DE4029732A1 - New 2-amino-thiazole derivs. - Google Patents

Abstract

2-Aminothiazoles of formula (I) and their tautomers are new: R1 = NH2 or N=C(T1)-NT2T3; T1 = H, 1-6C alkyl or Ph; T2 and T3 = 1-6C alkyl, 5-7C cycloalkyl or Ph, or NT2T3 is a satd. 5- to 7-membered ring opt. contg. other heteroatoms; R3 = S(O)nX, SH or Y; n = 0-2; X = 3-8C cycloalkyl or opt. substd. 1-20C alkyl, 3-6C alkenyl, 3-6C alkynyl or phenyl; Y = 1-20C mono- or dialkylamino (opt. substd. and/or interrupted by O), 3-8C cycloalkylamino, adamantylamino, 2-12C mono- or dialkenylamino, 3-12C alkynylamino, N-(1-5C alkyl)anilino, pyrrolidino, piperidino, morpholino, thiomorpholino, 1-piperazinyl, 4-(1-4C alkyl)-1-piperazinyl, hexamethylenimino, 1-imidazolyl, 1-pyrazolyl, opt. substd. anilino, pyridylamino, thienylamino, NHNH2, 1-4C mono- or dialkylhydrazino or phenylhydrazino; R4 = 1-6C alkanoyl, benzoyl, CN, COT4 or C(T6)T5; T4 = OH, 1-6C alkoxy, NH2 or Y; T5 = H, 1-6C alkyl or Ph; T6 = NOH, NQ or the residue of a cpd. contg. a reactive CH2 gp.; Q = opt. substd. 1-20C alkyl (opt. interrupted by O), an opt. substd. 3-6C alkenyl, 3-6C alkynyl, 3-12C cycloalkyl or phenyl gp., pyridyl, 3-6C alkoxycarbonylmethyl, NH2, dialkylamino or anilino; provided that: (a) R3 is not SCH(COMe)COOETt or SCH(COMe)2 when R1 = NH2 and R4 = COMe or COOEt; (b) R3 is not SMe when R1 = NH2 and R4 = CN; (c) R1 is not NH2 when R3 = piperidino or morpholino and R4 = CN.

Description

The present invention relates to new aminothiazoles of the formula I.

or their tautomers, where
R¹ and R² are each hydrogen or together a radical of the formula

wherein T¹ for hydrogen, C₁-C₆-alkyl or phenyl and T² and T³ are the same or different and independently of each other for C₁-C₆-alkyl, C₅-C₇-cycloalkyl or phenyl or T² and T³ together with the nitrogen atom connecting them for one 5- to 7-membered saturated heterocyclic radical which optionally contains further heteroatoms,
R³ is a radical of the formula

-S (O) _n -X,

wherein n for 0, 1 or 2 and X for optionally substituted C₁-C₂₀-alkyl, C₃-C₈-cycloalkyl, optionally substituted C₃-C₆-alkenyl, optionally substituted C₃-C₆-alkynyl, optionally substituted phenyl or, if n is the meaning has from 0, also stand for hydrogen and
R⁴ C₁-C₆ alkanoyl, benzoyl, cyano or a radical of the formula

mean in which T⁴ for hydroxy, C₁-C₆-alkoxy, amino or the radical Y, which has the meaning of C₁-C₂₀-mono- or dialkylamino, wherein the alkyl chain is optionally substituted and / or interrupted by one or more oxygen atoms, C₃- C₈-cycloalkylamino, adamantylamino, C₂-C₁₂-mono- or dialkenylamino, C₃-C₁₂-alkynylamino, N- (C₁-C₅-alkyl) -N-phenylamino, pyrrolidino, piperidino, morpholino, thiomorpholino, piperazino, N- (C₁- C₄-alkyl) piperazino, hexamethyleneimino, imidazol-1-yl, pyrazol-1-yl, optionally substituted phenylamino, pyridylamino, thienylamino, hydrazino, C₁-C₄-mono- or dialkylhydrazino or phenylhydrazino and T⁵ for hydrogen, C₁-C₆-alkyl or phenyl and T⁶ represent the rest of a methylene-active compound, hydroxyimino or the radical NX, in which X has the meaning of C₁-C₂₀-alkyl, which is optionally substituted and / or interrupted by one or more oxygen atoms, optionally substituted ertem C₃-C₆-alkenyl, optionally substituted C₃-C₆-alkynyl, optionally substituted C₃-C₁₂-cycloalkyl, optionally substituted phenyl, pyridyl, C₁-C₄-alkoxycarbonylmethyl, amino, C₁-C₄-dialkylamino or phenylamino,
with the proviso that

