Diaminothiophenes

Abstract

Diaminothiophenes of the formula ##STR1## or tautomers thereof, where R.sup.1 and R.sup.2 are each hydrogen or together are ##STR2## where T.sup.1 is hydrogen, alkyl or phenyl, T.sup.2 and T.sup.3 are, independently of one another, alkyl or phenyl, or T.sup.2 and T.sup.3 together with the nitrogen linking them are a heterocyclic radical,R.sup.3 is substituted amino andR.sup.4 is alkanoyl, benzoyl, cyano, nitro or ##STR3## where T.sup.4 is hydrogen, alkyl or phenyl and T.sup.5 is the radical of a primary amine or of an active methylene compound,are prepared as described. The present diaminothiophene compound is useful in the synthesis of dyes, crop protection agents and pharmaceuticals.

Description

The present invention relates to novel diaminothiophenes of the formula I ##STR4## or tautomers thereof, where R.sup.1 and R.sup.2 are each hydrogen or together are ##STR5## where T.sup.1 is hydrogen, C.sub.1 -C.sub.4 -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.4 -alkyl, C.sub.5 -C.sub.7 -cycloalkyl or phenyl or T.sup.2 and T.sup.3 together with the nitrogen linking them are a 5- to 7-membered saturated heterocyclic radical which can contain further hetero atoms,

R.sup.3 is C.sub.1 -C.sub.20 -mono- or dialkylamino, C.sub.2 -C.sub.10 -mono- or dialkylamino whose alkyl is substituted and/or interrupted by one or more oxygens, C.sub.3 -C.sub.8 -cycloalkylamino, adamantylamino, C.sub.2 -C.sub.12 -mono- or dialkenylamino, 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, C.sub.1 -C.sub.4 -mono- or dialkylhydrazino or phenylhydrazino and R.sup.4 is C.sub.1 -C.sub.6 -alkanoyl, benzoyl, cyano, nitro or ##STR6## where T.sup.4 is hydrogen, C.sub.1 -C.sub.4 -alkyl or phenyl, and T.sup.5 is the radical of an active methylene compound, or hydroxyimino or N-X where X is C.sub.1 -C.sub.20 -alkyl which can be substituted and/or interrupted by one or more oxygens, substituted or unsubstituted C.sub.3 -C.sub.6 -alkenyl, substituted or unsubstituted C.sub.3 -C.sub.6 -alkynyl, substituted or unsubstituted C.sub.3 -C.sub.10 -cycloalkyl, substituted or unsubstituted phenyl, pyridyl, C.sub.1 -C.sub.4 -alkoxycarbonylmethyl, amino, C.sub.1 -C.sub.4 -dialkylamino or phenylamino.

2,4-Diaminothiophene derivatives which have a substituted amino in position 2 and an unsubstituted amino in position 4 have been disclosed (see, for 10 example, J. Prakt. Chem. 326 (1986) 459 to 464; J. Chem. Soc. Perkin Trans. I (1986) 1171 to 1179 or Monatsh. Chem. 112 (1981) 1391 to 1404). Furthermore, CH-A 583,224 describes the preparation of 2,4-diamino-3,5-dicyanothiophene. The said diaminothiophenes are, however, not especially suitable diazo components for the preparation of azo dyes.

The object of the present invention was to prepare novel diaminothiophenes which have an unsubstituted amino in position 2 and a substituted amino in position 4.

In accordance with this, we have found the diaminothiophenes of the formula I defined above.

All the alkyls and alkenyls in the abovementioned formula I can be both straight-chain and branched.

When alkyls which are interrupted by one or more oxygens occur in the formula I, they are preferably interrupted by 1 to 3, in particular 1 or 2, oxygens.

Examples of suitable substituents for phenyls in the formula I are C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, halogen, in particular chlorine or bromine, nitro, hydroxyl, amino, C.sub.1 -C.sub.4 -dialkylamino, carboxyl or C.sub.1 -C.sub.4 -alkanoyl.

