Pyrrole derivatives useful as diazo and coupling components

The present invention relates to compounds of the general formula I ##STR4## or the tautomers thereof, where
R.sup.1 is hydrogen, C.sub.1 -C.sub.20 -alkyl which can be substituted and/or interrupted by one or more oxygens, C.sub.3 -C.sub.6 -alkenyl which can be substituted, C.sub.3 -C.sub.6 -alkynyl which can be substituted, C.sub.3 -C.sub.10 -cycloalkyl which can be substituted, phenyl which can be substituted, pyridyl, thienyl, amino, C.sub.1 -C.sub.4 -alkanoylamino, benzoylamino, C.sub.1 -C.sub.4 -dialkylamino or ##STR5## where X.sup.1 is C.sub.1 -C.sub.4 -alkyl or phenyl, and X.sup.2 is C.sub.1 -C.sub.4 -alkyl, alkyl,
R.sup.2 is hydrogen, C.sub.1 -C.sub.4 -alkyl, benzyl, C.sub.3 14 C.sub.6 -alkenyl, C.sub.5 -C.sub.7 -cycloalkyl, or phenyl which can be substituted,
R.sup.3 is hydrogen, C.sub.1 -C.sub.4 -alkyl, benzyl or C.sub.3 -C.sub.6 -alkenyl, or R.sup.2 and R.sup.3 together are ##STR6## where T.sup.1 is hydrogen, C.sub.1 -C.sub.4 -alkyl or phenyl, T.sup.2 is C.sup.1 -C.sub.4 -alkyl, or phenyl which can be substituted, and T.sup.3 is C.sub.1 -C.sub.4 -alkyl, or R.sup.2 and R.sup.3 together with the nitrogen connecting them are a 5- to 7-membered saturated heterocyclic radical which can contain other hetero atoms.
R.sup.4 is cyano, carbamoyl, C.sub.1 -C.sub.4 -mono- or dialkylcarbamoyl, thiocarbamoyl, C.sub.1 -C.sub.4 -mono- or dialkylthiocarbamoyl or ##STR7##
R.sup.5 is halogen, hydroxyl, C.sub.1 -C.sub.20 -alkanoyloxy, or benzoyloxy which can be substituted, and
R.sup.6 is hydrogen, C.sub.1 -C.sub.4 -alkyl, phenyl which can be substituted, cyano, halogen, nitro, hydroxysulfonyl, C.sub.1 -C.sub.10 -alkanoyl, benzoyl which can be substituted, or ##STR8## where T.sup.4 is C.sub.1 -C.sub.4 -alkyl, or phenyl which can be substituted, and T.sup.5 is the radical of an active methylene compound, hydroxyimino or N--X.sup.3 where X.sup.3 is C.sub.1 -C.sub.20 -alkyl which can be substituted and/or interrupted by one or more oxygens, C.sub.3 -C.sub.6 -alkenyl which can be substituted, C.sub.3 -C.sub.6 -alkynyl which can be substituted, C.sub.3 -C.sub.10 -cycloalkyl which can be substituted, phenyl which can be substituted, pyridyl, C.sub.1 -C.sub.4 -alkoxycarbonylmethyl, amino, C.sub.1 -C.sub.4 -dialkylamino or phenylamino, with the proviso that R.sup.1, R.sup.2 and R.sup.3 are not all hydrogen.
DD-A-126,389 discloses 5-methyl- and 5-ethyl-2-amino-3-cyanopyrrolin-4-one. However, these compounds are not particularly suitable as diazo components for the preparation of azo dyes.
The object of the present invention was to prepare novel pyrrole derivatives which are suitable, depending on the constitution, both as diazo components and as coupling components.
In accordance with this, we have found the pyrrole derivatives of the formula I which are identified in the introduction.
All the alkyls and alkenyls occurring 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, the preferred alkyls are interrupted by one to three, in particular one or two, oxygens.
When substituted phenyls occur in the formula I, examples of suitable substituents are C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, halogen, especially chlorine or bromine, nitro, hydroxyl or amino.