• a) when R¹ and R² are each hydrogen and R⁴ are acetyl or ethoxycarbonyl, R³ is not for the rest of the formula stand and
• b) when R¹ and R² each represent hydrogen and R⁴ cyano, R³ not for Methylthio stands.

From Tetrahedron Lett., Volume 22, pages 2285 to 2288, 1982, is already the Compound 2-amino-4-methylthio-5-cyanothiazole known. Furthermore, in Tetrahedron Lett., Vol. 28, pages 117 to 120, 1987, 2-aminothiazoles, that in ring position 5 is either the acetyl or ethoxycarbonyl group and in ring position 4 either the rest

exhibit.  

However, the thiazoles mentioned are not particularly suitable as diazo components for the production of azo dyes.

The object of the present invention was to provide new aminothiazoles, which have a thiol group in ring position 4 and are doing well as a diazo component or its precursor for the production of Azo dyes should be suitable.

Accordingly, the aminothiazoles of the formula I specified above found.

All alkyl and alkenyl groups occurring in the above formula I. can be straight or branched.

If in the formula I alkyl groups occur by one or more Oxygen atoms are interrupted, those are preferred, which are separated by one three, in particular one or two oxygen atoms are interrupted.

If substituted phenyl groups occur in the formula I, as Substituents e.g. B. C₁-C₆ alkyl, C₁-C₆ alkoxy, halogen, in particular Fluorine, chlorine or bromine, nitro, hydroxy, amino, C₁-C₆ mono- or dialkylamino, Acetylamino, carboxyl, carbamoyl, thiocarbamoyl, cyano, C₁-C₆ alkoxycarbonyl, Trifluoromethyl, hydroxy-C₁-C₃-alkyl or C₁-C₄-alkanoyl in Come into consideration.

If substituted alkyl groups occur in the formula I, as Substituents e.g. B. hydroxy, C₁-C₆-alkoxy, phenyl-C₁-C₄-alkoxy, phenoxy, Amino, C₁-C₆-mono- or dialkylamino, phenyl-C₁-C₆-alkylamino, diphenyl-C₁-C₄-alkylamino, Phenylamino, diphenylamino, C₃-C₆ mono- or dicycloalkylamino, C₃-C₆-cycloalkyl, hydroxy-C₁-C₆-alkylamino, morpholino, Piperazino, N- (C₁-C₆-alkyl) piperazino, thiomorpholino, piperidino, Pyrrolidino, hexamethyleneimino, thien-2-yl, furan-2-yl, 1H-pyrrol-2-yl, Pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, phenyl, carboxyl, C₁-C₃ alkoxycarbonyl, Carbamoyl, C₁-C₄ mono- or dialkylcarbamoyl, cyano, thiocarbamoyl, Phenoxycarbonyl, phenyl-C₁-C₄-alkoxycarbonyl, mono- or Diphenylcarbamoyl, mono- or bis (phenyl-C₁-C₄-alkyl) carbamoyl, mono- or Diphenylthiocarbamoyl, mono- or bis (phenyl-C₁-C₄-alkyl) thiocarbamoyl, C₁-C₆-alkylthio, phenylthio or phenyl-C₁-C₄-alkylthio come.

When substituted in formula I alkenyl, alkynyl or cycloalkyl groups can occur as substituents such. B. fluorine, chlorine or bromine in Come into consideration.  

When the residues T² and T³ together with the nitrogen atom connecting them a 5- to 7-membered saturated heterocyclic radical which, if appropriate contains further heteroatoms, mean z. B. Pyrrolidino, piperidino, morpholino, thiomorpholino, thiomorpholino-S, S-dioxide, Piperazino, N- (C₁-C₄-alkyl) piperazino or hexamethyleneimino in Come into consideration.