Examples of suitable substituents for alkyls in the formula I are C.sub.1 -C.sub.5 -alkylthio, substituted or unsubstituted phenoxy, halogen, in particular chlorine or bromine, hydroxyl, amino, C.sub.1 -C.sub.4 -mono- or dialkylamino, pyrrolidino, piperidino, morpholino, thiomorpholino, piperazino, N-(C.sub.1 -C.sub.4 -alkyl)piperazino, C.sub.1 -C.sub.5 -alkoxycarbonyl or substituted or unsubstituted phenyl.

Examples of suitable substituents for alkenyls, alkynyls or cycloalkyls in the formula I are fluorine, chlorine or bromine.

When T.sup.2 and T.sup.3 together with the nitrogen linking them are a 5- to 7-membered saturated heterocyclic radical which can contain further hetero atoms, suitable 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.4 are methyl, ethyl, propyl, isopropyl, butyl, isobutyl or sec-butyl.

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 in the oxo synthesis (cf. Ullmanns Encyklopadie der technischen Chemie, 4th edition, volume 7, pages 215 to 217, and volume 11, pages 435 and 436.)

--NX is derived from primary amines of the formula H.sub.2 NX. Examples of these which may be mentioned 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, 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-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.

T.sup.5 is derived from, for example, active methylene compounds of the formula H.sub.2 T.sup.5. Compounds of this type have, for example, the formula ##STR7## 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 C.sub.1 -C.sub.4 -mono- or dialkylcarbamoyl, or the formulae ##STR8##

Examples of some particularly important compounds are: ##STR9##

Examples of R.sup.3 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, allylamino, propargylamino, methallylamino, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cycloheptylamino, cyclooctylamino, cyclononylamino, cyclodecylamino, 2-hydroxyethylamino, 2-methoxyethylamino, 2-ethoxyethylamino, 2-benzyloxyethylamino, 3-hydroxypropylamino, 3-methoxypropylamino, 3-ethoxypropylamino, 3-(2-phenoxyethoxy)propylamino, 3-benzyloxypropylamino, 2-aminoethylamino, 2-(N,N-dimethylamino)ethylamino, 2-(N,N-diethylamino)ethylamino, 3-(N,N-dimethylamino)propylamino, 3-(N,N-diethylamino)propylamino, benzylamino, 2-phenylethylamino, 1-phenylethylamino, phenylamino, 2-hydroxyphenylamino, 3-hydroxyphenylamino, 4-hydroxyphenylamino, 2-methoxyphenylamino, 3-methoxyphenylamino, 4-methoxyphenylamino, 2-ethoxyphenylamino, 3-ethoxyphenylamino,4-ethoxyphenylamino,2-chlorophenylamino, 3-chlorophenylamino, 4-chlorophenylamino, 2-nitrophenylamino, 3-nitrophenylamino, 4-nitrophenylamino, 2-aminophenylamino, 3-aminophenylamino, 4-aminophenylamino, 2-methylphenylamino, 3-methylphenylamino, 4-methylphenylamino, 2-ethylphenylamino, 3-ethylphenylamino, 4-ethylphenylamino, 2-pyridylamino, 3-pyridylamino, 4-pyridylamino, methoxycarbonylmethylamino, ethoxycarbonylmethylamino, propoxycarbonylmethylamino, butoxycarbonylmethylamino, 2-methoxycarbonylmethylamino, 2-ethoxycarbonylmethylamino, 2-propoxycarbonylmethylamino, 2-butoxycarbonylmethylamino, 2-(3,4-dichlorophenyl)ethylamino, 2-(3-chloro-2-methylphenyl)ethylamino, 2-(3,4-dimethoxyphenyl)ethylamino, 2-(2-chlorophenyl)ethylamino, 2-thienylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, diallylamino, N-methyl-N-butylamino, N-methyl-N-phenylamino, N-methyl-N-benzylamino, N-ethyl-N-benzylamino, 3-morpholinopropylamino, 2-(1-piperazinyl)ethylamino, phenoxyethylamino, phenoxypropylamino, 2-methylthioethylamino, 3-methylthiopropylamino, 2-ethylthioethylamino, 3-ethylthiopropylamino, 2-aminoethylamino, 3-aminopropylamino, 2-dimethylaminoethylamino, 3-dimethylaminopropylamino, 2-diethylaminoethylamino, 3-diethylaminopropylamino, diethanolamino, N-ethyl-N-phenylamino, dibenzylamino, N-methylpiperazino, 2-pyrrolidinoethylamino, 2-piperidinoethylamino, 2-morpholinoethylamino, 2-thiomorpholinoethylamino, 2-hexamethyleneiminoethylamino, 2-(N-methylpiperazino)ethylamino, hydrazino, N-methylhydrazino, N-ethylhydrazino, phenylhydrazino, N,N-dimethylhydrazino, N,N-diethylhydrazino, N,N'-dimethylhydrazino, N,N'-diethylhydrazino, N,N-dipropylhydrazino, N,N-dibutylhydrazino, 1-imidazolyl, 1-pyrazolyl, 2,4-dimethylphenylamino, 3-dimethylaminophenylamino, 4-cyanophenylamino, 2-carboxyphenylamino, 4-acetylphenylamino or 2,4-dichlorophenylamino.

