Aminothiazoles

The present invention relates to novel aminothiazoles of the formula I ##STR4## or the tautomers thereof, where R.sup.1 and R.sup.2 are each hydrogen or together form a radical of the formula ##STR5## where T.sup.1 is hydrogen, C.sub.1 -C.sub.6 -alkyl or phenyl and T.sup.2 and T.sup.3 are identical or different and each, independently of one another, is C.sub.1 -C.sub.6 -alkyl, C.sub.5 -C.sub.7 -cycloalkyl or phenyl, or T.sup.2 and T.sup.3 form, together with the nitrogen connecting them, a 5- to 7-membered saturated heterocyclic radical which may contain further hetero atoms, R.sup.3 is
--S(O).sub.n --X,
where n is 0, 1 or 2 and X is substituted or unsubstituted C.sub.1 -C.sub.20 -alkyl, C.sub.3 -C.sub.8 -cycloalkyl, substituted or unsubstituted C.sub.3 -C.sub.6 -alkenyl, substituted or unsubstituted C.sub.3 -C.sub.6 -alkynyl, substituted or unsubstituted phenyl or, if n is 0, also hydrogen, or R.sub.3 is Y which means mono- or di-C.sub.1 -C.sub.20 -alkylamino, where the alkyl may be substituted and/or interrupted by one or more oxygen atoms, C.sub.3 -C.sub.6 -cycloalkylamino, adamantylamino, mono- or di-C.sub.2 -C.sub.12 -alkenylamino, C.sub.3 -C.sub.12 -alkynylamino, N-(C.sub.1 -C.sub.5 -alkyl)-N-phenylamino, pyrrolidino, piperidino, morpholino, thiomorpholino, piperazino, N-(C.sub.1 -C.sub.4 -alkyl)-piperazino, hexamethyleneimino, 1-imidazolyl, 1-pyrazolyl, substituted or unsubstituted phenylamino, pyridylamino, thienylamino, hydrazino, mono- or di-C.sub.1 -C.sub.4 -alkylhydrazino or phenylhydrazino and R.sup.4 is C.sub.1 -C.sub.6 -alkanoyl, benzoyl, cyano or ##STR6## where T.sup.4 is hydroxyl, C.sub.1 -C.sub.5 -alkoxy, amino or the abovementioned radical Y, T.sup.5 is hydrogen, C.sub.1 -C.sub.5 -alkyl or phenyl and T.sup.6 is the radical of an active methylene compound, hydroxyimino or N-Q where Q is C.sub.1 -C.sub.20 -alkyl which may be substituted and may be interrupted by one or more oxygen atoms, or C.sub.3 -C.sub.6 -alkenyl, C.sub.3 -C.sub.20 -alkynyl, C.sub.3 -C.sub.12 -cycloalkyl or phenyl, each of which may be substituted, pyridyl, C.sub.1 -C.sub.4 -alkoxycarbonylmethyl, amino, i-C.sub.1 -C.sub.4 -alkylamino or phenylamino, with the proviso that
a) R.sup.3 is not ##STR7## when R.sup.1 and R.sup.2 are each hydrogen and R.sup.4 is acetyl or ethoxycarbonyl,
b) R.sup.3 is not methylthio when R.sup.1 and R.sup.2 are each hydrogen and R.sup.4 is cyano, and
c) R.sup.1 and R.sup.2 are not both hydrogen when R.sup.3 is piperidino or morpholino and R.sup.4 is cyano.
Tetrahedron Lett. 22 (1982) 2285-2288 has disclosed the compound 2-amino-4-methylthio-5-cyanothiazole. Furthermore, Tetrahedron Lett. 28 (1987) 117-120 describes 2-aminothiazoles which have either acetyl or ethoxycarbonyl in position 5 and ##STR8## in position 4.
2,4-Diaminothiazole derivatives having a substituted amino group in position 2, a piperidino or morpholino group in position 4 and a cyano group in position 5 have also been disclosed (see, for example, Tetrahedron Lett. 22 (1981) 2285-2288).
However, these thiazoles are not especially suitable as diazo components for preparing azo dyes.
It was an object of the present invention to provide novel 2-aminothiazoles which have a mercapto group or a substituted amino group in position 4 and are intended to be especially suitable as diazo component or precursor thereof for preparing azo dyes.
We have accordingly found the aminothiazoles of the formula I defined above.
All the alkyl and alkenyl groups in the abovementioned formula I can be either straight-chain or branched.
Alkyl groups interrupted by one or more oxygen atoms in the formula I are preferably interrupted by from 1 to 3, in particular 1 to 2, oxygen atoms.
Examples of possible substituents for phenyl groups in the formula I are C.sub.1 -C.sub.6 -alkyl, C.sub.1 -C.sub.6 -alkoxy, halogen, especially fluorine, chlorine or bromine, nitro, hydroxyl, amino, mono- or di-C.sub.1 -C.sub.6 -alkylamino, acetylamino, carboxyl, carbamoyl, thiocarbamoyl, cyano, C.sub.1 -C.sub.6 -alkoxycarbonyl, trifluoromethyl, hydroxy-C.sub.1 -C.sub.3 -alkyl or C.sub.1 -C.sub.4 -alkanoyl.
Examples of possible substituents for alkyl groups in the formula I are hydroxyl, C.sub.1 -C.sub.6 -alkoxy, phenyl-C.sub.1 -C.sub.4 -alkoxy, phenoxy, amino, mono- or di-C.sub.1 -C.sub.6 -alkylamino, phenyl-C.sub.1 -C.sub.6 -alkylamino, diphenyl-C.sub.1 -C.sub.4 -alkylamino, phenylamino, diphenylamino, mono- or di-C.sub.3 -C.sub.6 -cycloalkylamino, C.sub.3 -C.sub.6 -cycloalkyl, hydroxy-C.sub.1 -C.sub.6 -alkylamino, morpholino, piperazino, N-(C.sub.1 -C.sub.6 -alkyl)piperazino, thiomorpholino, piperidino, pyrrolidino, hexamethyleneimino, 2-thienyl, 2-furyl, 1H-pyrrol-2-yl, 2-pyridyl, 3-pyridyl, 4-pyridyl, phenyl, carboxyl, C.sub.1 -C.sub.3 -alkoxycarbonyl, carbamoyl, mono- or di-C.sub.1 -C.sub.4 -alkylcarbamoyl, cyano, thiocarbamoyl, phenoxycarbamoyl, phenyl-C.sub.1 -C.sub.4 -alkoxycarbonyl, mono- or diphenylcarbamoyl, mono- or di(phenyl-C.sub.1 -C.sub.4 -alkyl)carbamoyl, mono- or diphenylthiocarbamoyl, mono- or di(phenyl-C.sub.1 -C.sub.4 -alkyl)thiocarbamoyl, C.sub.1 -C.sub.6 -alkylthio, phenylthio or phenyl-C.sub.1 -C.sub.4 -alkylthio.
Examples of possible substituents for alkenyl, alkynyl or cycloalkyl groups in the formula I are fluorine, chlorine or bromine.
When T.sup.2 and T.sup.3 form, together with the nitrogen connecting them, a 5- to 7-membered saturated heterocyclic radical which may contain further hetero atoms, possible examples are pyrrolidino, piperidino, morpholino, thiomorpholino, thiomorpholino S,S-dioxide, piperazino, N-(C.sub.1 -C.sub.4 -alkyl)piperazino or hexamethyleneimino.
Examples of T.sup.1, T.sup.2, T.sup.3 and T.sup.5 are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl or hexyl.
Examples of R.sup.4 are formyl, acetyl, propionyl, butyryl, isobutyryl, pentanoyl or hexanoyl.
(The names isooctyl, isononyl, isodecyl and isotridecyl used hereinafter are trivial names derived from the alcohols obtained by the oxo synthesis (cf. Ullmanns Encyklopadie der technischen Chemie, 4th Edition, Volume 7, pages 215 to 217 and Volume 11, pages 435 and 436.)
The radical --NQ is derived from a primary amine of the formula H.sub.2 NX. Examples are 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-dimathylamino)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 phenylhydrazine.
Examples of T.sup.4 are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, pentyloxy, isopentyloxy, neopentyloxy or hexyloxy.
The radical T.sup.6 is derived, for example, from an active methylene compound of the formula H.sub.2 T.sup.6. Examples of formulae of these compounds are ##STR9## where Z is cyano, nitro, C.sub.1 -C.sub.6 -alkanoyl, benzoyl, C.sub.1 -C.sub.4 -alkylsulfonyl, phenylsulfonyl, carboxyl, C.sub.1 -C.sub.4 -alkoxycarbonyl, carbamoyl or mono- or di-C.sub.1 -C.sub.4 -alkylcarbamoyl, or ##STR10##
Examples of some particularly important compounds are: ##STR11##
Examples of Y are 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-(1-piperazinyl)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-morpholino-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-carboxyethylamino, 3-carboxy-n-propylamino, 4-carboxy-n-butylamino, 5-carboxy-n-pentylamino, 10-carboxy-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-mathoxyphenylamino, 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-carboxyphenylamino, m-carboxyphenylamino, p-carboxyphenylamino, o-aminocarbonylphenylamino, m-aminocarbonylphenylamino, p-aminocarbonylphenylamino, 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, 1-imidazolyl, 1-pyrazolyl, 2-pyridylamino, 3-pyridylamino, 4-pyridylamino, 3-pyridylmethylamino, 2-furylmethylamino, thienylamino, benzylamino, o-methoxybenzylamino, p-methoxybenzylamino, p-fluorobenzylamino, o-chlorobenzylamino, p-chlorobenzylamino, 3,4-dimethoxybenzylamino, 2-phenylethylamino, (+/-)-.alpha.-methylbenzylamino, (+)-.alpha.-methylbenzylamino, (-)-.alpha.-methylbenzylamino, 3-phenyl-n-propylamino, 1-methyl-3-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-(2-ethylhexyl)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.
Examples of R.sup.3 are 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.
Preferred aminothiazoles of the formula I are those in which R.sup.1 and R.sup.2 are each hydrogen or together form the radical ##STR12## where T.sup.1 is hydrogen, C.sub.1 -C.sub.4 -alkyl or phenyl and T.sup.2 and T.sup.3 are each, independently of one another, C.sub.1 -C.sub.4 -alkyl or phenyl, or form, together with the nitrogen atom connecting them, pyrrolidino, piperidino, morpholino, thiomorpholino, piperazino, N-(C.sub.1 -C.sub.4 -alkyl)piperazino or hexamethyleneimino, and R.sup.3 and R.sup.4 each has the abovementioned meanings.
Particularly preferred aminothiazoles of the formula I are those in which R.sup.1 and R.sup.2 are each hydrogen or together form the radical ##STR13## where T.sup.1 is hydrogen and T.sup.2 and T.sup.3 are each, independently of one another, C.sub.1 -C.sub.4 -alkyl.
Further particularly preferred aminothiazoles of the formula I are those in which R.sup.4 is formyl, acetyl, propionyl, butyryl, benzoyl, cyano or ##STR14## where T.sup.5 is hydrogen, methyl, ethyl or phenyl, and T.sup.4 and T.sup.6 each has the abovementioned meanings.
Further particularly preferred aminothiazoles of the formula I are those in which Y is mono- or di-C.sub.1 -C.sub.6 -alkylamino, allylamino, methallylamino, propargylamino, C.sub.2 -C.sub.6 -alkylamino which is substituted by phenyl, hydroxyl, phenoxy, amino or mono- or di-C.sub.1 -C.sub.4 -alkylamino or interrupted by an oxygen atom, or phenylamino, pyrrolidino, piperidino, morpholino, piperazino or N-(C.sub.1 -C.sub.4 -alkyl)piperazino.
Further particularly preferred aminothiazoles of the formula I are those in which R.sup.3 is C.sub.1 -C.sub.6 -alkylthio, benzylthio, cyclohexylthio, C.sub.3 -C.sub.4 -alkenylthio, propargy thio, phenylthio, C.sub.1 -C.sub.6 -alkylsulfonyl, benzylsulfonyl, cyclohexylsulfonyl, C.sub.3 -C.sub.4 -alkenylsulfonyl, propargylsulfonyl or phenylsulfonyl.
Further particularly preferred aminothiazoles of the formula I are those in which R.sup.4 is cyano, formyl or ##STR15## where Z is cyano, nitro or C.sub.1 -C.sub.4 -alkoxycarbonyl.
Particularly important aminothiazoles of the formula I are those in which R.sup.1 and R.sup.2 are each hydrogen or together form the radical .dbd.CH--N(CH.sub.3).sub.2.
Further particularly noteworthy aminothiazoles of the formula I are those in which R.sup.4 is formyl, cyano or ##STR16## where T.sup.4 is hydroxyl, methoxy, ethoxy or amino, T.sup.5 is hydrogen, methyl, ethyl or phenyl and T.sup.6 has the abovementioned meanings.
Attention is drawn to aminothiazoles of the formula I in which R.sup.4 is formyl, cyano or ##STR17## where T.sup.6 has the abovementioned meanings.
Particular attention is drawn to aminothiazoles of the formula Ia ##STR18## or the tautomers thereof, where
L.sup.1 is amino,
L.sup.2 is C.sub.1 -C.sub.6 -alkylthio, benzylthio, cyclohexylthio, C.sub.3 -C.sub.4 -alkenylthio, propargylthio, phenylthio, C.sub.1 -C.sub.6 -alkylsulfonyl, benzylsulfonyl, cyclohexylsulfonyl, C.sub.3 -C.sub.4 -alkenylsulfonyl, propargylsulfonyl, phenylsulfonyl, mono- or di-C.sub.1 -C.sub.6 -alkylamino, allylamino, methallylamino, propargylamino, C.sub.2 -C.sub.6 -alkylamino which is substituted by phenyl, hydroxyl, phenoxy, amino or mono- or di-C.sub.1 -C.sub.4 -alkylamino or interrupted by an oxygen atom, or phenylamino, pyrrolidino, piperidino, morpholino, piperazino or N-(C.sub.1 -C.sub.4 -alkyl)piperazino and
L.sup.3 is cyano, formyl or the radical ##STR19## where Z is cyano, nitro or C.sub.1 -C.sub.4 -alkoxycarbonyl.
Particular industrial importance attaches to aminothiazoles of the formula I where n is 0 or 2 and X is benzyl or phenyl.
The aminothiazoles of the formula I according to the invention can be obtained, for example, by reacting haloaminothiazoles of the formula II ##STR20## where R.sup.1, R.sup.2 and R.sup.4 each has the abovementioned meanings, and Hal is chlorine or bromine, with a compound of the formula III
R.sup.3 --H (III)
where R.sup.3 has the abovementioned meanings. If R.sup.3 is --S(O).sub.n --X, the compounds are generally used in the form of their alkali metal salts.
For example, the haloaminothiazole II is reacted with the compound III (or its alkali metal salt) in an inert solvent (e.g. N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidone, 1,3-dimethylhexahydro-2-pyrimidone, 1,2-diethoxyethane, benzene, toluene, xylene, methylene chloride, chloroform, methanol, ethanol, propanol, isopropanol, butanol or isobutanol) at from -10.degree. to +150.degree. C., where appropriate in the presence of a base (e.g. triethylamine, tripropylamine, tributylamine, pyridine, 4-dimethylaminopyridine, sodium methylate, sodium ethylate, potassium tert-butylate, sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, sodium hydride or potassium hydride). The molar ratio of II:III is usually from 1:2 to 1:10. When the reaction is carried out in the presence of a base, the molar ratio of base to III is generally from 1:1 to 10:1.
The presence of a base is expedient for the reaction of compounds of the formula III where R.sup.3 is --S(O).sub.n --X.
The haloaminothiazoles of the formula II are known and described, for example, in U.S. Pat. No. 4,395,544 or can be obtained by methods similar to those detailed therein.
The novel aminothiazoles are valuable intermediates for the synthesis of dyes, crop protection agents or pharmaceuticals. They are used in particular as diazo components (R.sup.1, R.sup.2 .dbd.H) or precursors thereof for preparing azo dyes.
For preparing azo dyes the amino compound of the formula IV ##STR21## where R.sup.3 and R.sup.4 have the above mentioned meanings, can for example be reacted in an acidic aqueous medium with an alkali nitrite to give a diazonium salt of the formula IVa ##STR22## where An.crclbar. is an anion (e.g., chloride) and R.sup.3 and R.sup.4 have the abovementioned meanings, which in turn can be coupled with a coupling component of the formula V
H--K (V),
where K is the radical of a coupling compoent (e.g., dimethyl aniline) to yield an azo dye of the formula VI ##STR23## where R.sup.3, R.sup.4 and K have the above meanings.
Precursors of the amino compounds IV are thiazoles of the formula IVb ##STR24## where R.sup.3, R.sup.4, T.sup.1, T.sup.2 and T.sup.3 have the above meanings, which are easily converted to the amino compound by hydrolysis.
The Examples which follow are intended to illustrate the invention in detail.

