DD209454A1 - PROCESS FOR PREPARING COMPLETELY SUBSTITUTED 1-ARENSULFONYL-6-IMINO-4,4-DIOXO-HEXAHYDRO-2 LAMBOLA 4, 4 LAMBOLA 6, 1,3,5-DITHIATRIAZINES - Google Patents

Abstract

The invention relates to a process for preparing substituted 1-arenesulfonyl-6-imino-4,4-dioxo-hexa-hydro-2 lambda hoch4, 4 lambda hoch6, 1,3,5-dithiatriazines. Processes for the preparation of such compounds, even with different substituent patterns, have not previously been disclosed. The object was achieved by cyclizing N, N, N'-trisubstituted sulfamides with sulfur diimides or N-sulfinylamines to give the 2 lambda, 4, 4, lambda, 6, 1,3,5-dithiatriazines. As cyclic diamides of sulfuric and sulfuric acids, the dithiatriazines as pharmaceuticals and potential pesticides are of general interest.

Description

I, ι ¥ fa yy w

A process for the preparation of fully substituted 1-arenesulfonyl-VIII-amino, 4-Hiio2O-aahydro-2 ^, 45, 1,3j5-ibithiatriazines

Field of application of the invention

The invention relates to a process for the preparation of fully substituted 1-Arensulfonyl-6: üaino-4,4-dioxo-he2: ahydra-2 ^, 4 ^, 1,3 »5- <utniatriazinen · The compounds can also, as heterocyclic Suifamid © or "Diamiae the Iminoschwefligen acid be considered * derivatives of Suifamids and Sulfonyxverbindungen of guanidines are known for some time as drugs" · on the other hand, the herbicidal effect of 1 _t 3J5-triazines with wide substitution pattern is known. the 2Λ inventive "4 ^ _t 1,3t5 - dithiatriazines sina as potential biocidal compounds of general practical interest V

üharalrfceristik the known technical solutions

Completely substituted Perhydroverbindungen of Ί »3> 5 · · * ^ * ^ ί ιά.3 · ΐα * 1αζ1η8 are not known,"It's just a 1,2,3,4-Tetrah _y dro-2 '> ^4, 4 ^ ⁶ , 1,3,5-dithiatriazine, which was obtained by cyclization of an aminosulfonylguanidine derivative obtained from diethyl cyanamide and sulfuryl chloride and subsequent nucleophilic substitution with amines with iminothionyl chloride. Completely substituted 2: 1, 1, Dithiatriazines can not be produced in the known synthesis route.

Aim of the Invention

It is an object of the present invention to provide a novel process for the preparation of the substance of the invention of the fully substituted 1-arenesulfonyl-2-arenyl-L-pentonylimino (or -oxo) -b-ij-bino-dibenzoyl-oxydehydroxybenzene At the same time, the process based on available intermediates in simple reaction should lead to high yields of the desired end product.

Explanation of the essence of the invention

The object is achieved by N, U, IT * trisubstituted

i 2

SuIfamide of the general formula I in which R and R are an unbranched or branched Aikylrest with 1-4 O-Atojaen bzw.v an unsubstituted or substituted aromatic radical, in inert. Solvents, such as aromatic hydrocarbons, with TS ₉ K. * - * substituted sulfur diimides or N-sulfinylamines of the general formula II in which Ar is an unsubstituted or substituted aromatic radical and Σ is an arenesulfonylimino-G-group or pesticide, respectively, to give 1-arensulfonyl-2-arenesulfonylj mi no (or · -OZO) -6-imino-4,4-diozohexahydro "2T" _t ^ 4, 1,3,5-dithiatriazinen of the general formula III in which R, R,. Ar and X have the meaning given to be implemented · _{0 0}

R ² R ¹ -fT · ^ ^] J

+ Ar-SO ₅ - ^ T = S = X> j J

I II III SO

X = ArSO ₂ STj 0

Trisubstituted sulfamides of general formula I are obtainable from sulfamic acid chlorides by reaction with silylated primary amines by a known process. The reaction is carried out under normal pressure at temperatures between 20 ° and 120 ° C. and with the exclusion of moisture.