Preferred diaminothiophenes of the formula I are those in which

R.sup.1 and R.sup.2 are each hydrogen or together are ##STR10## where T.sup.1 is hydrogen, C.sub.1 -C.sub.4 -alkyl or phenyl, and T.sup.2 and T.sup.3 are, independently of one another, C.sub.1 -C.sub.4 -alkyl or phenyl, or together with the nitrogen linking them are 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 have the abovementioned meanings.

Particularly preferred diaminothiophenes of the formula I are those in which R.sup.1 and R.sup.2 are each hydrogen or together are ##STR11## where T.sup.1 is hydrogen and T.sup.2 and T.sup.3 are, independently of one another, C.sub.1 -C.sub.4 -alkyl.

Further particularly preferred diaminothiophenes of the formula I are those in which

R.sup.4 is formyl, acetyl, propionyl, butyryl, benzoyl, cyano, nitro or ##STR12## where T.sup.4 is hydrogen, methyl, ethyl or phenyl, and T.sup.5 has the abovementioned meaning.

Further particularly preferred diaminothiophenes of the formula I are those in which R.sup.3 is C.sub.1 -C.sub.6 -mono- or dialkylamino, allylamino, methallylamino, propargylamino, C.sub.2 -C.sub.6 -alkylamino which is substituted by phenyl, hydroxyl, phenoxy, amino or C.sub.1 -C.sub.4 -mono- or dialkylamino or interrupted by an oxygen, or phenylamino, pyrrolidino, piperidino, morpholino, piperazino or N-(C.sub.1 -C.sub.4 -alkyl)piperazino.

Further particularly preferred diaminothiophenes of the formula I are those in which R.sup.4 is cyano, nitro, formyl or ##STR13## where Z is cyano, nitro or C.sub.1 -C.sub.4 -alkoxycarbonyl.

Especially important are diaminothiophenes of the formula I in which R.sup.1 and R.sup.2 are each hydrogen or together are .dbd.CH--N(CH.sub.3).sub.2.

Very particularly important are diaminothiophenes of the formula Ia ##STR14## or tautomers thereof, where L.sup.1 is amino,

L.sup.2 is C.sub.1 -C.sub.6 -mono- or dialkylamino, allylamino, methallylamino, propargylamino, C.sub.2 -C.sub.6 -alkylamino which is substituted by phenyl, hydroxyl, phenoxy, amino or C.sub.1 -C.sub.4 -mono- or dialkylamino or interrupted by an oxygen, or phenylamino, pyrrolidino, piperidino, morpholino, piperazino or N-(C.sub.1 -C.sub.4 -alkyl)piperazino and L.sup.3 is cyano, nitro, formyl or ##STR15## where Z is cyano, nitro or C.sub.1 -C.sub.4 -alkoxycarbonyl.

The diaminothiophenes of the formula I according to the invention can be obtained, for example, by reaction of aminothiophenes of the formula II ##STR16## where R.sup.1, R.sup.2 and R.sup.4 each has the abovementioned meaning, and Hal is chlorine or bromine, with an amino compound of the formula III

R.sup.3 --H (III) where R.sup.3 has the abovementioned meaning.