EXAMPLE 1
3.7 g of sodium ethanolate were dissolved in 40 ml of ethanol. To this were added 4.5 g of n-butanethiol, 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. The solvent was then removed by distillation under reduced pressure, and the residue was stirred with 150 ml of hot water. The suspension was adjusted to pH 3 with concentrated hydrochloric acid, cooled to 10.degree. C. and stirred at this temperature for a further 2 hours. The precipitate was filtered off with suction, washed with water and dried in a vacuum oven at 50.degree. C. It was purified by recrystallization from a mixture of water and acetic acid with the addition of active carbon. 8.1 g (75% of theory) of the compound of the formula ##STR25## were obtained of melting point 131.degree. to 132.degree. C. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the indicated structure.
EXAMPLE 2
16.25 g of 2-amino-4-chloro-5-formylthiazole were dissolved in 100 ml of N,N-dimethylformamide. To this were added 19.6 g of sodium benzenesulfinate. The mixture was stirred at room temperature for one hour and at 70.degree. C. for 4 hours. The mixture was then poured into 600 ml of ice-water, and the precipitate was filtered off with suction, washed with water and dried at 50.degree. C. under reduced pressure. 21.6 g (81% of theory) of the compound ##STR26## were obtained of melting point 166.degree. to 167.degree. C. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the indicated formula.
The compounds of the formula ##STR27## which are listed in Table 1 which follows can be prepared in a similar manner.
TABLE 1__________________________________________________________________________ MeltingExample pointno. R.sup.3 NR.sup.1 R.sup.2 R.sup.4 (.degree.C.)__________________________________________________________________________ 3 SH NH.sub.2 CHO 4 S--CH.sub.3 NH.sub.2 CHO 5 S--C.sub.2 H.sub.5 NH.sub.2 CHO 6 S-nC.sub.3 H.sub.7 NH.sub.2 CHO 124-124.5 7 S-isoC.sub.3 H.sub.7 NH.sub.2 CHO 8 S-isoC.sub.4 H.sub.9 NH.sub.2 CHO 9 S-secC.sub.4 H.sub.9 NH.sub.2 CHO 10 S-tertC.sub.4 H.sub.9 NH.sub.2 CHO 11 S-nC.sub.5 H.sub.11 NH.sub.2 CHO 12 S-neoC.sub.5 H.sub.11 NH.sub.2 CHO 13 S-nC.sub.6 H.sub.13 NH.sub.2 CHO 123-125 14 S-nC.sub.7 H.sub.15 NH.sub.2 CHO 15 S-nC.sub.8 H.sub.17 NH.sub.2 CHO 106-107 16 S-nC.sub.9 H.sub.19 NH.sub.2 CHO 17 S-nC.sub.10 H.sub.21 NH.sub.2 CHO 18 S-nC.sub.11 H.sub.23 NH.sub.2 CHO 19 S-nC.sub.12 H.sub.25 NH.sub.2 CHO 20 S-nC.sub.13 H.sub.27 NH.sub.2 CHO 21 S-nC.sub.14 H.sub.29 NH.sub.2 CHO 22 S-nC.sub.15 H.sub.31 NH.sub.2 CHO 23 S-nC.sub.16 H.sub.33 NH.sub.2 CHO 24 S-nC.sub.17 H.sub.35 NH.sub.2 CHO 25 S-nC.sub.18 H.sub.37 NH.sub.2 CHO 26 S-nC.sub.19 H.sub.39 NH.sub.2 CHO 27 S-nC.sub.20 H.sub.41 NH.sub.2 CHO 28 S-Cyclopropyl NH.sub.2 CHO 29 S-Cyclopentyl NH.sub.2 CHO 30 S-Cyclohexyl NH.sub.2 CHO 162-163.5 31 S-Cycloheptyl NH.sub.2 CHO 32 S-Cyclooctyl NH.sub.2 CHO 33 S--C.sub.6 H.sub.5 NH.sub.2 CHO 174-175 34 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CHO 153-155 35 S--(CH.sub.2).sub.2 --C.sub.6 H.sub.5 NH.sub.2 CHO 36 S--CH.sub.2 CH.sub.2 OH NH.sub.2 CHO 37 S--CH.sub.2 --CH.dbd.CH.sub.2 NH.sub.2 CHO 38 S--CH.sub.2 --C.tbd.CH NH.sub.2 CHO 39 SH NH.sub.2 CN 40 S--C.sub.2 H.sub.5 NH.sub.2 CN 41 S-nC.sub.3 H.sub.7 NH.sub.2 CN 42 S-isoC.sub.3 H.sub.7 NH.sub.2 CN 43 S-nC.sub.4 H.sub.9 NH.sub.2 CN 44 S-isoC.sub.4 H.sub.9 NH.sub.2 CN 45 S-secC.sub.4 H.sub.9 NH.sub.2 CN 46 S-tertC.sub.4 H.sub.9 NH.sub.2 CN 47 S-nC.sub.5 H.sub.11 NH.sub.2 CN 48 S-neoC.sub.5 H.sub.11 NH.sub.2 CN 49 S-nC.sub.6 H.sub.13 NH.sub.2 CN 50 S-nC.sub.7 H.sub.15 NH.sub.2 CN 51 S-nC.sub.8 H.sub.17 NH.sub.2 CN 52 S-nC.sub.9 H.sub.19 NH.sub.2 CN 53 S-nC.sub.10 H.sub.21 NH.sub.2 CN 54 S-nC.sub.11 H.sub.23 NH.sub.2 CN 55 S-nC.sub.12 H.sub.23 NH.sub.2 CN 56 S-nC.sub.13 H.sub.25 NH.sub.2 CN 57 S-nC.sub.14 H.sub.29 NH.sub.2 CN 58 S-nC.sub.15 H.sub.31 NH.sub.2 CN 59 S-nC.sub.16 H.sub.33 NH.sub.2 CN 60 S-nC.sub.17 H.sub.35 NH.sub.2 CN 61 S-nC.sub.18 H.sub.37 NH.sub.2 CN 62 S-nC.sub.19 H.sub.39 NH.sub.2 CN 63 S-nC.sub.20 H.sub.41 NH.sub.2 CN 64 S-Cyclopropyl NH.sub.2 CN 65 S-Cyclopentyl NH.sub.2 CN 66 S-Cyclohexyl NH.sub.2 CN 67 S-Cycloheptyl NH.sub.2 CN 68 S-Cyclooctyl NH.sub.2 CN 69 S--C.sub.6 H.sub.5 NH.sub.2 CN 70 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CN 71 S--(CH.sub.2).sub.2 --C.sub.6 H.sub.5 NH.sub.2 CN 72 S--CH.sub.2 CH.sub.2 OH NH.sub.2 CN 73 S--CH.sub.2 --CH.dbd.CH.sub.2 NH.sub.2 CN 74 S--CH.sub.2 --C.tbd.CH NH.sub.2 CN 75 S--CH.sub.2 --C(CH.sub.3).dbd.CH.sub.2 NH.sub.2 CHO 76 SO.sub.2 --CH.sub.3 NH.sub.2 CHO 77 SO.sub.2 --C.sub.2 H.sub.5 NH.sub.2 CHO 78 SO.sub.2 -nC.sub.3 H.sub.7 NH.sub.2 CHO 79 SO.sub.2 -isoC.sub.3 H.sub.7 NH.sub.2 CHO 80 SO.sub.2 -nC.sub.4 H.sub.9 NH.sub.2 CHO 81 SO.sub.2 -isoC.sub.4 H.sub.9 NH.sub.2 CHO 82 SO.sub.2 -secC.sub.4 H.sub.9 NH.sub.2 CHO 83 SO.sub.2 -tertC.sub.4 H.sub.9 NH.sub.2 CHO 84 SO.sub. 2 -nC.sub.5 H.sub.11 NH.sub.2 CHO 85 SO.sub.2 -neoC.sub.5 H.sub.11 NH.sub.2 CHO 86 SO.sub.2 -nC.sub.6 H.sub.13 NH.sub.2 CHO 87 SO.sub.2 -nC.sub.7 H.sub.15 NH.sub.2 CHO 88 SO.sub.2 -nC.sub.8 H.sub.17 NH.sub.2 CHO 89 SO.sub.2 -nC.sub.9 H.sub.19 NH.sub.2 CHO 90 SO.sub.2 -nC.sub.10 H.sub.21 NH.sub.2 CHO 91 SO.sub.2 -nC.sub.11 H.sub.23 NH.sub.2 CHO 92 SO.sub.2 -nC.sub.12 H.sub.25 NH.sub.2 CHO 93 SO.sub.2 -nC.sub.13 H.sub.27 NH.sub.2 CHO 94 SO.sub.2 -nC.sub.14 H.sub.29 NH.sub.2 CHO 95 SO.sub.2 -nC.sub.15 H.sub.31 NH.sub.2 CHO 96 SO.sub.2 -nC.sub.16 H.sub.33 NH.sub.2 CHO 97 SO.sub.2 -nC.sub.17 H.sub.35 NH.sub.2 CHO 98 SO.sub.2 -nC.sub.18 H.sub.37 NH.sub.2 CHO 99 SO.sub.2 -nC.sub.19 H.sub.39 NH.sub.2 CHO100 SO.sub.2 -nC.sub.20 H.sub.41 NH.sub.2 CHO101 SO.sub.2 -Cyclopropyl NH.sub.2 CHO102 SO.sub.2 -Cyclopentyl NH.sub.2 CHO103 SO.sub.2 -Cyclohexyl NH.sub.2 CHO104 SO.sub.2 -Cycloheptyl NH.sub.2 CHO105 SO.sub.2 -Cyclooctyl NH.sub.2 CHO106 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 CH.dbd.C(CN) (COOC.sub.2 H.sub.5)107 SO.sub.2 --CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CHO108 SO.sub.2 --(CH.sub.2).sub.2 --C.sub.6 H.sub.5 NH.sub.2 CHO109 SO.sub.2 --CH.sub.2 CH.sub.2 OH NH.sub.2 CHO110 SO.sub.2 --CH.sub.2 --CH.dbd.CH.sub.2 NH.sub.2 CHO111 SO.sub.2 --CH.sub.2 --C.tbd.CH NH.sub.2 CHO112 S--CH.sub.2 --C(CH.sub.3).dbd.CH.sub.2 NH.sub.2 CN113 SO.sub.2 --CH.sub.3 NH.sub.2 CN114 SO.sub.2 --C.sub.2 H.sub.5 NH.sub.2 CN115 SO.sub.2 --nC.sub.3 H.sub.7 NH.sub.2 CN116 SO.sub.2 --isoC.sub.3 H.sub.7 NH.sub.2 CN117 SO.sub.2 --nC.sub.4 H.sub.9 NH.sub.2 CN118 SO.sub.2 -isoC.sub.4 H.sub.9 NH.sub.2 CN119 SO.sub.2 -secC.sub.4 H.sub.9 