The fully substituted 2 '^, 4 ^, 1,3,5-dithiatriazines of the general formula III are extremely poorly soluble and precipitate from the reaction solution as finely powdered substances which can be recrystallized from Dimethylsülfoxid if necessary ^ The advantage of the invention consists in the one-step synthesis of fully substituted 2 / T> 4 ^, 1,3,5-dithiatriazines in high yields from available trisubstituted sulfides and ΪΓ, Ν'-disubstituted sulfur diimides or · N-sulfinylamines · The starting materials are preferably in aromatic hydrocarbons without any technical Expense brought to the reaction. The invention will be explained with reference to exemplary embodiments without being limited thereto *

Embodiment 1

1. 5-Ethyl-3-isop: ropyl-6-iinino-4,4-dioxo-1-tosyl-2-tosylimino-hexahydro-2 ^, 4 ^, 1,3 »5-aithiatriazine 190 mg N-oyano -iT-ethyl-ir'-isopropyl-sulfamide are mixed with vigorous stirring in 50 ml ÜJoluen with 370 mg Ν, Ν'-Ditosylschwefeldiiffli d and heated to 110 ⁰ O for 10 h. Both starting materials are in intensive red color in solution · After about three hours, a finely powdered precipitate begins to precipitate * The precipitate is filtered off and recrystallized from much dimethylsulfoxide. F .: 208-211 ⁰ O Yield: 0.24 g = 42% of theory

2. ^ -Ethyl ^ -isopropyl-o-imino ^, 4,4-trioxo-1-tosyl-hexahydro- ZX , 4 ^, 1,3 »5-clithiatriazine According to Example 1, I90 mg of N-cyano-tert-butyl ethyl-N'-isopropyl-sulfamide with 220 mg of N-sulfinyl-p-toluenesulfonamide reacted. After 6 hours, O ₃ 3 g of reaction product are separated off. Fi: 196-198 ⁰ O Yield: 63% d, G h ·

3x3 -5-bis-C4-chlorophenyl) -1- (4-chlorophenylsulphonyl) -2- (4-chlorophenylsulphonylmino) -6-i mio-4,4-dioxo-he: ga-

342 mg of N, ISf ^# -Bis- (4-chlorophenyl) -Ü-cyano-sulfamide are in 150 ml m- / p-Zylen mixture with 420 mg of 1, H * - bis (4-chlorophenylsulfonyl) -schwefeldiiiaid to Eeaktion brought · It is for 14 h at reflux (138 ⁰ C) heated. Thereafter, the precipitated fine powdery precipitate is separated »F: 228-220 ⁰ O Yield: 0.4 g = 5% of theory.

4. 3,5-Bis- (4-chlorophenyl) -1- (4-chlorophenylsulfonyl) -6-imino-2,4-trioxo-hexahydro ^^, 4 ^ T 11 »3> 5 * üthiatriazine According to Example 3 34-2 mg of Ή , N * -bis (4-chlorophenyl) -H-cyano-sulfamide are reacted with 240 mg of H-sulfonyl-4-chlorobenzene-sulfone amide - after 8 h 0.46 g reaction product separated, J.ι 216 - 218 ⁰ O yield: 70% d.üJh ·

Claims (3)

Erfjjidungsanspruch 1 «A process for the preparation of fully substituted 1-Arensülfonyl-6-imino-4 ·, ^ -dioxo-hexahydro - ^^ ·, 4 / r, 1,3,5-dithiatriazines of the general formula III, in the E and R is an unbranched or branched alkyl radical having 1-4 C atoms or an unsubstituted or substituted aromatic radical and Σ is an arensulfonyl * imino group or · oxygen, characterized in that ΪΤ, Η, ϊΓ-trisubstituted sulfamide of the formula I having a cyano group as a reactive substituent with NjlT-disubstituted sulfur diimides or H ^ uif inylarensulf onamiden the lOrmel II in aprotic solvents
become" medium at temperatures between 20 ° and 120 0 reacted 2 «method according to item 1 ·, characterized in that the reaction with H, U * -disubstituted Schwefeldiimiden to 1 -Arensulf onyl-2-arens ulf onylimino - ^ - imino-4,4-di 020-he2ahydro-2> ⁴ , 4, ⁶ , 1,3,5-dithiatriazines leads · 3 · Process according to item 1, characterized in that the reaction with H-sulfinyl-arensulfonamides to 1-arenesulfonyl-6-imino-2,4,4-trioxo-hexahydro-2 ^ ⁴ , 4 ^ ⁶ , 1.3 , 5-dithiatriazinen leads.