This entails, for example, the aminothiophene II being reacted with the amino compound III in an inert solvent (e.g. N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoric trisamide, 1,3-dimethylimidazolin-2-one, 1,3-dimethylhexylhydropyrimidin-2-one or 1,2-diethoxyethane) at from -10.degree. to +150.degree. C. The molar ratio II:III is usually 1:2 to 1:10.

The aminothiophenes of the formula II have been disclosed, for example, in EP-A 193,885 or can be obtained by methods similar to those detailed therein.

The novel diaminothiophenes are valuable intermediates for the synthesis of dyes, crop protection agents or pharmaceuticals. They are especially used as diazo components (R.sup.1 and R.sup.2 =H) for the preparation of azo dyes.

The Examples which follow are intended to illustrate the invention in detail.

EXAMPLE 1

2-Amino-3,5-dicyano-4-piperidinothiophene

4,6 g of 2-amino-4-chloro-3,5-dicyanothiophene were dissolved in 25 ml of N,N-dimethylformamide (DMF). 5.3 g of piperidine were added dropwise to this at room temperature, and the mixture was stirred at room temperature for 4 hours. The reaction mixture was then stirred into 800 g of water. The precipitate was filtered off with suction, washed with water and dried in an oven at 50.degree. C. 5.4 g (93% of theory) of the compound of the formula ##STR17## were obtained with melting point 183.degree. to 184.degree. C. The NMR, IR, UV and mass spectra and the elemental analysis are consistent with the structure indicated above.

The compounds listed in the following table are obtained in a similar manner.