NH.sub.2 CN120 SO.sub.2 -tertC.sub.4 H.sub.9 NH.sub.2 CN121 SO.sub.2 -nC.sub.5 H.sub.11 NH.sub.2 CN122 SO.sub.2 -neoC.sub.5 H.sub.11 NH.sub.2 CN123 SO.sub.2 -nC.sub.6 H.sub.13 NH.sub.2 CN124 SO.sub.2 -nC.sub.7 H.sub.15 NH.sub.2 CN125 SO.sub.2 -nC.sub.8 H.sub.17 NH.sub.2 CN126 SO.sub.2 -nC.sub.9 H.sub.19 NH.sub.2 CN127 SO.sub.2 -nC.sub.10 H.sub.21 NH.sub.2 CN128 SO.sub.2 -nC.sub.11 H.sub.23 NH.sub.2 CN129 SO.sub.2 -nC.sub.12 H.sub.25 NH.sub.2 CN130 SO.sub.2 -nC.sub.13 H.sub.27 NH.sub.2 CN131 SO.sub.2 -nC.sub.14 H.sub.29 NH.sub.2 CN132 SO.sub.2 -nC.sub.15 H.sub.31 NH.sub.2 CN133 SO.sub.2 -nC.sub.16 H.sub.33 NH.sub.2 CN134 SO.sub.2 -nC.sub.17 H.sub.35 NH.sub.2 CN135 SO.sub.2 -nC.sub.18 H.sub.37 NH.sub.2 CN136 SO.sub.2 -nC.sub.19 H.sub.39 NH.sub.2 CN137 SO.sub.2 -nC.sub.20 H.sub.41 NH.sub.2 CN138 SO.sub.2 -Cyclopropyl NH.sub.2 CN139 SO.sub.2 -Cyclopentyl NH.sub.2 CN140 SO.sub.2 -Cyclohexyl NH.sub.2 CN141 SO.sub.2 -Cycloheptyl NH.sub.2 CN142 SO.sub.2 -Cyclooctyl NH.sub. 2 CN143 SO.sub.2 -C.sub.6 H.sub.5 NH.sub.2 CN144 SO.sub.2 --CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CN145 SO.sub.2 --(CH.sub.2).sub.2 --C.sub.6 H.sub.5 NH.sub.2 CN146 SO.sub.2 CH.sub.2 CH.sub.2 OH NH.sub.2 CN147 SO.sub.2 --CH.sub.2 --CH.dbd.CH.sub.2 NH.sub.2 CN148 SO.sub.2 --CH.sub.2 --C.tbd.CH.sub.2 NH.sub.2 CN149 SH NH.sub.2 COOH150 S--CH.sub.3 NH.sub.2 COOH151 S--C.sub.2 H.sub.5 NH.sub.2 COOH152 S-nC.sub.3 H.sub.7 NH.sub.2 COOH153 S-isoC.sub.3 H.sub.7 NH.sub.2 COOH154 S-isoC.sub.4 H.sub.9 NH.sub.2 COOH155 S-secC.sub.4 H.sub.9 NH.sub.2 COOH156 S-tertC.sub.4 H.sub.9 NH.sub.2 COOH157 S-nC.sub.5 H.sub.11 NH.sub.2 COOH158 S-neoC.sub.5 H.sub.11 NH.sub.2 COOH159 S-nC.sub.6 H.sub.13 NH.sub.2 COOH160 S-nC.sub.7 H.sub.15 NH.sub.2 COOH161 S-nC.sub.8 H.sub.17 NH.sub.2 COOH162 S-nC.sub.9 H.sub.19 NH.sub.2 COOH163 S-nC.sub.10 H.sub.21 NH.sub.2 COOH164 S-nC.sub.11 H.sub.23 NH.sub.2 COOH165 S-nC.sub.12 H.sub.25 NH.sub.2 COOH166 S-nC.sub.13 H.sub.27 NH.sub.2 COOH167 S-nC.sub.14 H.sub.29 NH.sub.2 COOH168 S-nC.sub.15 H.sub.31 NH.sub.2 COOH169 S-nC.sub.16 H.sub.33 NH.sub.2 COOH170 S-nC.sub.17 H.sub.35 NH.sub.2 COOH171 S-nC.sub.18 H.sub.37 NH.sub.2 COOH172 S-nC.sub.20 H.sub.39 NH.sub.2 COOH173 S-nC.sub.20 H.sub.41 NH.sub.2 COOH174 S-Cyclopropyl NH.sub.2 COOH175 S-Cyclopentyl NH.sub.2 COOH176 S-Cyclohexyl NH.sub.2 COOH177 S-Cycloheptyl NH.sub.2 COOH178 S-Cyclooctyl NH.sub.2 COOH179 S--C.sub.6 H.sub.5 NH.sub.2 COOH180 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 COOH181 S--(CH.sub.2).sub.2 --C.sub.6 H.sub.5 NH.sub.2 COOH182 S--CH.sub.2 CH.sub.2 OH NH.sub.2 COOH183 S--CH.sub.2 --CH.dbd.CH.sub.2 NH.sub.2 COOH184 S--CH.sub.2 --C.tbd.CH NH.sub.2 COOH185 SH NH.sub.2 COOCH.sub.3186 S--CH.sub.3 NH.sub.2 COOCH.sub.3187 S--C.sub.2 H.sub.5 NH.sub.2 COOCH.sub.3188 S-nC.sub.3 H.sub.7 NH.sub.2 COOCH.sub.3189 S-isoC.sub. 3 H.sub.7 NH.sub.2 COOCH.sub.3190 S-nC.sub.4 H.sub.9 NH.sub.2 COOCH.sub.3191 S-isoC.sub.4 H.sub.9 NH.sub.2 COOCH.sub.3102 S-secC.sub.4 H.sub.9 NH.sub.2 COOCH.sub.3193 S-tertC.sub.4 H.sub.9 NH.sub.2 COOCH.sub.3194 S-nC.sub.5 H.sub.11 NH.sub.2 COOCH.sub.3195 S-neoC.sub.5 H.sub.11 NH.sub.2 COOCH.sub.3196 S-nC.sub.6 H.sub.13 NH.sub.2 COOCH.sub.3197 S-nC.sub.7 H.sub.15 NH.sub.2 COOCH.sub.3198 S-nC.sub.8 H.sub.17 NH.sub.2 COOCH.sub.3199 S-nC.sub.9 H.sub.19 NH.sub.2 COOCH.sub.3200 S-nC.sub.10 H.sub.21 NH.sub.2 COOCH.sub.3201 S-nC.sub.11 H.sub.23 NH.sub.2 COOCH.sub.3202 S-nC.sub.12 H.sub.25 NH.sub.2 COOCH.sub.3203 S-nC.sub.13 H.sub.27 NH.sub.2 COOCH.sub.3204 S-nC.sub.14 H.sub.29 NH.sub.2 COOCH.sub.3205 S-nC.sub.15 H.sub.31 NH.sub.2 COOCH.sub.3206 S-nC.sub.16 H.sub.33 NH.sub.2 COOCH.sub.3207 S-nC.sub.17 H.sub.35 NH.sub.2 COOCH.sub.3208 S-nC.sub.18 H.sub.37 NH.sub.2 COOCH.sub.3209 S-nC.sub.19 H.sub.39 NH.sub.2 COOCH.sub.3210 S-nC.sub.20 H.sub.41 NH.sub.2 COOCH.sub.3211 S-Cyclopropyl NH.sub.2 COOCH.sub.3212 S-Cyclopentyl NH.sub.2 COOCH.sub.3213 S-Cyclohexyl NH.sub.2 COOCH.sub.3214 S-Cycloheptyl NH.sub.2 COOCH.sub.3215 S-Cyclooctyl NH.sub.2 COOCH.sub.3216 S--C.sub.6 H.sub.5 NH.sub.2 COOCH.sub.3217 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 COOCH.sub.3218 S--(CH.sub.2).sub.2 --C.sub.6 H.sub.5 NH.sub.2 COOCH.sub.3219 S--CH.sub.2 CH.sub.2 OH NH.sub.2 COOCH.sub.3220 S--CH.sub.2 --CH.dbd.CH.sub.2 NH.sub.2 COOCH.sub.3221 S--CH.sub.2 --C.tbd.CH NH.sub.2 COOCH.sub.3222 S--CH.sub.2 --C(CH.sub.3).dbd.CH.sub.2 NH.sub.2 COOH223 SO.sub.2 --CH.sub.3 NH.sub.2 COOH224 SO.sub.2 --C.sub.2 H.sub.5 NH.sub.2 COOH225 SO.sub.2 -nC.sub.3 H.sub.7 NH.sub.2 COOH226 SO.sub.2 -isoC.sub.3 H.sub.7 NH.sub.2 COOH227 SO.sub.2 -nC.sub.4 H.sub.9 NH.sub.2 COOH228 SO.sub.2 -isoC.sub.4 H.sub.9 NH.sub.2 COOH229 SO.sub.2 -secC.sub.4 H.sub.9 NH.sub.2 COOH230 SO.sub.2 -tertC.sub.4 H.sub.9 NH.sub.2 COOH231 SO.sub.2 -nC.sub.5 H.sub.11 NH.sub.2 COOH232 SO.sub.2 -neoC.sub.5 H.sub.11 NH.sub.2 COOH233 SO.sub.2 -nC.sub.6 H.sub.13 NH.sub.2 COOH234 SO.sub.2 -nC.sub.7 H.sub.15 NH.sub.2 COOH235 SO.sub.2 -nC.sub.8 H.sub.17 NH.sub.2 COOH236 SO.sub.2 -nC.sub.9 H.sub.21 NH.sub.2 COOH237 SO.sub.2 -nC.sub.10 H.sub.21 NH.sub.2 COOH238 SO.sub.2 -nC.sub.11 H.sub.23 NH.sub.2 COOH239 SO.sub.2 -nC.sub.12 H.sub.25 NH.sub.2 COOH240 SO.sub.2 -nC.sub.13 H.sub.27 NH.sub.2 COOH241 SO.sub.2 -nC.sub.14 H.sub.29 NH.sub.2 COOH242 SO.sub.2 -nC.sub.15 H.sub.31 NH.sub.2 COOH243 SO.sub.2 -nC.sub.16 H.sub.33 NH.sub.2 COOH244 SO.sub.2 -nC.sub.17 H.sub.35 NH.sub.2 COOH245 SO.sub.2 -nC.sub.18 H.sub.37 NH.sub.2 COOH246 SO.sub.2 -nC.sub.19 H.sub.39 NH.sub.2 COOH247 SO.sub.2 -nC.sub.20 H.sub.41 NH.sub.2 COOH248 S-Cyclopropyl NH.sub.2 COOH249 S-Cyclopentyl NH.sub.2 COOH250 S-Cyclophexyl NH.sub.2 COOH251 S-Cycloheptyl NH.sub.2 COOH252 S-Cyclooctyl NH.sub.2 COOH253 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 COOH254 SO.sub.2 -- CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 COOH255 SO.sub.2 --(CH.sub.2).sub.2 --C.sub.6 H.sub.5 NH.sub.2 COOH256 SO.sub.2 --CH.sub.2 CH.sub.2 OH NH.sub.2 COOH257 SO.sub.2 --CH.sub.2 --CH.dbd.CH.sub.2 NH.sub.2 COOH258 SO.sub.2 --CH.sub.2 --C.tbd.CH NH.sub.2 COOH259 S--CH.sub.2 --C(CH.sub.3).dbd.CH.sub.2 NH.sub.2 COOCH.sub.3260 SO.sub.2 --CH.sub.3 NH.sub.2 COOCH.sub.3261 SO.sub.2 --C.sub.2 H.sub.5 NH.sub.2 COOCH.sub.3262 SO.sub.2 -nC.sub.3 H.sub.7 NH.sub.2 COOCH.sub.3263 SO.sub.2 -isoC.sub.3 H.sub.7 NH.sub.2 COOCH.sub.3264 SO.sub.2 -nC.sub.4 H.sub.9 NH.sub.2 COOCH.sub.3265 SO.sub.2 -isoC.sub.4 H.sub.9 NH.sub.2 COOCH.sub.3266 SO.sub.2 -secC.sub.4 H.sub.9 NH.sub.2 COOCH.sub.3267 SO.sub.2 -tertC.sub.4 H.sub.9 NH.sub.2 COOCH.sub.3268 SO.sub.2 -nC.sub.5 H.sub.11 NH.sub.2 COOCH.sub.3269 