DD142338A1 - PROCESS FOR PREPARING 2-POSSUBLE-SUBSTITUTED 4,6-DIALKOXY-2 GAMMA HIGH 4,1,3,5-THIATRIAZINES - Google Patents

Abstract

Substituted in 2-, 4- and 6-position

Description

Process for the preparation of substituted 2-position

^ ^{i /} l, 3j5-thiatriazines.

Application of the technique

The invention relates to a process for the preparation of 2-substituted 4,6-dialkoxy-2,5-dihydro-2 ^, 1, 3,5-thiatriazines. Such compounds serve as intermediates in the synthesis of sulfur-containing organics, other biologically active compounds, the synthesis of Iharmaka, and sulfur-containing dyes.

Characteristic of the known technical solutions

The unsubstituted parent of the heterocyclic class of ^ [, 1,3,5-03iiatriazines is not known and obvious

also can not be produced because its stability is insufficient. The stability of the substituted 2 ^, 1,3,5-thiatriazines certain requirements are met, which are met only by a few synthetic routes. Thus, 2,4,6-triaryl-24, 1,3j5-thiatriazines can be prepared by reacting N-bromo-amidines and mercaptides, although the breadth of variation is not very great. Another elegant preparation is the reaction of sodium dicyanamide with thionyl chloride to give 2,4,6-trichloro-2 ^ T, 1,3} 5-thiatriazine, which is still accessible to nucleophilic substitution reactions. The production of substituted 2J | However, 1,3j-2-thiatriazines by nucleophilic substitution of 2,4,6-trichloro-2J, 1,3} 5-thiatriazine is also subject to considerable limitations, since the nucleophilic agent has to meet considerable requirements for its steric Eaumausfüllung. In the presence of protic solvents

are such syntheses, not possible. Derivatives of 2,5-dihydro-2Ä, 1 »3» 5- "fckia.tria2iine can not be synthesized in the hitherto known ways, and a synthesis of the new heterocyclic class of 2,5-dihydro is known.

Object of the invention

The invention has for its object to provide a process for the preparation of 2 ₎ 5-DihjäJ? O-2) k , 1,3> 5-thiatriazines from commonly available starting materials in an easy to carry out synthesis.

Explanation of the invention of the invention

The object is achieved in that imino-bis-carbimic acid

1 ?

dialkyl esters of general formula I, in which R. and R is an alkyl radical having 1-8 C atoms, with unsubstituted or substituted N-sulfinyl-arylsulfonamides of the general formula II in which R- * is an alkyl radical having 1-3 C atoms, an alkoxy radical having 1 3 C atoms, represents hydrogen, fluorine, chlorine and bromine, a nitro group or a disubstituted amino group, to 4,6-dialkoxy-2,5-

jl

dlhydro-24, 1,3 * 5-thiatriazinen of the general formula III, in • .der of the radicals R - R- * have the above meaning, 'be implemented. '' *

XVIjL <^

R ¹ OC ^ C-OR ²

η ι)

m NH

I II

R ¹ OQ; ^ c OR ²

Il ti

N. N

III

-3-21

As solvents for the unpredictable reaction, which proceeds with elimination of SOp and arylsulfonamide and formation of III and not of 1,3,5-triazines as Cycloadditionsprodukte serve aprotic ' ^v compounds such as diethyl ether, benzene, toluene, carbon tetrachloride, preferably with Boiling temperatures below 140 ⁰ C. The reaction is carried out without pressure in the temperature range between 0 ° and 120 ⁰ C, preferably at 20 ° to 60 ⁰ C, by slowly adding to a solution or suspension of I in a suitable solvent or dispersant with stirring the solution II in benzene, "ether or carbon tetrachloride is dropped in. The reaction components I and II have completely reacted after 2 to 8 hours to III The work-up of the reaction product III is carried out by separating off the crystalline reaction mass and subsequent washing with hot water to The 27Τ, 1,3,5> - £ hiatriazine m be separated recrystallized from alcohols for further purification. Imino, bis-carbimic acid esters I are according to WP. (DDR) 70296 easy and in good yields to produce

 The method is explained using exemplary embodiments.

Examples .

I, 4,6-dimethoxy-2- (p-tolylsulfonyl) imino-2,5-dihydro-2-y, 1,3,5-

thiatriazine · _% '.

To a suspension of 10.0 mmol (1.3 g) of imino-bis-carbimic acid dimethyl ester in 10 21 l of anhydrous benzene are added slowly with stirring 20.0 μl of N-sulfinyl-p-toluenesulfonamide. (4 »35 g) was added dropwise in 20 ml of anhydrous benzene. The reaction mixture is kept at 25 ° C and stirred for 4 hours. After that the mixture stops for 63 hours. The resulting crystalline mass is then separated, listed in 30 ml of hot ^water: taken and hot filtered to separate from beigemengtem p-toluenesulfonamide. The remaining residue is taken up, dried and recrystallized from methanol. The yield of analytically pure compound (mp. = 170 ° C) is 76%.

- 4 - d

2. Analogously to Example 1, the reaction to 4,6-dimetho: xy-2 ~ (p-tolylsulfonyl) imino-2,5-dihydro-2 ^, 1,3> 5-thiatriazine carried out in carbon tetrachloride. A yield of analytically pure compound (Ip. = 170 ⁰ O) of 4-2% is achieved.

3 ·. 4,6-dimethoxy: xy-2- (p-chlorophenylsulfonyl) imino-2,5- <lihydro-2 ^ f, 1,3,5-thiatriazine

20.0 mmol (4.79 s) of N-sulfinyl-p-chlorophenyl "') sulfonamide in 20 ml of anhydrous benzene are slowly added dropwise with stirring to a suspension of 10.0 mmol of imino-bis-carbinic acid diester in 10 ml of anhydrous benzene . the reaction mixture is kept at 60 ⁰ G and stirred for 2 hours. Thereafter, the resultant massecuite is separated, dried added. in 30 ml of hot water, and hot filtered to separate additions of p-chlorophenylsulfonamide * the remaining residue was and recrystallized from ethanol. The yield of analytically pure compound (pp = 151 * 4 ⁰ C) is 10%.

4. 4,6-Dimetho2 -5- ^r- , 2- (phenylsulfonyl) imino-2,5-dihycylro-2λ'i- ¹ ', 1,3,5-thiatriazine

To a suspension of 50 mmol (6.55 g) of dimethyl imino-bis-carbimide acid in 50 ml of anhydrous benzene are added, while stirring, 100 mmol. (20.5 g) of N-sulfinyl-benzenesulfonamide 100 ml of anhydrous benzene was added dropwise. The reaction temperature is maintained at 25 ° C and the mixture allowed to stand for 48 hours. Thereafter, the resulting crystal mass is separated, j. taken up in 100 ml of hot water and filtered hot to separate from the added benzenesulfonamide. The remaining residue is dried and recrystallized from isopropanol. The yield of analytically pure compound (S ¹ P ₀ = IOe ⁰ C) is 27% /

Claims (1)

invention claim A process for the preparation of substituted in 2-position 4,6-dialkoxy-2,5-dihydro-2 / ( ¹ ", ^x l, 3> 5-thiatriazines, characterized in that imino-bis-carbimic acid dialkyl ester of the general formula I in Solution at temperatures between O ⁰ and 120 ⁰ C with N-sulfinyl-arylsulfonamiden the general formula II with elimination of sulfur dioxide and Arensulfonamid be reacted.