When substituted alkyls occur in the formula I,
examples of suitable substituents are C.sub.1 -C.sub.5 -alkylthio, phenoxy which can be substituted, halogen, especially 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, hexamethyleneimino, C.sub.1 -C.sub.5 -alkoxycarbonyl, or phenyl which can be substituted.
When substituted alkenyls, alkynyls or cycloalkyls occur in the formula I, examples of suitable substituents are fluorine, chlorine or bromine.
When R.sup.2 and R.sup.3 together with the nitrogen connecting 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 R.sup.1 are hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, allyl, propinyl, methallyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 2- or 3-hydroxypropyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3-(2-phenoxyethoxy)propyl, 2- or 3-benzyloxypropyl, 2-methylthioethyl, 2-ethylthioethyl, 2- or 3-methylthiopropyl, 2- or 3-ethylthiopropyl, 2-aminoethyl, 2-(N,N-dimethylamino)ethyl, 2-(N,N-diethylamino)ethyl, 2- or 3-(N,N-dimethylamino)propyl, 2- or 3-(N,N-diethylamino)propyl, 2- or 3-aminopropyl, benzyl, 1-phenylethyl, 2-phenylethyl, phenyl, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 2-aminophenyl, 3-aminophenyl, 4-aminophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, pyrid-2-yl, pyrid-3-yl, pyrid-4-yl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-propoxycarbonylethyl, 2-butoxycarbonylethyl, 2-(3,4-dichlorophenyl)ethyl, diphenylmethyl, 2-(3-chloro-2-methylphenyl)ethyl, 2-(3,4-dimethoxyphenyl)ethyl, 2-(2-chlorophenyl)ethyl, amino, dimethylamino, diethylamino, thien-2-yl, 2-morpholinoethyl, 2- or 3-morpholinopropyl or 2-piperazinoylethyl. (The terms isooctyl, isononyl, isodecyl and isotridecyl used above are trivial names and derive from the alcohols obtained in the oxo synthesis--cf. in this connection Ullmanns Enzyklopadie der technischen Chemie, 4th edition, volume 7, pages 215 to 217, and volume 11, pages 435 and 436.
Examples of R.sup.2 and R.sup.3 are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or allyl.
Examples of R.sup.5 are chlorine, bromine, acetyloxy, propionyloxy, butyryloxy, isobutyryloxy, hexanoyloxy or benzoyloxy.
Examples of R.sup.6 are methyl, ethyl, formyl, acetyl, propionyl, butyryl, isobutyryl, pentanoyl, hexanoyl, benzoyl, chlorine or bromine.
--NX.sup.3 is derived from primary amines of the formula H.sub.2 NX.sup.3. 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 active methylene compounds of the formula H.sub.2 T.sup.5. Examples of such compounds are those of the formula ##STR9## where Z.sup.3 is hydrogen, 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 of the formula ##STR10## Some particularly important compounds are, e.g.: ##STR11## Pyrrole derivatives of the formula Ia or Ib ##STR12## where R.sup.1, R.sup.2, R.sup.3 and R.sup.6 each have the abovementioned meanings, are advantageously prepared by reacting the compound of the formula II ##STR13## where R.sup.6 has the abovementioned meaning, and cat.sym. is a cation (e.g. an alkali metal ion or, preferably, a trialkylammonium ion), with an amine of the formula IIIa or IIIb ##STR14## where R.sup.1, R.sup.2 and R.sup.3 each have the abovementioned meanings.
The reaction is expediently carried out 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 or 1,2-diethoxyethane) in the presence of a base (e.g. triethylamine, tripropylamine, tributylamine, N-methylpiperidine or N,N-dimethylaniline) at from 0.degree. to 150.degree. C. The molar ratio of compound III to amine is 1:1 to 1:5 as a rule.
The compound of the formula II can be prepared in a conventional manner from malononitrile and the carbonyl chloride of the formula IV ##STR15## where R.sup.6 has the abovementioned meaning.
The pyrrole derivatives of the formula Ia and Ib can be reacted by conventional methods (e.g. by the Vilsmeier reaction) to give further compounds of the formula I.