SO.sub.2 -neoC.sub.5 H.sub.11 NH.sub.2 COOCH.sub.3270 SO.sub.2 -nC.sub.6 H.sub.13 NH.sub.2 COOCH.sub.3271 SO.sub.2 -nC.sub.7 H.sub.15 NH.sub.2 COOCH.sub.3272 SO.sub.2 -nC.sub.8 H.sub.17 NH.sub.2 COOCH.sub.3273 SO.sub.2 -nC.sub.9 H.sub.19 NH.sub.2 COOCH.sub.3274 SO.sub.2 -nC.sub.10 H.sub.21 NH.sub.2 COOCH.sub.3275 SO.sub.2 -nC.sub.11 H.sub.23 NH.sub.2 COOCH.sub.3276 SO.sub.2 -nC.sub.12 H.sub.25 NH.sub.2 COOCH.sub.3277 SO.sub.2 -nC.sub.13 H.sub.27 NH.sub.2 COOCH.sub.3278 SO.sub.2 -nC.sub.14 H.sub.29 NH.sub.2 COOCH.sub.3279 SO.sub.2 -nC.sub.15 H.sub.31 NH.sub.2 COOCH.sub.3280 SO.sub.2 -nC.sub.16 H.sub.33 NH.sub.2 COOCH.sub.3281 SO.sub.2 -nC.sub.17 H.sub.35 NH.sub.2 COOCH.sub.3282 SO.sub.2 -nC.sub.18 H.sub.37 NH.sub.2 COOCH.sub.3283 SO.sub.2 -nC.sub.19 H.sub.39 NH.sub.2 COOCH.sub.3284 SO.sub.2 -nC.sub.20 H.sub.41 NH.sub.2 COOCH.sub.3285 S-Cyclopropyl NH.sub.2 COOCH.sub.3286 S-Cycloprentyl NH.sub.2 COOCH.sub.3287 S-Cyclohexyl NH.sub.2 COOCH.sub.3288 S-Cycloheptyl NH.sub.2 COOCH.sub.3289 S-Cyclooctyl NH.sub.2 COOCH.sub.3290 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 COOCH.sub.3291 SO.sub.2 --CH.sub.2 C.sub. 6 H.sub.5 NH.sub.2 COOCH.sub.3292 SO.sub.2 --(CH.sub.2).sub.2 --C.sub.6 H.sub.5 NH.sub.2 COOCH.sub.3293 SO.sub.2 --CH.sub.2 CH.sub.2 OH NH.sub.2 COOCH.sub.3294 SO.sub.2 --CH.sub.2 --CH.dbd.CH.sub.2 NH.sub.2 COOCH.sub.3295 SO.sub.2 --CH.sub.2 --CH.tbd.CH NH.sub.2 COOCH.sub.3296 S--CH.sub.2 COOH NH.sub.2 CHO297 S--CH.sub.2 COOCH.sub.3 NH.sub.2 CHO298 S--CH.sub.2 COOC.sub.2 H.sub.5 NH.sub.2 CHO299 S--CH.sub.2 COOH NH.sub.2 CN300 S--CH.sub.2 COOCH.sub.3 NH.sub.2 CN301 S--CH.sub.2 COOC.sub.2 H.sub.5 NH.sub.2 CN302 S--C.sub.2 H.sub.5 NH.sub.2 CH.dbd.C(CN).sub.2303 S--C.sub.6 H.sub.5 NH.sub.2 CH.dbd.C(CN).sub.2304 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CH.dbd.C(CN).sub.2305 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 CH.dbd.C(CN).sub.2306 S--C.sub.2 H.sub.5 NH.sub.2 CH.dbd.C(CN)(COOCH.sub.3)307 S--C.sub.6 H.sub.5 NH.sub.2 CH.dbd.C(CN)(COOCH.sub.3)308 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CH.dbd.C(CN)(COOCH.sub.3)309 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 CH.dbd.C(CN)(COOCH.sub.3)310 S-nC.sub.4 H.sub.9 N.dbd.CH--N(CH.sub.3).sub.2 CHO311 S--C.sub.6 H.sub.5 N.dbd.CH--N(CH.sub.3).sub.2 CHO312 S--CH.sub.2 C.sub.6 H.sub.5 N.dbd.CH--N(CH.sub.3).sub.2 CHO313 S--C.sub.2 H.sub.5 N.dbd.CH--N(CH.sub.3).sub.2 CHO314 SH N.dbd.CH--N(CH.sub.3).sub.2 CHO315 SO.sub.2 --C.sub.6 H.sub.5 N.dbd.CH--N(CH.sub.3).sub.2 CHO316 S-nC.sub.4 H.sub.9 N.dbd.CH--N(CH.sub.3).sub.2 CN317 S--C.sub.6 H.sub.5 N.dbd.CH--N(CH.sub.3).sub.2 CN318 S--CH.sub.2 C.sub.6 H.sub.5 N.dbd.CH--N(CH.sub.3).sub.2 CN319 S--C.sub.2 H.sub.5 N.dbd.CH--N(CH.sub.3).sub.2 CN320 SH N.dbd.CH--N(CH.sub.3).sub.2 CN321 SO.sub.2 --C.sub.6 H.sub.5 N.dbd.CH--N(CH.sub.3).sub.2 CN322 SO.sub.2 --(CH.sub.2).sub.3 C.sub.6 H.sub.5 NH.sub.2 CHO323 S--(CH.sub.2).sub.3 C.sub.6 H.sub.5 NH.sub. 2 CHO324 S--CH(CH.sub.3)C.sub.6 H.sub.5 NH.sub.2 CHO325 S--CH(C.sub.2 H.sub.5)C.sub.6 H.sub.5 NH.sub.2 CHO326 S--C(CH.sub.3).sub.2 C.sub.6 H.sub.5 NH.sub.2 CHO327 SO.sub.2 --(CH.sub.2).sub.3 C.sub.6 H.sub.5 NH.sub.2 CN328 S--(CH.sub.2).sub.3 C.sub.6 H.sub.5 NH.sub.2 CN329 S--CH(CH.sub.3)C.sub.6 H.sub.5 NH.sub.2 CN330 S--CH(C.sub.2 H.sub.5)C.sub.6 H.sub.5 NH.sub.2 CN331 S--C(CH.sub.3).sub.2 C.sub.6 H.sub.5 NH.sub.2 CN332 S--C.sub.6 H.sub.5 N.dbd.CH-morpholino CHO333 S--CH.sub.2 C.sub.6 H.sub.5 N.dbd.CH-pyrollidino CHO334 SO.sub.2 --C.sub.6 H.sub.5 N.dbd.CH-piperidino CHO335 S--C.sub.2 H.sub.5 N.dbd.CH-piperazino CN336 S--C.sub.6 H.sub.5 N.dbd.CH-thiomorpholino CHO337 S--CH.sub.2 C.sub.6 H.sub.5 N.dbd.CH-hexamethyleneimino CN338 S--C.sub.6 H.sub.5 NH.sub.2 COCH.sub.3339 S--C.sub.2 H.sub.5 NH.sub.2 COCH.sub.3340 S--nC.sub.4 H.sub.9 NH.sub.2 COCH.sub.3341 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 COCH.sub.3342 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 COCH.sub.3343 S--C.sub.6 H.sub.5 NH.sub.2 CO.sub.2 C.sub.2 H.sub.5344 S--C.sub.2 H.sub.5 NH.sub.2 COC.sub.2 H.sub.5345 S--nC.sub.4 H.sub.9 NH.sub.2 COC.sub.2 H.sub.5346 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 COC.sub.2 H.sub.5347 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 COC.sub.2 H.sub.5348 S--C.sub.6 H.sub.5 NH.sub.2 CO-nC.sub.3 H.sub.7349 S--C.sub.2 H.sub.5 NH.sub.2 CO-nC.sub.4 H.sub.9350 S-nC.sub.4 H.sub.9 NH.sub.2 CO-nC.sub.5 H.sub.11351 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CO-nC.sub.6 6.sub.13352 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 CO-nC.sub.6 H.sub.13353 S--C.sub.6 H.sub.5 NH.sub.2 COC.sub.6 H.sub.5354 S--C.sub.2 H.sub.5 NH.sub.2 COC.sub.6 H.sub.5355 S-nC.sub.4 H.sub.9 NH.sub.2 COC.sub.6 H.sub.5356 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 COC.sub.6 H.sub.5357 SO.sub.2 -- C.sub.6 H.sub.5 NH.sub.2 COC.sub.6 H.sub.5358 S--C.sub.2 H.sub.5 NH.sub.2 COOC.sub.2 H.sub.5359 S--nC.sub.4 H.sub.9 NH.sub.2 COOC.sub.2 H.sub.5360 S--nC.sub.6 H.sub.13 NH.sub.2 COOC.sub.2 H.sub.5361 S--C.sub.6 H.sub.5 NH.sub.2 COOC.sub.2 H.sub.5362 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 COOC.sub.2 H.sub.5363 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 COOC.sub.2 H.sub.5364 S--C.sub.2 H.sub.5 NH.sub.2 COO-nC.sub.3 H.sub.7365 S--nC.sub.4 H.sub.9 NH.sub.2 COO-nC.sub.3 H.sub.7366 S--nC.sub.6 H.sub.13 NH.sub.2 COO-nC.sub.3 H.sub.7367 S--C.sub.6 H.sub.5 NH.sub.2 COO-nC.sub.3 H.sub.7368 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 COO-nC.sub.3 H.sub.7369 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 COO-nC.sub.3 H.sub.7370 S--C.sub.2 H.sub.5 NH.sub.2 COO-nC.sub.4 H.sub.9371 S-nC.sub.4 H.sub.9 NH.sub.2 COO-nC.sub.4 H.sub.9372 S-nC.sub.6 H.sub.13 NH.sub.2 COO-nC.sub.4 H.sub.9373 S--C.sub.6 H.sub.5 NH.sub.2 COO-nC.sub.4 H.sub.9374 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 COO-nC.sub.4 H.sub.9375 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 COO-nC.sub.4 H.sub.9376 S--C.sub.2 H.sub.5 NH.sub.2 COO-nC.sub.5 H.sub.11377 S-nC.sub.4 H.sub.9 NH.sub.2 COO-nC.sub.5 H.sub.11378 S-nC.sub.6 H.sub.13 NH.sub.2 COO-nC.sub.5 H.sub.11379 S--C.sub.6 H.sub.5 NH.sub.2 COO-nC.sub.5 H.sub.11380 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 COO-nC.sub.5 H.sub.11381 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 COO-nC.sub.5 H.sub.11382 S--C.sub.2 H.sub.5 NH.sub.2 COO-nC.sub.6 H.sub.13383 S-nC.sub.4 H.sub.9 NH.sub.2 COO-nC.sub.6 H.sub.13384 S-nC.sub.6 H.sub.13 NH.sub.2 COO-nC.sub.6 H.sub.13385 S--C.sub.6 H.sub.5 NH.sub.2 COO-nC.sub.6 H.sub.13386 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 