T¹, T², T³ and T⁵ are for example methyl, ethyl, propyl, isopropyl, Butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl or hexyl.

R⁴ are for example formyl, acetyl, propionyl, butyryl, isobutyryl, Pentanoyl or hexanoyl.

(The terms isooctyl, isononyl, isodecyl and isotridecyl are trivial names and come from the after the Oxosynthesis obtained alcohols [cf. in addition Ullmanns encyclopedia of technical chemistry, 4th edition, volume 7, pages 215 to 217, and volume 11, Pages 435 and 436].)

The rest -NX is derived from primary amines of the formula H₂NX. As such are, for example, methylamine, ethylamine, propylamine, isopropylamine, Butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, Isopentylamine, neopentylamine, hexylamine, heptylamine, n-octylamine, isooctylamine, 2-ethylhexylamine, nonylamine, isononylamine, decylamine, isodecylamine, Undecylamine, dodecylamine, tridecylamine, isotridecylamine, tetradecylamine, Pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, Nonadecylamine, eicosylamine, allylamine, methallylamine, propargylamine, Cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, cycloheptylamine, Cyclooctylamine, cyclononylamine, cyclodecylamine, cycloundecylamine, Cyclododecylamine, 2-hydroxyethylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-hydroxypropylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3- (2-phenoxyethoxy) propylamine, 3-benzyloxypropylamine, 2- (N, N-dimethylamino) ethylamine, 2- (N, N-diethylamino) ethylamine, 3- (N, N-dimethylamino) propylamine, 3- (N, N-diethylamino) propylamine, benzylamine, 2-phenylethylamine, 3-phenylpropylamine, aniline, 2-hydroxyaniline, 3-hydroxyaniline, 4-hydroxyaniline, o-anisidine, m-anisidine, p-anisidine, o-phenetidine, m-phenetidine, p-phenetidine, 2-chloroaniline, 3-chloroaniline, 3-nitroaniline, 4, nitroaniline, o-toluidine, m-toluidine, p-toluidine, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2-trifluoromethylaniline, 3-trifluoromethylaniline, 4-trifluoromethylaniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline,  2-aminopyridine, 3-aminopyridine, 4-aminopyridine, glycine methyl ester, Glycine ethyl ester, glycine propyl ester, glycine butyl ester, hydrazine, N, N-dimethylhydrazine or to name phenylhydrazine.

T⁴ are z. B. methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, pentyloxy, isopentyloxy, neopentyloxy or hexyloxy.

The rest T⁶ derives z. B. of methylene compounds of the formula H₂T⁶ from. Such compounds obey the formula, for example

in the Z cyano, nitro, C₁-C₆-alkanoyl, benzoyl, C₁-C₄-alkylsulfonyl, Phenylsulfonyl, carboxyl, C₁-C₄ alkoxycarbonyl, carbamoyl or C₁-C₄ mono- or dialkylcarbamoyl, or the formula  

Some particularly important connections are e.g. B .:

Radicals Y are, for example, methylamino, ethylamino, propylamino, isopropylamino, Butylamino, isobutylamino, sec-butylamino, pentylamino, Isopentylamino, neopentylamino, hexylamino, heptylamino, octylamino, Isooctylamino, 2-ethylhexylamino, nonylamino, isononylamino, decylamino, Isodecylamino, undecylamino, dodecylamino, tridecylamino, isotridecylamino, Tetradecylamino, pentadecylamino, hexadecylamino, heptadecylamino, Octadecylamino, nonadecylamino, eicosylamino, (R) - (-) - 1-cyclohexylethylamino, (S) - (+) - 1-cyclohexylethylamino, 2-cyclohexylethylamino, 2-hydroxyethylamino, 2-methoxyethylamino, 2-ethoxyethylamino, 2-phenoxyethylamino, 2- (2'-hydroxyethoxy) ethylamino, 2- (2'-hydroxyethyl) aminoethylamino, 2-aminoethylamino, 2-dimethylaminoethylamino, 2-diethylaminoethylamino, 2-diisopropylaminoethylamino, 2- (piperazin-1-yl) ethylamino, 3-hydroxy-n-propylamino, 3-methoxy-n-propylamino, 3-ethoxy-n-propylamino, 3-isopropoxy-n-propylamino, 3-phenoxy-n-propylamino, 3-benzyloxy-n-propylamino, 3- (2′-methoxyethoxy) -n-propylamino, 3- (2′-ethoxyethoxy) -n-propylamino, 3- (2'-phenoxyethoxy) -n-propylamino, 3-amino-n-propylamino, 3-dimethylamino-n-propylamino, 3-diethylamino-n-propylamino, 3-di-n-propylamino-n-propylamino, 3-diisopropylamino-n-propylamino, 3-di-n-butylamino-n-propylamino, 3-morpholin-1-yl-n-propylamino, 4-hydroxy-n-butylamino, 4-amino-n-butylamino, 5-hydroxy-n-pentylamino, 5-amino-n-pentylamino, 6-hydroxy-n-hexylamino, 6-amino-n-hexylamino, 7-hydroxy-n-heptylamino, 7-amino-n-heptylamino, 8-hydroxy-n-octylamino, 8-amino-n-octylamino, 9-hydroxy-n-nonylamino, 9-amino-n-nonylamino, 10-hydroxy-n-decylamino, 10-amino-n-decylamino, 11-amino-n-undecylamino, 4-diethylamino-1-methyl-n-butylamino, 2-hydroxy-n-propylamino, 1-ethyl-2-hydroxyethylamino, 2-hydroxy-1,1-dimethylethylamino, 1,1-bis (hydroxymethyl) ethylamino, 1-ethyl-2-hydroxyethylamino, 2-hydroxycarbonylethylamino, 3-hydroxycarbonyl-n-propylamino, 4-hydroxycarbonyl-n-butylamino, 5-hydroxycarbonyl-n-pentylamino, 10-hydroxycarbonyl-n-decylamino, phenylamino, o-methylphenylamino, m-methylphenylamino, p-methylphenylamino, o-ethylphenylamino,  m-ethylphenylamino, p-ethylphenylamino, o-trifluoromethylphenylamino, m-trifluoromethylphenylamino, p-trifluoromethylphenylamino, o-hydroxyphenylamino, m-hydroxyphenylamino, p-hydroxyphenylamino, o-methoxyphenylamino, m-methoxyphenylamino, p-methoxyphenylamino, o-ethoxyphenylamino, m-ethoxyphenylamino, p-ethoxyphenylamino, o-chlorophenylamino, m-chlorophenylamino, p-chlorophenylamino, o-fluorophenylamino, m-fluorophenylamino, p-fluorophenylamino, o-bromophenylamino, m-bromophenylamino, p-bromophenylamino, o-iodophenylamino, m-iodophenylamino, p-iodophenylamino, o-aminophenylamino, m-aminophenylamino, p-aminophenylamino, p-acetylaminophenylamino, o-hydroxymethylphenylamino, m-hydroxymethylphenylamino, p-hydroxymethylphenylamino, o-hydroxycarbonylphenylamino, m-hydroxycarbonylphenylamino, p-hydroxycarbonylphenylamino, o-aminocarbonylphenylamino, m-hydroxycarbonylphenylamino, p-hydroxycarbonylphenylamino, o-cyanophenylamino, m-cyanophenylamino, p-cyanophenylamino, 2,6-dimethylphenylamino, 3,5-dimethylphenylamino, 2-hydroxy-5-methylphenylamino, 2-hydroxy-4-methylphenylamino, 4-hydroxy-2-methylphenylamino, 2-hydroxy-5-chlorophenylamino, Imidazol-1-yl, pyrazol-1-yl, pyrid-2-ylamino, pyrid-3-ylamino, Pyrid-4-ylamino, pyrid-3-ylmethylamino, fur-2-ylmethylamino, thienylamino, Benzylamino, o-methoxybenzylamino, p-methoxybenzylamino, p-fluorobenzylamino, o-chlorobenzylamino, p-chlorobenzylamino, 3,4-dimethoxybenzylamino, 2-phenylethylamino, (+/-) - α-methylbenzylamino, (+) - α-methylbenzylamino, (-) - α-methylbenzylamino, 3-phenyl-n-propylamino, α-methyl-γ-phenyl-n-propylamino, Cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, Cycloheptylamino, cyclooctylamino, cyclononylamino, cyclodecylamino, Cyclododecylamino, allylamino, propargylamino, methallylamino, Dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino, diisopropylamino, Diisobutylamino, di-sec-butylamino, di-n-pentylamino, Diisopentylamino, di-n-hexylamino, di (α-ethyl-n-hexyl) amino, di-n-octylamino, Diallylamino, dicyclohexylamino, N-methyl-n-butylamino, N-methylcyclohexylamino, N-ethylcyclohexylamino, N-methylethanolamino, N-ethyl-1,3-dimethyl-n-propylamino, N-ethylethanolamino, N-ethyl-2-hydroxy-n-propylamino, N-tert-butylethanolamino, N-methylphenylamino, N-ethylphenylamino, N-n-propylphenylamino, N-isopropylphenylamino, N-n-butylphenylamino, dibenzylamino, N-methylbenzylamino, N-ethylbenzylamino, N-isopropylbenzylamino, N-tert-butylbenzylamino, N- (2-hydroxyethyl) benzylamino, N-phenylbenzylamino, N-benzyl-2-phenylethylamino, Pyrrolidino, piperidino, hexamethyleneimino, morpholino, N-methylpiperazino, piperazino, N-ethylpiperazino or thiomorpholino.