__________________________________________________________________________ ##STR18##Ex. MeltingNo. Y.sup.1 Y.sup.2 Y.sup.3 point__________________________________________________________________________ [.degree.C.]2 NH.sub.2 NHCH.sub.3 CN3 NH.sub.2 NHC.sub.2 H.sub.5 CN4 NH.sub.2 NH-n-C.sub.3 H.sub.7 CN 177-1805 NH.sub.2 NH-iso-C.sub.3 H.sub.7 CN 170-1716 NH.sub.2 NH-n-C.sub.4 H.sub.9 CN 211-2127 NH.sub.2 NH-sec-C.sub.4 H.sub.9 CN 121-1268 NH.sub.2 NH-iso-C.sub.4 H.sub.9 CN 1789 NH.sub.2 NH-tert-C.sub.4 H.sub.9 CN 139-14210 NH.sub.2 NH-n-C.sub.5 H.sub.11 CN 177-17811 NH.sub.2 NH-iso-C.sub.5 H.sub.11 CN12 NH.sub.2 NH-neo-C.sub.5 H.sub.11 CN13 NH.sub.2 NH-n-C.sub.6 H.sub.13 CN14 NH.sub.2 NH-n-C.sub.7 H.sub.15 CN 92-9715 NH.sub.2 NH-n-C.sub.8 H.sub.17 CN16 NH.sub.2 NH-n-C.sub.9 H.sub.19 CN17 NH.sub.2 NH-n-C.sub.10 H.sub.21 CN18 NH.sub.2 NH-n-C.sub.11 H.sub.23 CN19 NH.sub.2 NH-n-C.sub.12 H.sub.25 CN20 NH.sub.2 NH-n-C.sub.13 H.sub.27 CN21 NH.sub.2 NH-n-C.sub.14 H.sub.29 CN22 NH.sub.2 NH-n-C.sub.15 H.sub.31 CN23 NH.sub.2 NH-n-C.sub.16 H.sub.33 CN24 NH.sub.2 NH-n-C.sub.17 H.sub.35 CN25 NH.sub.2 NH-n-C.sub.18 H.sub.37 CN26 NH.sub.2 NH-n-C.sub.19 H.sub.39 CN27 NH.sub.2 NH-n-C.sub.20 H.sub.41 CN28 NH.sub.2 NHCH.sub.2CHCH.sub.2 CN29 NH.sub.2 NHCH.sub.2CCH CN30 NH.sub.2 NHCH.sub.2CHCHCH.sub.3 CN31 NH.sub.2 NHCH.sub.2CH.sub.2OH CN 17032 NH.sub.2 NHCH.sub.2CH.sub.2OCH.sub.3 CN33 NH.sub.2 NHCH.sub.2CH.sub.2OC.sub.2 H.sub.5 CN 17534 NH.sub.2 NHCH.sub.2CH.sub.2O-nC.sub.3 H.sub.7 CN35 NH.sub.2 NHCH.sub.2CH.sub.2OC.sub.6 H.sub.5 CN36 NH.sub.2 NHCH.sub.2CH.sub.2OCH.sub.2C.sub.6 H.sub.5 CN37 NH.sub.2 NH CH.sub.2CH.sub.2NH.sub.2 CN38 NH.sub.2 NHCH.sub.2CH.sub.2N(CH.sub.3).sub.2 CN39 NH.sub.2 NHCH.sub.2CH.sub.2N(C.sub.2 H.sub.5).sub.2 CN 125-12940 NH.sub.2 NH(CH.sub.2).sub.3OH CN 171-17241 NH.sub.2 NH(CH.sub.2).sub.3OCH.sub.3 CN42 NH.sub.2 NH(CH.sub.2).sub.3OC.sub.2 H.sub.5 CN43 NH.sub.2 NH(CH.sub.2).sub.3O-n-C.sub.3 H.sub.7 CN44 NH.sub.2 NH(CH.sub.2).sub.3OC.sub.6 H.sub.5 CN45 NH.sub.2 NH(CH.sub.2).sub.3OCH.sub.2 C.sub.6 H.sub.5 CN46 NH.sub.2 NH(CH.sub.2).sub.3O(CH.sub.2).sub.2OC.sub.6 H.sub.5 CN47 NH.sub.2 NH(CH.sub.2).sub.3NH.sub.2 CN48 NH.sub.2 NH(CH.sub.2).sub.3N(CH.sub.3).sub.2 CN49 NH.sub.2 NH(CH.sub.2).sub.3N(C.sub.2 H.sub.5).sub.2 CN50 NH.sub.2 NHC.sub.6 H.sub.5 CN51 NH.sub.2 NHCH.sub.2 C.sub.6 H.sub.5 CN52 NH.sub.2 NHCH.sub.2 CH.sub.2 C.sub.6 H.sub.5 CN53 NH.sub.2 NHCH.sub.2 (CH.sub.3)C.sub.6 H.sub.5 CN54 NH.sub.2 NH-cyclo-C.sub.3 H.sub.5 CN55 NH.sub.2 NH-cyclo-C.sub.4 H.sub.7 CN56 NH.sub.2 NH-cyclo-C.sub.5 H.sub.9 CN57 NH.sub.2 NH-cyclo-C.sub.6 H.sub.11 CN58 NH.sub.2 NH-cyclo-C.sub.7 H.sub.13 CN59 NH.sub.2 NH-cyclo-C.sub.8 H.sub.15 CN60 NH.sub.2 NHCH.sub.2CH.sub.2SCH.sub.3 CN61 NH.sub.2 NHCH.sub.2CH.sub.2SC.sub.2 H.sub.5 CN62 NH.sub.2 NH(CH.sub.2).sub.3 SCH.sub.3 CN63 NH.sub.2 NH(CH.sub.2).sub.3 