COO-nC.sub.6 H.sub.13387 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 COO-nC.sub.6 H.sub.13388 S--C.sub.2 H.sub.5 NH.sub.2 COOC.sub.6 H.sub.5389 S-nC.sub.4 H.sub. 9 NH.sub.2 COOC.sub.6 H.sub.5390 S-nC.sub.6 H.sub.13 NH.sub.2 COOC.sub.6 H.sub.5391 S--C.sub.6 H.sub.5 NH.sub.2 COOC.sub.6 H.sub.5392 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 COOC.sub.6 H.sub.5393 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 COOC.sub.6 H.sub.5394 S--C.sub.2 H.sub.5 NH.sub.2 CONH.sub.2395 S-nC.sub.4 H.sub.9 NH.sub.2 CONH.sub.2396 S-nC.sub.6 H.sub.13 NH.sub.2 CONH.sub.2397 S--C.sub.6 H.sub.5 NH.sub.2 CONH.sub.2398 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CONH.sub.2399 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 CONH.sub.2400 S--C.sub.6 H.sub.5 NH.sub.2 C(CH.sub.3).dbd.C(CN).sub.2401 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 C(C.sub.6 H.sub.5).dbd.C(CN).sub.2402 S--C.sub.2 H.sub.5 NH.sub.2 CON(CH.sub.3).sub.2403 S-nC.sub.4 H.sub.9 NH.sub.2 CON(CH.sub.3).sub.2404 S-nC.sub.6 H.sub.13 NH.sub.2 CON(CH.sub.3).sub.2405 S--C.sub.6 H.sub.5 NH.sub.2 CON(CH.sub.3).sub.2406 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CON(CH.sub.3).sub.2407 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 CON(CH.sub.3).sub.2408 S--C.sub.2 H.sub.5 NH.sub.2 CON(C.sub.2 H.sub.5).sub.2409 S-nC.sub.4 H.sub.9 NH.sub.2 CON(C.sub.2 H.sub.5).sub.2410 S-nC.sub.6 H.sub.13 NH.sub.2 CON(C.sub.2 H.sub.5).sub.2411 S--C.sub.6 H.sub.5 NH.sub.2 CON(C.sub.2 H.sub.5).sub.2412 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CON(C.sub.2 H.sub.5).sub.2413 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 CON(C.sub.2 H.sub.5).sub.2414 S--C.sub.2 H.sub.5 NH.sub.2 CON(C.sub.3 H.sub.7).sub.2415 S-nC.sub.4 H.sub.9 NH.sub.2 CON(C.sub.3 H.sub.7).sub.2416 S-nC.sub.6 H.sub.13 NH.sub.2 CON(C.sub.3 H.sub.7).sub.2417 S--C.sub.6 H.sub.5 NH.sub.2 CON(C.sub.3 H.sub.7).sub.2418 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CON(C.sub.3 H.sub.7).sub.2419 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 CON(C.sub.3 H.sub.7).sub.2420 S--C.sub.2 H.sub.5 NH.sub.2 CON(C.sub.4 H.sub.9).sub.2421 S-nC.sub.4 H.sub.9 NH.sub.2 CON(C.sub.5 H.sub.11).sub.2422 S-nC.sub.6 H.sub.13 NH.sub.2 CON(C.sub.6 H.sub.11).sub.2423 S--C.sub.6 H.sub.5 NH.sub.2 CON(CH.sub.3)(C.sub.6 H.sub.5)424 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CON(C.sub.2 H.sub.5)(C.sub.6 H.sub.5)425 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 CON(CH.sub.3)(C.sub.2 H.sub.5)426 S--C.sub.6 H.sub.5 NH.sub.2 CON(n-C.sub.3 H.sub.7)(C.sub.6 H.sub.5)427 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 CON(n-C.sub.4 H.sub.9)(C.sub.6 H.sub.5)428 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 CON(n-C.sub.6 H.sub.13)(C.sub.6 H.sub.5)429 S--C.sub.2 H.sub.5 NH.sub.2 CH.dbd.C(CN)(NO.sub.2)430 S-nC.sub.4 H.sub.9 NH.sub.2 CH.dbd.C(CN)(NO.sub.2)431 S-nC.sub.6 H.sub.13 NH.sub.2 CH.dbd.C(CN)(CONH.sub.2)432 S--C.sub.6 H.sub.5 NH.sub.2 CH.dbd.C(CN)(CONH.sub.2)433 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CH.dbd.C(CN)(CONH.sub. 2)434 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 CH.dbd.C(CN)(CONH.sub.2)435 S--C.sub.2 H.sub.5 NH.sub.2 C(CH.sub.3).dbd.C(CN).sub.2436 S-nC.sub.4 H.sub.9 NH.sub.2 C(CH.sub.3).dbd.C(CN)(NO.sub.2)437 S-nC.sub.6 H.sub.13 NH.sub.2 C(C.sub.6 H.sub.5).dbd.C(CN).sub.2438 S--C.sub.6 H.sub.5 NH.sub.2 C(C.sub.6 H.sub.5).dbd.C(CN).sub.2439 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 C(C.sub.6 H.sub.5).dbd.C(CN).sub.2440 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 C(C.sub.6 H.sub.5).dbd.C(CN).sub.2441 S--C.sub.6 H.sub.4 -p-CH.sub.3 NH.sub.2 CHO 204.5-205442 S--C.sub.2 H.sub.5 NH.sub.2 CO-Morpholino443 S-nC.sub.4 H.sub.9 NH.sub.2 CO-Morpholino444 S-nC.sub.6 H.sub.13 NH.sub.2 CO-Morpholino445 S--C.sub.6 H.sub.5 NH.sub.2 CO-Morpholino446 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CO-Morpholino447 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 CO-Morpholino448 S--C.sub.2 H.sub.5 NH.sub.2 CO-Piperidino449 S-nC.sub.4 H.sub.9 NH.sub.2 CO-Piperidino450 S-nC.sub.6 H.sub.13 NH.sub.2 CO-Piperidino451 S--C.sub.6 H.sub.5 NH.sub.2 CO-Piperidino452 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CO-Piperidino453 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 CO-Piperidino454 S--C.sub.2 H.sub.5 NH.sub.2 CO-Pyrrolidino455 S-nC.sub.4 H.sub.9 NH.sub.2 CO-Pyrrolidino456 S-nC.sub.6 H.sub.13 NH.sub.2 CO-Pyrrolidino457 S--C.sub.6 H.sub.5 NH.sub.2 CO-Pyrrolidino458 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CO-Pyrrolidino459 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 CO-Pyrrolidino460 S--C.sub.2 H.sub.5 NH.sub.2 CO-Thiomorpholino461 S-nC.sub.4 H.sub.9 NH.sub.2 CO-Thiomorpholino462 S-nC.sub.6 H.sub.13 NH.sub.2 CO-Thiomorpholino463 S--C.sub.6 H.sub.5 NH.sub.2 CO-hexamethyleneimino464 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CO-hexamethyleneimino465 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 CO-hexamethyleneimino466 S--C.sub.2 H.sub.5 NH.sub.2 CO--(N-Methyl-piperazino)467 S-nC.sub.4 H.sub.9 NH.sub.2 CO--(N-Methyl-piperazino)468 S-nC.sub.6 H.sub.13 NH.sub.2 CO--(N-Ethyl-piperazino)469 S--C.sub.6 H.sub.5 NH.sub.2 CO--(N-Ethyl-piperazino)470 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CO--(N-Ethyl-piperazino)471 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 CO--(N-Ethyl-piperazino)472 S--C.sub.2 H.sub.5 NH.sub.2 COO-Cyclopropyl473 S-nC.sub.4 H.sub.9 NH.sub.2 COO-Cyclopropyl474 S-nC.sub.6 H.sub.13 NH.sub.2 COO-Cyclopentyl475 S--C.sub.6 H.sub.5 NH.sub.2 COO-Cyclopentyl476 S--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 COO-Cyclohexyl477 SO.sub.2 --C.sub.6 H.sub.5 NH.sub.2 COO-Cyclohexyl__________________________________________________________________________
EXAMPLE 478
8.1 g of 2-amino-4-chloro-5-formylthiazole were dissolved in 40 ml of N,N-dimethylformamide and, at 35.degree. to 40.degree. C., 9.9 ml of piperidine were added dropwise. The reaction mixture was then stirred at room temperature for 4 hours and subsequently poured into 150 ml of ice-water. The precipitate was filtered off with suction, washed with water and dried at 50.degree. C. under reduced pressure. 6.3 g (60% of theory) of the compound of the formula ##STR28## were obtained of melting point 160.degree. C. (decomposition). The NMR, IR, UV and mass spectra and the elemental analysis are consistent with the indicated structure.
EXAMPLE 479