R³ are z. B. mercapto, methylthio, ethylthio, propylthio, isopropylthio, Butylthio, isobutylthio, sec-butylthio, pentylthio, isopentylthio, Neopentylthio, tert-pentylthio, hexylthio, heptylthio, octylthio, 2-ethylhexylthio, Benzylthio, 1- or 2-phenylethylthio, cyclopentylthio,  Cyclohexylthio, cycloheptylthio, allylthio, methallylthio, propargylthio, Phenylthio, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, Butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, pentylsulfinyl, Isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, Hexylsulfinyl, heptylsulfinyl, octylsulfinyl, 2-ethylhexylsulfinyl, Benzylsulfinyl, 1- or 2-phenylethylsulfinyl, cyclopentylsulfinyl, cyclohexylsulfinyl, Cycloheptylsulfinyl, allylsulfinyl, methallylsulfinyl, Propargylsulfinyl, phenylsulfinyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl, Isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, Pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, Hexylsulfonyl, heptylsulfonyl, octylsulfonyl, 2-ethylhexylsulfonyl, Benzylsulfonyl, 1- or 2-phenylethylsulfonyl, cyclopentylsulfonyl, Cyclohexylsulfonyl, cycloheptylsulfonyl, allylsulfonyl, Methallylsulfonyl, propargylsulfonyl or phenylsulfonyl.

Aminothiazoles of the formula I are preferred in which
R¹ and R² are each hydrogen or together the rest

wherein T¹ for hydrogen, C₁-C₄-alkyl or phenyl and T² and T³ independently of one another for C₁-C₄-alkyl or phenyl or together with the nitrogen atom connecting them for pyrrolidino, piperidino, morpholino, thiomorpholino, piperazino, N- (C₁-C₄ -Alkyl) piperazino or hexamethyleneimino, mean and
R³ and R⁴ each have the meaning given above.

Aminothiazoles of the formula I in which R 1 and R 2 are particularly preferred each hydrogen or together the rest

mean, T¹ for hydrogen and T² and T³ independently stand for C₁-C₄-alkyl.

Also particularly preferred are diaminothiazoles of the formula I in which C₁-C₆-alkylthio, benzylthio, cyclohexylthio, C₃-C₄-alkenylthio, propargylthio, Phenylthio, C₁-C₆ alkylsulfonyl, benzylsulfonyl, cyclohexylsulfonyl, C₃-C₄-alkenylsulfonyl, propargylsulfonyl or phenylsulfonyl means.  

Further particularly preferred are aminothiazoles of the formula I in which R⁴ Cyano, formyl or the rest

means, wherein Z is cyano, nitro or C₁-C₄ alkoxycarbonyl.