SC.sub.2 H.sub.5 CN64 NH.sub.2 NHC.sub.6 H.sub.4 -(2)-CH.sub.3 CN65 NH.sub.2 NHC.sub.6 H.sub.4 -(3)-CH.sub.3 CN66 NH.sub.2 NHC.sub.6 H.sub.4 -(4)-CH.sub.3 CN67 NH.sub.2 NHC.sub.6 H.sub.4 -(2)-C.sub.2 H.sub.5 CN68 NH.sub.2 NHC.sub.6 H.sub.4 -(3)-C.sub.2 H.sub.5 CN69 NH.sub.2 NHC.sub.6 H.sub.4 -(4)-C.sub.2 H.sub.5 CN70 NH.sub.2 NHC.sub.6 H.sub.4 -(2)-OH CN71 NH.sub.2 NHC.sub.6 H.sub.4 -(3)-OH CN72 NH.sub.2 NHC.sub.6 H.sub.4 -(4)-OH CN73 NH.sub.2 NHC.sub.6 H.sub.4 -(2)-Cl CN74 NH.sub.2 NHC.sub.6 H.sub.4 -(3)-Cl CN75 NH.sub.2 NHC.sub.6 H.sub.4 -(4)-Cl CN76 NH.sub.2 NHC.sub.6 H.sub.4 -(2)-OCH.sub.3 CN77 NH.sub.2 NHC.sub.6 H.sub.4 -(3)-OCH.sub.3 CN78 NH.sub.2 NHC.sub.6 H.sub.4 -(4)-OCH.sub.3 CN79 NH.sub.2 NHC.sub.6 H.sub.4 -(2)-OC.sub.2 H.sub.5 CN80 NH.sub.2 NHC.sub.6 H.sub.4 -(3)-OC.sub.2 H.sub.5 CN81 NH.sub.2 NHC.sub.6 H.sub.4 -(4)-OC.sub.2 H.sub.5 CN82 NH.sub.2 NHC.sub.6 H.sub.4 -(2)-NH.sub.2 CN83 NH.sub.2 NHC.sub.6 H.sub.4 -(3)-NH.sub.2 CN84 NH.sub.2 NHC.sub.6 H.sub.4 -(4)-NH.sub.2 CN85 NH.sub.2 NHC.sub.6 H.sub.3 -(2,3)-(CH.sub.3).sub.2 CN86 NH.sub.2 NHC.sub.6 H.sub.3 -(2,4)-(CH.sub.3).sub.2 CN87 NH.sub.2 NHC.sub.6 H.sub.3 -(2,5)-(CH.sub.3).sub.2 CN88 NH.sub.2 NHC.sub.6 H.sub.3 -(2,6)-(CH.sub.3).sub.2 CN89 NH.sub.2 NHC.sub.6 H.sub.3 -(3,4)-(CH.sub.3).sub.2 CN90 NH.sub.2 NHC.sub.6 H.sub.3 -(3,5)-(CH.sub.3).sub.2 CN91 NH.sub.2 NHC.sub.6 H.sub.4 -(2)-N(CH.sub.3).sub.2 CN92 NH.sub.2 NHC.sub.6 H.sub.4 -(3)-N(CH.sub.3).sub.2 CN93 NH.sub.2 NHC.sub.6 H.sub.4 -(4)-N(CH.sub.3).sub.2 CN94 NH.sub.2 NHC.sub.6 H.sub.4 -(2)-CN CN95 NH.sub.2 NHC.sub.6 H.sub.4 -(3)-CN CN96 NH.sub.2 NHC.sub.6 H.sub.4 -(4)-CN CN97 NH.sub.2 NHC.sub.6 H.sub.4 -(2)-COOH CN98 NH.sub.2 NHC.sub.6 H.sub.4 -(3)-COOH CN99 NH.sub.2 NHC.sub.6 H.sub.4 -(4)-COOH CN100 NH.sub.2 NHC.sub.6 H.sub.4 -(2)-COCH.sub.3 CN101 NH.sub.2 NHC.sub.6 H.sub.4 -(3)-COCH.sub.3 CN102 NH.sub.2 NHC.sub.6 H.sub.4 -(4)-COCH.sub.3 CN103 NH.sub.2 NHC.sub.6 H.sub.4 -(2,3)-Cl.sub.2 CN104 NH.sub.2 NH-pyrid-2-yl CN105 NH.sub.2 NH-pyrid-3-yl CN106 NH.sub.2 NH-pyrid-4-yl CN107 NH.sub.2 NH-thien-2-yl CN108 NH.sub.2 N(CH.sub.3).sub.2 CN109 NH.sub.2 N(C.sub.2 H.sub.5).sub.2 CN110 NH.sub.2 N(n-C.sub.3 H.sub.7).sub.2 CN111 NH.sub.2 N(n-C.sub.4 H.sub.9).sub.2 CN112 NH.sub.2 N(CH.sub.2 CHCH.sub.2).sub.2 CN113 NH.sub.2 N(CH.sub.3)(C.sub.6 H.sub.5) CN114 NH.sub.2 N(C.sub.2 H.sub.5)(CH.sub.2 C.sub.6 H.sub.5) CN115 NH.sub.2 N(CH.sub.3)(C.sub.6 H.sub.5) CN116 NH.sub.2 N(C.sub.2 H.sub.5)(CH.sub.2 C.sub.6 H.sub.5) CN117 NH.sub.2 N(CH.sub.2 C.sub.6 H.sub.5).sub.2 CN118 NH.sub.2 N(CH.sub.2 CH.sub.2 OH).sub.2 CN119 NH.sub.2 ##STR19## CN120 NH.sub.2 ##STR20## CN121 NH.sub.2 ##STR21## CN122 NH.sub.2 ##STR22## CN123 NH.sub.2 ##STR23## CN124 NH.sub.2 ##STR24## CN125 NH.sub.2 ##STR25## CN126 NH.sub.2 ##STR26## CN127 NH.sub.2 ##STR27## CN128 NH.sub.2 ##STR28## CN129 NH.sub.2 ##STR29## CN130 