Further details of the preparation can be taken from the Examples.
The novel pyrrole derivatives of the formula I are suitable, depending on the constitution, as diazo or coupling components for azo dyes.
Preferred pyrrole derivatives of the formula I are those where
R.sup.1 is hydrogen, C.sub.1 -C.sub.15 -alkyl, C.sub.5 -C.sub.7 -cycloalkyl, C.sub.3 -C.sub.5 -alkenyl, C.sub.2 C.sub.5 -hydroxyalkyl, C.sub.2 -C.sub.5 -halogenoalkyl, C.sub.1 -C.sub.5 -alkoxy-C.sub.2 -C.sub.5 -alkyl, phenoxy-C.sub.2 -C.sub.5 -alkoxy-C.sub.2 -C.sub.5 -alkyl, phenyl-C.sub.1 -C.sub.5 -alkoxy-C.sub.2 -C.sub.5 -alkoxy-C.sub.2 -C.sub.5 -alkyl, C.sub.1 -C.sub.5 -alkylthio-C.sub.2 -C.sub.5 -alkyl, C.sub.1 -C.sub.5 -dialkylamino-C.sub.2 -C.sub.2 -alkyl, phenyl-C.sub.1 -C.sub.5 -alkyl, C.sub.1 -C.sub.5 -alkoxycarbonyl-C.sub.1 C.sub.5 -alkyl, --(CH.sub.2).sub.n --Y where n is from 1 to 5 and Y is pyrrolidino, piperidino, morpholino, thiomorpholino, piperazino, N-(C.sub.1 -C.sub.4 -alkyl)piperazino or hexamethyleneimino, or phenyl, pyridyl, amino or C.sub.1 -C.sub.5 -dialkylamino,
R.sup.2 is hydrogen, C.sub.1 -C.sub.4 -alkyl, allyl, benzyl or phenyl,
R.sup.3 is hydrogen, C.sub.1 -C.sub.4 -alkyl, allyl or benzyl, or R.sup.2 and R.sup.3 together are ##STR16## where T.sup.1 is hydrogen or C.sub.1 -C.sub.4 -alkyl, T.sup.2 is C.sub.1 -C.sub.4 -alkyl or phenyl, and T.sup.3 is C.sub.1 -C.sub.4 -alkyl, or R.sup.2 and R.sup.3 together with the nitrogen connecting them are pyrrolidino, piperidino, morpholino, thiomorpholino, piperazino, N-(C.sub.1 -C.sub.4 -alkyl)piperazino or hexamethyleneimino,
R.sup.4 is cyano, carbamoyl, thiocarbamoyl or ##STR17##
R.sup.5 is fluorine, chlorine, bromine, hydroxyl, C.sub.1 -C.sub.6 -alkanoyloxy or benzoyloxy and
R.sup.6 is hydrogen, C.sub.1 -C.sub.4 -alkyl, phenyl, C.sub.1 -C.sub.6 -alkanoyl, benzoyl, cyano, chlorine, bromine, nitro, hydroxysulfonyl or ##STR18## where T.sup.4 and T.sup.5 each have the abovementioned meanings.
Particularly preferred pyrrole derivatives of the formula I are those in which
R.sup.1 is hydrogen, C.sub.1 -C.sub.10 -alkyl, C.sub.3 -C.sub.4 -alkenyl, benzyl, phenyl or amino,
R.sup.2 is hydrogen, C.sub.1 -C.sub.4 -alkyl, allyl, benzyl or phenyl,
R.sup.3 is hydrogen C.sub.1 -C.sub.4 -alkyl or allyl, or R.sup.2 and R.sup.3 together with the nitrogen connecting the nitrogen connecting them are pyrrolidino, piperidino, morpholino, thiomorpholino, N-methylpiperazino or hexamethyleneimino,
R.sup.4 is cyano, carbamoyl, thiocarbamoyl or ##STR19##
R.sup.5 is chlorine, bromine, hydroxyl, C.sub.1 -C.sub.6 -alkanoyloxy or benzoyloxy and
R.sup.6 is hydrogen, C.sub.1 -C.sub.4 -alkyl, phenyl, C.sub.1 -C.sub.6 -alkanoyl, benzoyl, cyano or ##STR20## where Z.sup.1 and Z.sup.2 are identical or different and, independently of one another, are each cyano, C.sub.1 -C.sub.4 -alkoxycarbonyl or nitro, and X.sup.3 has the abovementioned meaning.