8 g of 2-amino-4-chloro-5-cyanothiazole were dissolved in 50 ml of N,N-dimethylformamide and, at 35.degree. C., 7.9 ml of 70% by weight aqueous ethylamine solution were added dropwise. The reaction mixture was stirred at room temperature for 1 hour and then a further 1 ml of 70% by weight aqueous ethylamine solution was added. The reaction mixture was stirred at room temperature for a further 0.5 hour and then poured into 400 ml of ice-water and 5 ml of hydrochloric acid (M 100). The precipitate was filtered off with suction, washed with water and dried at 50.degree. C. under reduced pressure. 4.0 g (48% of theory of the compound of the formula ##STR29## were obtained of melting point 171.degree.-174.degree. C. The NMR, IR, UV and mass spectra and the elemental analysis are consistent with the structure indicated above.
The compounds of the formula ##STR30## which are listed in Table 2 which follows can be prepared in a similar manner.
TABLE 2__________________________________________________________________________ MeltingExample pointno. R.sup.3 NR.sup.1 R.sup.2 R.sup.4 (.degree.C.)__________________________________________________________________________480 NH--CH.sub.3 NH.sub.2 CN481 NH-nC.sub.3 H.sub.7 NH.sub.2 CN 121-23482 NH-isoC.sub.3 H.sub.7 NH.sub.2 CN 134-36483 NH-nC.sub.4 H.sub.9 NH.sub.2 CN484 NH-secC.sub.4 H.sub.9 NH.sub.2 CN485 NH-isoC.sub.4 H.sub.9 NH.sub.2 CN 203-05486 NH-tertC.sub.4 H.sub.9 NH.sub.2 CN 152-53487 NH-nC.sub.5 H.sub.11 NH.sub.2 CN488 NH-isoC.sub.5 H.sub.11 NH.sub.2 CN489 NH--CH(CH.sub.3)--CH(CH.sub.3).sub.2 NH.sub.2 CN490 NH-neoC.sub.5 H.sub.11 NH.sub.2 CN 117-19491 NH-nC.sub.6 H.sub.13 NH.sub.2 CN492 NH-nC.sub.7 H.sub.15 NH.sub.2 CN493 NH-nC.sub.8 H.sub.17 NH.sub.2 CN494 NH-nC.sub.9 H.sub.19 NH.sub.2 CN495 NH-nC.sub.10 H.sub.21 NH.sub.2 CN496 NH-nC.sub.12 H.sub.25 NH.sub.2 CN497 NH-nC.sub.13 H.sub.27 NH.sub.2 CN498 NH-nC.sub.16 H.sub.33 NH.sub.2 CN499 NH-nC.sub.18 H.sub.37 NH.sub.2 CN500 NH--CH(CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.3 NH.sub.2 CN501 NH--CH(CH.sub.3)--(CH.sub.2).sub.3 CH.sub.3 NH.sub.2 CN502 NH--CH(CH.sub.3)--(CH.sub.2).sub.2 --CH(CH.sub.3).sub.2 NH.sub.2 CN503 NH--CH(CH.sub.3)--(CH.sub.2).sub.5 --CH.sub.3 NH.sub.2 CN504 NH--CH(C.sub.2 H.sub.5)--(CH.sub.2).sub.4 --CH.sub.3 NH.sub.2 CN505 NH--CH(CH.sub.3)--(CH.sub.2).sub.3 --CH(CH.sub.3).sub.2 NH.sub.2 CN506 (R)--(-)--NH--CH(CH.sub.3)-Cyclohexyl NH.sub.2 CN507 (S)--(+)--NH--CH(CH.sub.3)-Cyclohexyl NH.sub.2 CN508 NH--CH.sub.2 CH.sub.2 -Cyclohexyl NH.sub.2 CN509 NH--(CH.sub.2).sub.2 --OH NH.sub.2 CN510 NH--(CH.sub.2).sub.2 --OCH.sub.3 NH.sub.2 CN511 NH--(CH.sub.2).sub.2 --OC.sub.2 H.sub.5 NH.sub.2 CN512 NH--(CH.sub.2).sub.2 --OC.sub.6 H.sub.5 NH.sub.2 CN513 NH--(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2 OH NH.sub.2 CN514 NH--(CH.sub.2).sub.2 --NH--(CH.sub.2).sub.2 OH NH.sub.2 CN515 NH--(CH.sub.2).sub.2 --NH.sub.2 NH.sub.2 CN516 NH--(CH.sub.2).sub.2 --N(CH.sub.3).sub.2 NH.sub.2 CN517 NH--(CH.sub.2).sub.2 --N(C.sub.2 H.sub.5).sub.2 NH.sub.2 CN518 NH--(CH.sub.2).sub.2 --N(iso-C.sub.3 H.sub.7).sub.2 NH.sub.2 CN519 NH--(CH.sub.2).sub.2 -Piperazino NH.sub.2 CN520 NH--(CH.sub.2).sub.3 OH NH.sub.2 CN521 NH--(CH.sub.2).sub.3 OCH.sub.3 NH.sub.2 CN522 NH--(CH.sub.2).sub.3 OC.sub.2 H.sub.5 NH.sub.2 CN523 NH--(CH.sub.2).sub.3 --OCH(CH.sub.3).sub.2 NH.sub.2 CN524 NH--(CH.sub.2).sub.3 --OC.sub.6 H.sub.5 NH.sub.2 CN525 NH--(CH.sub.2).sub.3 --O--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CN526 NH--(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--CH.sub.3 NH.sub.2 CN527 NH--(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2 --O--C.sub.2 H.sub. NH.sub.2 CN528 NH--(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub.6 H.sub.5 NH.sub.2 CN529 NH--(CH.sub.2).sub.3 --NH.sub.2 NH.sub.2 CN530 NH--(CH.sub.2).sub.3 --N(CH.sub.3).sub.2 NH.sub.2 CN531 NH--(CH.sub.2).sub.3 --N(C.sub.2 H.sub.5).sub.2 NH.sub.2 CN532 NH--(CH.sub.2).sub.3 --N(n-C.sub.4 H.sub.9).sub.2 NH.sub.2 CN533 NH--(CH.sub.2).sub.3-Morpholino NH.sub.2 CN534 NH--(CH.sub.2).sub.4--OH NH.sub.2 CN535 NH--(CH.sub.2).sub.5--NH.sub.2 NH.sub.2 CN536 NH--(CH.sub.2).sub.6--OH NH.sub.2 CN537 NH--(CH.sub.2).sub.6--NH.sub.2 NH.sub.2 CN538 NH--(CH.sub.2).sub.7--NH.sub.2 NH.sub.2 CN539 NH--(CH.sub.2).sub.8--NH.sub.2 NH.sub.2 CN540 NH--(CH.sub.2).sub.9--NH.sub.2 NH.sub.2 CN541 NH--(CH.sub.2).sub.10--NH.sub.2 NH.sub.2 CN542 NH--(CH.sub.2).sub.12--NH.sub.2 NH.sub.2 CN543 NH--CH(CH.sub.3)--(CH.sub.2).sub.3 --N(C.sub. 2 H.sub.5).sub.2 .times. HCl NH.sub.2 CN544 NH--(CH.sub.2)--CH(CH.sub.3)--OH NH.sub.2 CN545 NH--CH(CH.sub.3)--CH.sub.2 --OH NH.sub.2 CN546 NH--CH.sub.2 -2-Thienyl NH.sub.2 CN547 NH--C(CH.sub.3).sub.2 --CH.sub.2 --OH NH.sub.2 CN548 NH--C(CH.sub.3)--(CH.sub.2 --OH).sub.2 NH.sub.2 CN549 NH--CH(C.sub.2 H.sub.5)--CH.sub.2 --OH NH.sub.2 CN550 NH--(CH.sub.2).sub.2 --COOH NH.sub.2 CN551 NH--(CH.sub.2).sub.5 --COOH NH.sub.2 CN552 NH--(CH.sub.2).sub.10 --COOH NH.sub.2 CN553 NH--C.sub.6 H.sub.5 NH.sub.2 CN554 NH--C.sub.6 H.sub.4 -(2)-CH.sub.3 NH.sub.2 CN555 NH--C.sub.6 H.sub.4 -(3)-CH.sub.3 NH.sub.2 CN556 NH--C.sub.6 H.sub.4 -(4)-CH.sub.3 NH.sub.2 CN557 NH--C.sub.6 H.sub.5 -(2)-C.sub.2 H.sub.5 NH.sub.2 CN558 NH--C.sub.6 H.sub.4 -(4)-C.sub.2 H.sub.5 NH.sub.2 CN559 NH--C.sub.6 H.sub.4 -(2)-CF.sub.3 NH.sub.2 CN560 NH--C.sub. 6 H.sub.4 -(3)-CF.sub.3 NH.sub.2 CN561 NH--C.sub.6 H.sub.4 -(4)-CF.sub.3 NH.sub.2 CN562 NH--C.sub.6 H.sub.5 -(2)-OH NH.sub.2 CN563 NH--C.sub.6 H.sub.5 -(3)-OH NH.sub.2 CN564 NH--C.sub.6 H.sub.5 -(4)-OH NH.sub.2 CN565 NH--C.sub.6 H.sub.4 -(2)-OCH.sub.3 NH.sub.2 CN566 NH--C.sub.6 H.sub.4 -(3)-OCH.sub.3 NH.sub.2 CN567 NH--C.sub.6 H.sub.4 -(4)-OCH.sub.3 NH.sub.2 CN568 NH--C.sub.6 H.sub.4 -(2)-OC.sub.2 H.sub.5 NH.sub.2 CN569 NH--C.sub.6 H.sub.4 -(3)-OC.sub.2 H.sub.5 NH.sub.2 CN570 NH--C.sub.6 H.sub.4 -(4)-OC.sub.2 H.sub.5 NH.sub.2 CN571 NH--C.sub.6 H.sub.4 -(2)-Cl NH.sub.2 CN572 NH--C.sub.6 H.sub.4 -(3)-Cl NH.sub.2 CN573 NH--C.sub.6 H.sub.4 -(4)-Cl NH.sub.2 CN574 NH--C.sub.6 H.sub.4 -(2)-F NH.sub.2 CN575 NH--C.sub.6 H.sub.4 -(3)-F NH.sub.2 CN576 NH--C.sub.6 H.sub.4 -(4)-F NH.sub.2 CN577 NH--C.sub.6 H.sub.4 -(2)-Br NH.sub.2 CN578 NH--C.sub.6 H.sub.4 -(3)-Br NH.sub.2 CN579 NH--C.sub.6 H.sub.4 -(4)-Br NH.sub.2 CN580 NH--C.sub.6 H.sub.4 -(2)-I NH.sub.2 CN581 NH--C.sub.6 H.sub.4 -(3)-I NH.sub.2 CN582 NH--C.sub.6 H.sub.4 -(4)-I NH.sub.2 CN583 NH--C.sub.6 H.sub.4 -(2)-NH.sub.2 NH.sub.2 CN584 NH--C.sub.6 H.sub.4 -(3)-NH.sub.2 NH.sub.2 CN585 NH--C.sub.6 H.sub.4 -(4)-NH.sub.2 NH.sub.2 CN586 NH--C.sub.6 H.sub.4 -(4)-NH--COCH.sub.3 NH.sub.2 CN587 NH--C.sub.6 H.sub.4 -(2)-CH.sub.2 OH NH.sub.2 CN588 NH--C.sub.6 H.sub.4 -(3)-CH.sub.2 