NH.sub.2 ##STR30## CN131 NH.sub.2 ##STR31## CN132 NH.sub.2 ##STR32## CN133 NH.sub.2 ##STR33## CN134 NH.sub.2 NHNH.sub.2 CN135 NH.sub.2 NHN(CH.sub.3).sub.2 CN136 NH.sub.2 NHNHC.sub.6 H.sub.5 CN137 NH.sub.2 NHNHCH.sub.3 CN138 NH.sub.2 N(CH.sub.3)NHCH.sub.3 CN139 NH.sub.2 NHN(C.sub.2 H.sub.5).sub.2 CN140 NH.sub.2 NHN(n-C.sub.3 H.sub.7).sub.2 CN141 NH.sub.2 NHN(n-C.sub.4 H.sub.9).sub.2 CN142 NCHN(CH.sub.3).sub.2 N(C.sub.2 H.sub.5).sub.2 CN143 NCHN(CH.sub.3).sub.2 N(CH.sub.3).sub.2 CN144 NCHN(C.sub.2 H.sub.5).sub.2 N(CH.sub.3).sub.2 CN145 NCHN(C.sub.2 H.sub.5).sub.2 N(C.sub.2 H.sub.5).sub.2 CN146 NH.sub.2 NHCH.sub.3 NO.sub.2147 NH.sub.2 NHC.sub.2 H.sub.5 NO.sub.2148 NH.sub.2 NH-n-C.sub.3 H.sub.7 NO.sub.2149 NH.sub.2 NH-iso-C.sub.3 H.sub.7 NO.sub.2150 NH.sub.2 NH-n-C.sub.4 H.sub.9 NO.sub.2151 NH.sub.2 NH-n-C.sub.5 H.sub.11 NO.sub.2152 NH.sub.2 NH-cyclo-C.sub.3 H.sub.5 NO.sub.2153 NH.sub.2 NH-cyclo-C.sub.6 H.sub.11 NO.sub.2154 NH.sub.2 ##STR34## NO.sub.2 >315155 NH.sub.2 ##STR35## NO.sub.2156 NH.sub.2 ##STR36## NO.sub.2157 NH.sub.2 ##STR37## NO.sub.2 275-276158 NH.sub.2 ##STR38## NO.sub.2159 NH.sub.2 NHCH.sub.3 CHNCH.sub.3160 NH.sub.2 NHC.sub.2 H.sub.5 CHNC.sub.2 H.sub.5161 NH.sub.2 N(CH.sub.3).sub.2 CHO162 NH.sub.2 N(C.sub.2 H.sub.5).sub.2 CHO163 NH.sub.2 N(n-C.sub.3 H.sub.7).sub.2 CHO164 NH.sub.2 N(n-C.sub.4 H.sub.9).sub.2 CHO165 NH.sub.2 ##STR39## CHO166 NH.sub.2 ##STR40## CHO167 NH.sub.2 ##STR41## CHO168 NH.sub.2 ##STR42## CHO169 NH.sub.2 ##STR43## CHO170 NH.sub.2 ##STR44## CHO171 NH.sub.2 ##STR45## CHO172 NH.sub.2 N(CH.sub.3).sub.2 COCH.sub.3173 NH.sub.2 N(C.sub.2 H.sub.5).sub.2 COCH.sub.3174 NH.sub.2 N(CH.sub.3).sub.2 COC.sub.2 H.sub.5175 NH.sub.2 N(C.sub.2 H.sub.5).sub.2 CO-n-C.sub.3 H.sub.7176 NH.sub.2 N(CH.sub.3).sub.2 CO-iso-C.sub.3 H.sub.7177 NH.sub.2 N(CH.sub.3).sub.2 COC.sub.6 H.sub.5178 NH.sub.2 N(CH.sub.3).sub.2 CHC(CN).sub.2179 NH.sub.2 N(C.sub.2 H.sub.5).sub.2 CHC(CN).sub.2 107-109180 NH.sub.2 N(n-C.sub.3 H.sub.7).sub.2 CHC(CN).sub.2181 NH.sub.2 N(n-C.sub.4 H.sub.9).sub.2 CHC(CN).sub.2182 NH.sub.2 ##STR46## CHC(CN).sub.2183 NH.sub.2 ##STR47## CHC(CN).sub.2 225184 NH.sub.2 ##STR48## CHC(CN).sub.2185 NH.sub.2 ##STR49## CHC(CN).sub.2 270186 NH.sub.2 NHCH(C.sub.6 H.sub.5).sub.2 ##STR50##187 NH.sub.2 NHCH.sub.3 ##STR51##188 NH.sub.2 NHC.sub.2 H.sub.5 ##STR52##189 NH.sub.2 ##STR53## ##STR54##190 NH.sub.2 N(C.sub.2 H.sub.5).sub.2 ##STR55##191 NH.sub.2 ##STR56## ##STR57##192 NH.sub.2 NHCH.sub. 3 ##STR58##193 NH.sub.2 NHC.sub.2 H.sub.5 ##STR59##194 NH.sub.2 ##STR60## ##STR61##195 NH.sub.2 ##STR62## ##STR63##196 NH.sub.2 ##STR64## ##STR65##197 NH.sub.2 NHCH.sub.3 ##STR66##198 NH.sub.2 NHC.sub.2 H.sub.5 CHC(CO.sub.2 CH.sub.3).sub.2199 NH.sub.2 N(CH.sub.3).sub.2 ##STR67##200 NH.sub.2 NHC.sub.6 H.sub.5 ##STR68##__________________________________________________________________________