Of special interest are pyrrole derivatives of the formula I where
R.sup.1 is C.sub.1 -C.sub.4 -alkyl, phenyl or amino and
R.sup.2 and R.sup.3 are each hydrogen or
R.sup.1 is hydrogen,
R.sup.2 is methyl, ethyl, allyl, benzyl or phenyl,
R.sup.3 is methyl, ethyl or allyl or R.sup.2 and R.sup.3 together with the nitrogen connecting them are pyrrolidino, piperidino, morpholino, N-methylpiperazino or hexamethyleneimino,
R.sup.4 is cyano or carbamoyl,
R.sup.5 is chlorine, bromine or hydroxyl,
R.sup.6 is hydrogen, formyl, cyano or ##STR21## where Z.sup.1 and Z.sup.2 are identical or different and, independently of one another, are each cyano, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxycarbonyl or nitro.
Particularly important pyrrole derivatives in this connection are those in which the radicals Z.sup.1 and Z.sup.2 are, independently of one another, cyano or C.sub.1 -C.sub.4 -alkoxycarbonyl or else one of the two radicals is hydrogen.

The Examples which follow are intended to illustrate the invention.
EXAMPLE 1
2-Amino-3-cyano-1-methyl-pyrrolin-4-one
99 g of malononitrile were dissolved in 150 ml of N,N-dimethylformamide (DMF) and cooled to 0.degree. C. While cooling, 556 g of tributylamine and 169.5 g of chloroacetyl chloride were simultaneously added dropwise to this, and the mixture was then stirred at 10.degree. C. for 10 minutes. The reaction mixture was subsequently added to a mixture of 1.5 kg of ice and 327 ml of 40% by weight aqueous methylamine solution and stirred at room temperature for 8 hours. The precipitate was filtered off with suction, washed and dried in an oven at 50.degree. C. 124 g (60% of theory) of the compound of the formula ##STR22## of melting point 300.degree. C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.
EXAMPLE 2
2-Amino-3-cyano-1-ethylpyrrolin-4-one
19.8 g of malononitrile were dissolved in 30 ml of DMF and cooled to 0.degree. C. While cooling, 61 g of triethylamine and 32 g of chloroacetyl chloride were simultaneously added dropwise to this, and the mixture was then stirred at 10.degree. C. for 10 minutes. Subsequently, while cooling, 49 g of 70% by weight aqueous ethylamine solution were added dropwise, and the mixture was stirred at room temperature for 8 hours. The precipitate was filtered off with suction, washed and dried at 50.degree. C. 41.8 g (92%) of impure crude product were obtained and were recrystallized from 1:1 isopropanol/water with the addition of active carbon. This resulted in 10.9 g (24% of theory) of the compound of the formula ##STR23## of melting point 278.degree. to 280.degree. C. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.
EXAMPLE 3
2-Amino-3-cyano-1-isopropylpyrrolin-4-one
99 g of malononitrile were dissolved in 150 ml of DMF and cooled to 0.degree. C. While cooling, 306 g of triethylamine and 159 g of chloroacetyl chloride were simultaneously added dropwise to this. The reaction mixture was stirred at 10.degree. C. for 10 minutes and subsequently added to a mixture of 1.5 kg of ice and 158 g of isopropylamine. The mixture was stirred at room temperature for 8 hours. The volatiles were then removed by distillation under atmospheric pressure at 100.degree. C., and the distillation residue was cooled to 5.degree. C. The precipitate was filtered off with suction, washed and dried. 105.6 g (43% of theory) of the compound of the formula ##STR24## of melting point 285.degree. to 290.degree. C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.