OH NH.sub.2 CN589 NH--C.sub.6 H.sub.4 -(4)-COCH.sub.3 NH.sub.2 CN590 NH--C.sub.6 H.sub.4 -(2)-COOH NH.sub.2 CN591 NH--C.sub.6 H.sub.4 -(3)-COOH NH.sub.2 CN592 NH--C.sub.6 H.sub.4 -(4)-COOH NH.sub.2 CN593 NH--C.sub.6 H.sub.4 -(2)-CONH.sub.2 NH.sub.2 CN594 NH--C.sub.6 H.sub.4 -(4)-CONH.sub.2 NH.sub.2 CN595 NH--C.sub.6 H.sub.4 -(2)-CN NH.sub.2 CN596 NH--C.sub.6 H.sub.4 -(3)-CN NH.sub.2 CN597 NH--C.sub.6 H.sub.4 -(4)-CN NH.sub.2 CN598 NH--C.sub.6 H.sub.3 -(2,6)-(CH.sub.3).sub.2 NH.sub.2 CN599 NH--C.sub.6 H.sub.3 -(3,5)-(CH.sub.3).sub.2 NH.sub.2 CN600 NH--C.sub.6 H.sub.3 -(2)-OH-(5)-CH.sub.3 NH.sub.2 CN601 NH--C.sub.6 H.sub.3 -(2)-OH-(4)-CH.sub.3 NH.sub.2 CN602 NH--C.sub.6 H.sub.3 -(2)-OH-(2)-CH.sub.3 NH.sub.2 CN603 NH--C.sub.6 H.sub.3 -(2)-OH-(5)-Cl NH.sub.2 CN604 NH-2-Pyridyl NH.sub.2 CN605 NH-3-Pyridyl NH.sub.2 CN606 NH-4-Pyridyl NH.sub.2 CN607 NH--CH.sub.2 -3-Pyridyl NH.sub.2 CN NH--CH.sub.2 -2-Furyl NH.sub.2 CN608 NH--CH.sub.2 --C.sub.6 H.sub.5 NH.sub.2 CN 119-22609 NH--CH.sub.2 --C.sub.6 H.sub.4 -(2)-OCH.sub.3 NH.sub.2 CN610 NH--CH.sub.2 --C.sub.6 H.sub.4 -(4)-OCH.sub.3 NH.sub.2 CN611 NH--CH.sub.2 --C.sub.6 H.sub.4 -(4)-F NH.sub.2 CN612 NH--CH.sub.2 --C.sub.6 H.sub.4 -(2)-Cl NH.sub.2 CN613 NH--CH.sub.2 --C.sub.6 H.sub.4 -(4)-Cl NH.sub.2 CN614 NH--CH.sub.2 --C.sub.6 H.sub.3 -(3,4)-(OCH.sub.3).sub.2 NH.sub.2 CN615 NH--CH.sub. 2 --CH.sub.2 --C.sub.6 H.sub.5 NH.sub.2 CN616 NH--CH(CH.sub.3)--C.sub.6 H.sub.5 (+/-) NH.sub.2 CN617 NH--(CH.sub.2).sub.3 --C.sub.6 H.sub.5 NH.sub.2 CN618 NH--CH(CH.sub.3)--(CH.sub.2).sub.2 --C.sub.6 H.sub.5 NH.sub.2 CN619 NH-Cyclopropyl NH.sub.2 CN620 NH-Cyclopentyl NH.sub.2 CN621 NH-Cyclohexyl NH.sub.2 CN622 NH-Cycloheptyl NH.sub.2 CN623 NH-Cyclooctyl NH.sub.2 CN624 NH-Cyclododecyl NH.sub.2 CN625 NH--CH.sub.2 --CH.dbd.CH.sub.2 NH.sub.2 CN626 NH--CH.sub.2 --C.tbd.CH NH.sub.2 CN627 N(CH.sub.3).sub.2 NH.sub.2 CN628 N(C.sub.2 H.sub.5).sub.2 NH.sub.2 CN629 N(n-C.sub.3 H.sub.7).sub.2 NH.sub.2 CN630 N(n-C.sub.4 H.sub.9).sub.2 NH.sub.2 CN631 N(iso-C.sub.4 H.sub.9).sub.2 NH.sub.2 CN632 N(n-C.sub.5 H.sub.11).sub.2 NH.sub.2 CN633 N(sec-C.sub.4 H.sub.9).sub.2 NH.sub.2 CN634 N(iso-C.sub.5 H.sub.11).sub.2 NH.sub.2 CN635 N(n-C.sub.6 H.sub.13).sub.2 NH.sub.2 CN636 N(CH(C.sub.2 H.sub.5)--(CH.sub.2).sub.4 --CH.sub.3).sub.2 NH.sub.2 CN637 N(n-C.sub.8 H.sub.17).sub.2 NH.sub.2 CN638 N(CH.sub.2 --CH.dbd.CH.sub.2).sub.2 NH.sub.2 CN639 N(Cyclohexyl).sub.2 NH.sub.2 CN640 N(CH.sub.3)-nC.sub.4 H.sub.9 NH.sub.2 CN641 N(CH.sub.3)-Cyclohexyl NH.sub.2 CN642 N(C.sub.2 H.sub.5)-Cyclohexyl NH.sub.2 CN643 N(CH.sub.3)--(CH.sub.2).sub.2 --OH NH.sub.2 CN644 N(C.sub.2 H.sub.5)--CH(CH.sub.3)--CH(CH.sub.3).sub.2 NH.sub.2 CN645 N(C.sub.2 H.sub.5)--(CH).sub.2 --OH NH.sub.2 CN646 N(C.sub.2 H.sub.5)--CH.sub.2 --CH(OH)--CH.sub.3 NH.sub.2 CN647 N(tert-C.sub.4 H.sub.9)--(CH.sub.2).sub.2 --OH NH.sub.2 CN648 N(CH.sub.3)--C.sub.6 H.sub.5 NH.sub.2 CN649 N(C.sub.2 H.sub.5)--C.sub.6 H.sub.5 NH.sub.2 CN650 N(iso-C.sub.3 H.sub.7)--C.sub.6 H.sub.5 NH.sub.2 CN651 N(nC.sub.4 H.sub.9)--C.sub.6 H.sub.5 NH.sub.2 CN652 N(CH.sub.2 C.sub.6 H.sub.5).sub.2 NH.sub.2 CN653 N(CH.sub.3)--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CN654 N(C.sub.2 H.sub.5)--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CN655 N(iso-C.sub.3 H.sub.7)--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CN656 N(tert-C.sub.4 H.sub.9)--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CN657 N(CH.sub.2 C.sub.6 H.sub.5)--(CH.sub.2).sub.2 --)OH NH.sub.2 CN658 N(C.sub.6 H.sub.5)--CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CN659 N(CH.sub.2 C.sub.6 H.sub.5)--((CH.sub.2).sub.2 --C.sub.6 H.sub.5) NH.sub.2 CN660 Pyrrolidino NH.sub.2 CN661 Hexamethyleneimino NH.sub.2 CN662 N-Methylpiperazino NH.sub.2 CN663 NH--NH.sub.2 NH.sub.2 CN664 NH--NH--CH.sub.3 NH.sub.2 CN665 NH--NH--C.sub.6 H.sub.5 NH.sub.2 CN666 NH--N(CH.sub.3).sub.2 NH.sub.2 CN667 NH--OH NH.sub.2 CN668 NH--CH.sub.3 NH.sub.2 CHO669 NH--C.sub.2 H.sub.5 NH.sub.2 CHO670 NH-nC.sub.3 H.sub.7 NH.sub.2 CHO671 NH-isoC.sub.3 H.sub.7 NH.sub.2 CHO672 NH-secC.sub.4 H.sub.9 NH.sub.2 CHO673 NH-nC.sub.5 H.sub.11 NH.sub.2 CHO674 NH-Cyclohexyl NH.sub.2 CHO675 NH--C.sub.6 H.sub.5 NH.sub.2 CHO676 N(C.sub.2 H.sub.5).sub.2 NH.sub.2 CHO677 NH--CH.sub.3 N.dbd.CH--N(CH.sub.3).sub.2 CN678 NH--C.sub.2 H.sub.5 N.dbd.CH--N(CH.sub.3).sub.2 CN679 NH--CH.sub.3 NH.sub.2 CH.dbd.C(CN).sub.2680 NH--C.sub.2 H.sub.5 NH.sub.2 CH.dbd.C(CN).sub.2681 NH-nC.sub.3 H.sub.7 NH.sub.2 CH.dbd.C(CN).sub.2682 NH-nC.sub.4 H.sub.9 NH.sub.2 CH.dbd.C(CN).sub.2683 NH-secC.sub.4 H.sub.9 NH.sub.2 CH.dbd.C(CN).sub.2684 NH-nC.sub.6 H.sub.13 NH.sub.2 CH.dbd.C(CN).sub.2685 NH-nC.sub.7 H.sub.15 NH.sub.2 CH.dbd.C(CN).sub.2686 NH--C.sub.2 H.sub.4 --OH NH.sub.2 CH.dbd.C(CN).sub.2687 NH--C.sub.2 H.sub.4 --OCH.sub.3 NH.sub.2 CH.dbd.C(CN).sub.2688 NH-Cyclohexyl NH.sub.2 CH.dbd.C(CN).sub.2689 NH--C.sub.6 H.sub.5 NH.sub.2 CH.dbd.C(CN).sub.2690 NH--C.sub.6 H.sub.4 -(3)-CH.sub.3 NH.sub.2 CH.dbd.C(CN).sub.2691 NH--CH.sub.2 --C.tbd.CH NH.sub.2 CH.dbd.C(CN).sub.2692 NH(CH.sub.3).sub.2 NH.sub.2 CH.dbd.C(CN).sub.2693 Pyrrolidino NH.sub.2 CH.dbd.C(CN).sub.2694 Piperidino NH.sub.2 CH.dbd.C(CN).sub.2695 Morpholino NH.sub.2 CH.dbd.C(CN).sub.2696 NH--NH.sub.2 NH.sub.2 CH.dbd.C(CN).sub.2697 NH-nC.sub.3 H.sub.7 NH.sub.2 CH.dbd.C(CN) (COOCH.sub.3)698 NH-nC.sub.4 H.sub.9 NH.sub.2 CH.dbd.C(CN) (COOCH.sub.3)699 NH-secC.sub.4 H.sub.9 NH.sub.2 CH.dbd.C(CN) (COOCH.sub.3)700 NH-nC.sub.5 H.sub.11 NH.sub.2 CH.dbd.C(CN) (COOC.sub.2 H.sub.5)701 N(C.sub.2 H.sub.5).sub.2 NH.sub.2 CH.dbd.C(CN) (COOC.sub.2 H.sub.5)702 NH--CH.sub.3 NH.sub.2 CH.dbd.C(CN) (NO.sub.2)703 NH-isoC.sub.3 H.sub.7 NH.sub.2 CH.dbd.C(CN) (NO.sub.2)704 (R/S)--NH--CH(CH.sub.3)-Cyclohexyl NH.sub.2 CN705 NH--(CH.sub.2).sub.3 --N(n-C.sub.3 H.sub.7).sub.2 NH.sub.2 CN706 NH--(CH.sub.2).sub.3 --N(iso-C.sub.3 H.sub.7).sub.2 NH.sub.2 CN707 NH--(+)--CH(CH.sub.3)--C.sub.6 H.sub.5 NH.sub.2 CN708 NH--(-)--CH(CH.sub.3)--C.sub.6 H.sub.5 NH.sub.2 CN709 NH-Cyclobutyl NH.sub.2 CN710 NH-Adamantyl NH.sub.2 CN711 NH-Cyclononyl NH.sub.2 CN712 NH-Cyclodecyl NH.sub.2 CN713 NH-Methallyl NH.sub.2 CN714 N(isoC.sub.3 H.sub.7).sub.2 NH.sub.2 CN715 N-Ethylpiperazino NH.sub.2 CN716 Thiomorpholino NH.sub.2 CN717 NH--NH--C.sub.2 H.sub.5 NH.sub.2 CN718 NH--N(C.sub.2 H.sub.5).sub.2 NH.sub.2 CN719 N(CH.sub.3)--NH--CH.sub.3 NH.sub.2 CN720 1-Imidazolyl NH.sub.2 CN721 1-Pyrazolyl NH.sub.2 CN722 NH--CH(CH.sub.3)--(CH.sub.2).sub.4 CH.sub.3 NH.sub.2 CN723 Pyrrolidino NH.sub.2 CHO 174--176__________________________________________________________________________