Of particular importance are aminothiazoles of the formula I in which R 1 and R² each represent hydrogen or together the radical = CH-N (CH₃) ₂.

Also to be mentioned in particular are aminothiazoles of the formula I in which
R⁴ formyl, cyano or a radical of the formula

means, wherein T⁴ for hydroxy, methoxy, ethoxy or amino and T⁵ for Are hydrogen, methyl, ethyl or phenyl and T⁶ the above Has meaning.

Emphasis should be given to aminothiazoles of the formula I in which
R⁴ formyl, cyano or a radical of the formula

means, where T⁶ has the meaning given above.

Aminothiazoles of the formula Ia are particularly noteworthy

or their tautomers, where
L¹ amino,
L² C₁-C₆-alkylthio, benzylthio, cyclohexylthio, C₃-C₄-alkenylthio, propargylthio, phenylthio, C₁-C₆-alkylsulfonyl, benzylsulfonyl, cyclohexylsulfonyl, C₃-C₄-alkenylsulfonyl, propargylsulfonyl, propargylsulfonyl, propargylsulfonyl
L³ cyano, formyl or the rest

mean, wherein Z is cyano, nitro or C₁-C₄ alkoxycarbonyl.

Of particular technical importance are aminothiazoles of the formula I, in n is 0 or 2 and X is benzy or phenyl.

The aminothiazoles of formula I according to the invention can, for. B. by Implementation of halogen aminothiazoles of the formula II

in which R¹, R² and R⁴ each have the meaning given above and Hal represents chlorine or bromine, with a mercapto compound of the formula III

R³-H (III),

in which R³ has the meaning given above, or its alkali salt be preserved.

To do this, e.g. B. the Halogenaminothiazol II with the mercapto compound III or its alkali salt in an inert solvent (e.g. N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidinone, hexamethylphosphoric trisamide, 1,3-dimethylimidazolidin-2-one, 1,3-dimethylhexahydropyrimidin-2-one, 1,2-diethoxyethane, benzene, toluene, xylene, Methylene chloride, chloroform, methanol, ethanol, propanol, isopropanol, Butanol or isobutanol) at a temperature of -10 to + 150 ° C, if appropriate in the presence of a base (e.g. triethylamine, tripropylamine, Tributylamine, pyridine, 4-dimethylaminopyridine, sodium methylate, sodium ethylate, Potassium tert-butoxide, sodium hydrogen carbonate, sodium carbonate, Potassium hydrogen carbonate, potassium carbonate, sodium hydride or potassium hydride)  around. The molar ratio II: III is usually 1: 2 to 1:10 and that of base: mercapto compound generally 1: 1 to 10: 1.

The Halogenaminothiazole of formula II are known per se and z. B. in the US-A 43 95 544 described or can be analogous to those listed there Methods can be obtained.

The new aminothiazoles are valuable intermediates for synthesis of dyes, crop protection agents or pharmaceuticals. In particular they serve as a diazo component (R¹, R² = H) or their precursor for the Manufacture of azo dyes.

The following examples are intended to explain the invention in more detail.

example 1

3.7 g of sodium ethanolate was dissolved in 40 ml of ethanol. For this purpose, 4.5 g n-Butanethiol was added and the mixture was stirred at room temperature for 15 minutes. Then 8.1 g of 2-amino-4-chloro-5-formylthiazole were added and the mixture was stirred at room temperature for 2 hours. After that it was The solvent is distilled off under reduced pressure and the residue is added Mix 150 ml of hot water. The suspension was concentrated. hydrochloric acid adjusted to a pH of 3, cooled to 10 ° C and another 2 Stirred for hours at this temperature. The precipitate was suctioned off, washed with water and dried at 50 ° C in a vacuum drying cabinet. For cleaning was made from a mixture of water and acetic acid Addition of activated carbon recrystallized. 8.1 g (75% of theory) were obtained the compound of the formula

melting point 131-132 ° C. The IR, NMR, UV and mass spectra as well the elementary analysis is correct with the constitutional formula given above match.

