoxy-1,3,5-triazine (I). So pl. 258-260oC. the resulting product did not give temperature depression when combined the technology with examples 1-3 (see table).

Use as the base of the pyridine or aqueous solution of alkali reduces the yield of the target product.

1. The method of obtaining substituted amino-1,3,5-triazines of the formula

< / BR>
where R1WITH4-alkyl, haloalkyl, phenyl, 4-nitrophenyl, heterocyclic aromatic five - or six-membered cycle, which contains an oxygen atom or nitrogen;

R1WITH1WITH4-alkyl, methoxyethyl, allyl, cyclohexyl;

R2a hydrogen atom, methyl, ethyl, cyclopropyl, phenyl, benzyl,

through the cooperation of languageyou formula II

< / BR>
where R2have the above values,

with alcohols of the formula III, R1OH, where R1have the above meanings, in the presence of chloride divalent transition metal followed by treatment of the resulting complex 0-alkyl-guanidinoacetic and metal chloride relevant allerease agents of the formula IV RC(O)Y, where R has the above significance, and J is a halogen or the group RC(O)O, in the presence of an organic base in an environment of an organic solvent, characterized in that as chloride divalent transition metal using zinc chloride in the ratio of languagein (II): zinc chloride from 1 1 to 1 2 formed with the which are processed with the proper allermuir agent in the environment of acetonitrile in the presence of triethylamine.

2. The method according to p. 1, characterized in that the process of obtaining the target product is carried out with the selection or without isolating the intermediate formed monocomplex O-ancillarisation and of zinc chloride of the formula V.

 

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