Number	Date	Country	Kind
3942581	Dec 1989	DEX
4029732	Sep 1990	DEX

Number	Date	Country
160818	Nov 1985	EPX
963847	Jul 1950	FRX

Aminothiazoles

Information

Patent Number

Date Filed

Date Issued

Inventors

Original Assignees

Examiners

Agents

CPC

US Classifications

Field of Search

US

International Classifications

Abstract

Description

Claims

Priority Claims (2)

Parent Case Info

US Referenced Citations (1)

Foreign Referenced Citations (2)

Non-Patent Literature Citations (4)

Continuation in Parts (1)

Entry
Tetrahedron Letters. Bd. 28, Nr. 1, 1981, Oxford GB Seiten 117-120; Robert G. Guy et al: `Reactions of alpha-thiocyanato-beta-dicarbonyl compounds: a C-S-C+ C-N Route to thiazoles` "Insgesamt".
Tetrahedron Letters. Bd. 22, Nr. 24, 1981, Oxford GB Seiten 2285-2288; Masataka Yokohama et al: "Diaminothiazoles and Diaminothiophenes'Insgesamt".
Tetrahedron Letters, vol. 22, No. 24, pp. 2285-2288, 1981, M. Yokoyama, et al, "Diaminothiazoles and Diaminothiophenes".
Tetrahedron Letter, vol. 28, No. 1, pp. 117-120, 1987, R. G. Guy, et al., "Reactions of .alpha.-Thiocyanato-.beta.-Dicarbonyl Compounds: A C-S-C+ C-N Route to Thiazoles".