Example 2

16.25 g of 2-amino-4-chloro-5-formylthiazole was dissolved in 100 ml of N, N-dimethylformamide solved. 19.6 g of sodium benzenesulfinate were added to this. The Reaction mixture is one hour at room temperature and 4 hours 70 ° C stirred. The mixture was then added to 600 ml of ice water  and the resulting precipitate is suctioned off, washed with water and dried under reduced pressure at 50 ° C. 21.6 g (81% of theory) were obtained the connection

melting point 166-167 ° C. The IR, NMR, UV and mass spectra as well the elementary analysis agree with the formula given above.

The following table can be used in an analogous manner Make connections.  

Claims (3)

1. aminothiazoles of the formula I. or their tautomers, where
R¹ and R² are each hydrogen or together a radical of the formula wherein T¹ for hydrogen, C₁-C₆-alkyl or phenyl and T² and T³ are the same or different and independently of each other for C₁-C₆-alkyl, C₅-C₇-cycloalkyl or phenyl or T² and T³ together with the nitrogen atom connecting them for one 5- to 7-membered saturated heterocyclic radical, which optionally contains further heteroatoms, R³ is a radical of the formula-S- (O) _n -X, where n is 0, 1 or 2 and X is optionally substituted C₁-C₂₀-alkyl, C₃-C₈-cycloalkyl, optionally substituted C₃-C₆-alkenyl, optionally substituted C₃-C₆-alkynyl, optionally substituted phenyl or, if n is 0, are also hydrogen, and
R⁴ C₁-C₆ alkanoyl, benzoyl, cyano or a radical of the formula mean in which T⁴ for hydroxy, C₁-C₆-alkoxy, amino or the radical Y, which has the meaning C₁-C₂o--mono- or dialkylamino, wherein the alkyl chain is optionally substituted and / or interrupted by one or more oxygen atoms, C₃-C₈ -Cycloalkylamino, adamantylamino, C₂-C₁₂ mono- or dialkenylamino, C₃-C₁₂-alkynylamino, N- (C₁-C₅) alkyl) -N-phenylamino, pyrrolidino, piperidino, morpholino, thiomorpholino, piperazino, N- (C₁- C₄-alkyl) -piperazino, hexamethyleneimino, imidazol-1-yl, pyrazol-1-yl, optionally substituted phenylamino, pyridylamino, thienylamino, hydrazino, C₁-C₄-mono- or dialkylhydrazino or phenylhydrazino, T⁵ for hydrogen, C₁-C₆ -Alkyl or phenyl and T⁶ represent the rest of a methylene-active compound, hydroxyimino or the radical NX, in which X is C₁-C₂₀-alkyl, which is optionally substituted and / or interrupted by one or more oxygen atoms, optionally subs substituted C₃-C₆-alkenyl, optionally substituted C₃-C₆-alkynyl, optionally substituted C₃-C₁₂-cycloalkyl, optionally substituted phenyl, pyridyl, C₁-C₄-alkoxycarbonylmethyl, amino, C₁-C₄-dialkylamino or phenylamino,
with the proviso that

• a) when R¹ and R² are each hydrogen and R⁴ are acetyl or ethoxycarbonyl, R³ is not for the rest of the formula stands and
• b) when R¹ and R² are each hydrogen and R⁴ cyano, R³ is not methylthio.

2. Aminothiazoles according to claim 1, characterized in that
R¹ and R² are each hydrogen or together the rest wherein T¹ for hydrogen, C₁-C₄-alkyl or phenyl and T² and T³ independently of one another for C₁-C₄-alkyl or phenyl or together with the nitrogen atom connecting them for pyrrolidino, piperidino, morpholino, thiomorpholino, piperazino, N- (C₁-C₄ -Alkyl) piperazino or hexamethyleneimino, mean and R³ and R⁴ each have the meaning given in claim 1. 3. A process for the preparation of aminothiazoles according to claim 1, characterized in that halogenamino thiazoles of the formula II in which R¹, R² and R⁴ each have the meaning given in Claim 1 and Hal represents chlorine or bromine, with a mercapto compound of the formula IIIR³-H (III) in which R³ has the meaning given in Claim 1.