DD222022A1 - PROCESS FOR THE PREPARATION OF ALKYLAMMONIUM 2-ARYL-5-BENZYLIDEN-AMINOTHIAZOL-4-THIOLATE - Google Patents

Abstract

The invention relates to a process for the preparation of alkylammonium 2-aryl-5-benzylideneamino-thiazole-4-thiolates by reacting dithiooxamide with aromatic aldehydes and secondary amines. The aim of the invention is to find a simple one-step process and thus to provide the title compounds as reactive intermediates for subsequent syntheses.

Description

Title of the invention.

Process for the preparation of alkylammonium 2-aryl-5-benzylidenairino-thiazole-4-diolates

Field of the Invention - '

The invention relates to a process for preparing alkyl ammonium 2-aryl-5-benzylidenamino-thiazole-4-thiolates by reacting dithiooxamide with secondary amines and aromatic aldehydes. These ammonium thiolates are important intermediates for the preparation of variously substituted 4-mercapto-5-amino-thiazoles and are of interest as potentially biologically active compounds.

Characteristic of the known technical solutions

Alkylammonium 2-aryl-5-benzylideneamino-tniazole-4-thiolates have hitherto been prepared by thermal treatment of N, N ^f -bis (aminobenzyl) dithiooxa nides (HU KIBBEL, G. GÖTZ DD-WP 13Ö.659i Z. f. Chem. 21 (19E1), 138). The required N, N'-bis (aminobenzyl) dithiooxamides must be prepared beforehand by reaction of dithiooxamide with secondary amines and aromatic aldehydes (Ö WALLACH, J. FRÖHLICH Nachr. D. Königl Gesell, d. Wiss. Göttingen 1Ö99, Issue 2, 1024). '"^

Object of the invention

The aim of the invention is the Aufrainden a process for the preparation of alkylammonium 2 ~ Ai>; yl-5-benzylidenaminotMazol-4-thiolates in a simple way in a one-step synthesis of technically readily available starting materials. _k

Explanation of the essence of the invention

The object is achieved by reacting dithiooxamide with secondary amines and with aromatic or heteroaromatic aldehydes which may be monosubstituted or polysubstituted, identically or differently, in different positions.

As secondary amines dialkylamines or cyclic amines such as morpholine or piperidine can be used. Duron short-term heating of 1 mole of dithiooxamide with 2 moles of aldehyde and 1 to 2 moles of amine to the boiling point of the solvent used give deep red solutions from which in the cold, possibly on addition of ether or petroleum ether, the Alkylämmonium-thiolates of the general formula I. in which R is an unsubstituted or in various positions mono- or polysubstituted, identically or differently, by halogen atoms, alkyl- * alkoxy-, nitro- or cyano-substituted aryl or heteroaryl radical and A is a secondary amino group, preferably a morpholino or piperidino group is crystallized as orange to deep red crystalline compounds.

Suitable solvents may be C 1 - to C 4 -alcohols, aromatic hydrocarbons, such as benzene or olefins. polyvalent or cyclic ethers such as dioxane, monoglyme or diglyme be used. When using monoglyme, diglymei dimethyl sulfoxide or dimethylformamide is preferably carried out at temperatures of 25 ⁰ G. The reaction times are then 12 to 14 hours.

The advantage of the invention consists in a simple process for the production of the title compounds / the general formula, with avoidance of intermediates directly from technically easily accessible and inexpensive starting products.

A further advantage is that for subsequent reactions the Tite! Compounds need not be isolated, but the red reaction solutions can be used directly.

embodiments

The invention is further illustrated by the general examples and the data of the table, without being limited thereto.

example 1

0.01 mol of dithiooxamide, 0.02 mol of aldenyi and 0.01 to 0.02 mol of secondary amine are heated to boiling point in 50 ml of solvent until the dithiooxamide is dissolved. As it cools, the orange-red to deep red alkyl ammonium thiolates crystallize out. The precipitate can be completed by addition of ether or petroleum ether. After suction, Ίηΐΐ ether or petroleum ether is washed and dried in air. The salts are produced in an analytically pure form. Recrystallization is possible only with partial decomposition.

Example 2

0.01 mol of dithiooxamide, 0.02 mol of aldehyde and 0.01 to 0.02 mol of secondary amine are dissolved in 4-0 ml of solvent by shaking at room temperature and filtered with suction after 12 to 24 hours standing and worked up as in Example 1.

Table: Production data. Alkylammonium 2-aryl-5-behzylidenamino-thia2iol-4-thiolates of the general formula I.

Solvent tempera Austur (° C) prey

^C 6 ^H 5

pip, pip,

MeOH EtOH

4-CH ₃ ^) ₆ H ₄

pip. Dig yme morph. ² EtOH

pip

 pip.

Pip ·, pip.

3-CH ₃ OC ₆ H ₄ pip

4-CH ₃ OC ₆ H ₄ pip.

2-Cl-C ₆ H ₄ 4-Cl-C ₆ H ₄

EtOH EtOH EtOH Toluene ^J EtOH EtOH pip. EtOH pip. EtOH pip. toluene

pip. , MonoglJi pip. diglyme

pip. DMSO

pip. DME pip. EtOH.

65 78 25 78 78 78 78

110 78 78 78 78 110

25 25

25 78

58 57

55 60 48

43 74 56 45 65 44 80

68 65.5

59

71 70

143

142-142- 107-108 133-164 154-

153-114- 153-154

149-183-84 182-184

184

183-

183

183-153-

solvent

l'empera- Aus Fp ( ⁰ G) door (C) loot '()

2,4- (CH ₃ O) ₂ G ₆ H ₃

pyrid-3-yl furfur-2-yl

pip. EtOH, 7Ö pip. ^ EtOH 78 pip. EtOH 76 pip" i-PrOH 82 Pip· iDoluen 110 pip. EtOH 78 Pip- EtOH 78 Pip" EtOH 78 pip. Stoh 78 pip. MeOH 64 pip. EtOH 78 pip. η-Ρι · 0ίί 97 pip. i-prob 82 pip. n-Buol · 11? pip. benzene 80 pip. toluene 110 pip. dioxane 101 pip. DiglyiLd .25 Pip. toluene 110

70 58

52 44

50

, 54 85

17 60 71

red oil

65

red

Oil

273-78

360

192-94

193

192-94 · 162

154 * - 56 133- 35 73

35 151-53

50,152

31 151-52

56 151-53

149 150-52

155-57

155

piperidino

morpholino

S _V NH ₂

+ 2RCHO

RCH

Claims (2)

Invention s claim. , , , 1. A process for the preparation of Alkylaitiiaonium 2-aryl-5-benzylideneamino-t; hia2ol-4-thiolates of the general formula I in which R is a substituted or in different positions singly or multiply, identically or differently, by halogen atoms, alkyl, Alkoxy-, Hitro- or cyano groups substituted aryl or heteroaryl radical and A is a secondary amino group, characterized in that dithiooxamide with aldehydes, in which R has the above meaning, and secondary amines, in which A has the above meaning, in C, - to C. alcohols or aromatic hydrocarbons are briefly heated to boiling temperature or reacted in polybasic or cyclic ethers, Diiuethylsulioxid or dimethylformamide at room temperature. 2. The method according to item 1, characterized in that are used as secondary amines, piperidine or morpholine.