Claims

1. A diaminothiophene of Formula I: ##STR69## or tautomers thereof, wherein R.sup.1 and R.sup.2 are each hydrogen, R.sup.3 is C.sub.1 -C.sub.20 -mono- or dialkylamino, C.sub.2 -C.sub.10 -mono or dialkylamino whose alkyl is substituted and/or interrupted by one or more oxygen atoms, C.sub.2 -C.sub.12 -mono- or dialkenylamino, C.sub.3 -C.sub.12 -alkynylamino, N-(C.sub.1 -C.sub.5 -alkyl)-N-phenylamino, hydrazino, C.sub.1 -C.sub.4 -mono- or dialkylhydrazino or phenylhydrazino, and R.sup.4 C.sub.1 -C.sub.6 -alkanoyl, benzoyl, cyano, nitro or ##STR70## where T.sup.4 is hydrogen, C.sub.1 -C.sub.4 -alkyl or phenyl, and T.sup.5 is the radical of an active methylene compound, or hydroxyimino or N-X where X is C.sub.1 -C.sub.20 -alkyl which can be substituted and/or interrupted by one or more oxygens, substituted or unsubstituted C.sub.3 -C.sub.6 -alkenyl, substituted or unsubstituted C.sub.3 -C.sub.6 -alkynyl, substituted or unsubstituted C.sub.3 -C.sub.10 -cycloalkyl, substituted or unsubstituted phenyl, pyridyl, C.sub.1 -C.sub.4 -alkoxycarbonylmethyl, amino, C.sub.1 -C.sub.4 -dialkylamino or phenylamino.