EXAMPLE 4
2-Amino-3-cyano-1-tridecylpyrrolin-4-one
19.8 g of malononitrile were dissolved in 30 ml of DMF and cooled to 0.degree. C. While cooling, 61 g of triethylamine and 27 g of chloroacetyl chloride were simultaneously added dropwise to this, and the mixture was stirred at 10.degree. C. for 10 minutes. 65.7 g of tridecylamine were then added dropwise, and the reaction mixture was stirred at room temperature for 48 hours. 300 ml of isopropylamine were then added to the mixture, which was refluxed for 2 hours, 10 g of active carbon were added, and the mixture was filtered hot. After cooling, the precipitate was filtered off with suction, washed and dried at 50.degree. C. 40 g (44% of theory) of the compound of the formula ##STR25## of melting point 214.degree. to 215.degree. C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.
EXAMPLE 5
1-Allyl-2-amino-3-cyanopyrrolin-4-one
19.8 g of malononitrile were dissolved in 30 ml of DMF and cooled to 0.degree. C. While cooling, 87 g of tributylamine and 27 g of chloroacetyl chloride were simultaneously added dropwise to this, and the mixture was stirred at 10.degree. C. for 10 minutes. The mixture was then added to a mixture of 300 g of ice and 43 g of allylamine and stirred at room temperature for 8 hours. The precipitate was filtered off with suction, washed and dried. 38.1 g (78% of theory) of impure crude product were obtained and were boiled in 150 ml of isopropanol to purify. After cooling to 5.degree. C., the precipitate was filtered off with suction, washed and dried. 31.2 g (64% of theory) of the compound of the formula ##STR26## of melting point 275.degree. to 278.degree. C. were obtained The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.
EXAMPLE 6
2-cyano-3-cyano-1-(2-methoxyethyl)pyrrolin-4-one
99 g of malononitrile were dissolved in 150 ml of DMF and cooled to 0.degree. C. While cooling, 306 g of triethylamine and 159 g of chloracetyl chloride were simultaneously added dropwise to this, and the mixture was stirred at 10.degree. C. for 10 minutes. The mixture was then added to a mixture of 1.5 kg of ice and 291 g of 2-methoxyethylamine and stirred at room temperature for 8 hours. The volatiles were removed by distillation at 100.degree. C. under atmospheric pressure, and the distillation residue was concentrated in a rotary evaporator at the water pump. The residue was recrystallized from 500 ml of isopropanol. The precipitate was filtered off with suction, washed and dried at 50.degree. C. 205.5 g (76% of theory) of the compound of the formula ##STR27## of melting point 108.degree. to 110.degree. C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.
EXAMPLE 7
2-Amino-3-cyano-1-phenylpyrrolin-4-one Variant A
26.4 g of malononitrile were dissolved in 150 ml of DMF and cooled to 0.degree. C. While cooling, 148 g of tributylamine and 45 g of chloracetyl chloride were simultaneously added dropwise to this, and the mixture was stirred at room temperature for 30 minutes. 42 g of aniline were then added to the mixture, which was stirred at 80.degree. C. for 15 hours and then 200 g of water were added. After cooling to room temperature, the organic phase was separated off and digested with dichloromethane. The precipitate was filtered off with suction, washed and dried. 37.4 g (46% of theory) of the compound of the formula ##STR28## of melting point 285.degree. to 290.degree. C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula
Variant B
19.8 g of malononitrile were dissolved in 30 ml of DMF and cooled to 0.degree. C. While cooling, 61 g of triethylamine and 27 g of chloracetyl chloride were simultaneously added dropwise to this, and the mixture was stirred at 10.degree. C. for 10 minutes. 27.6 g of aniline were then added, and the reaction mixture was stirred at room temperature for 8 hours. 1 kg of water was added, and the mixture was then refluxed for 2 hours and cooled to 10.degree. C., and the precipitate was filtered off with suction, washed and dried. 39.2 g (66% of theory) of the compound identical in all data to the product synthesized in Variant A) were obtained. The compounds listed in the following Table 1 are obtained in a similar manner.
TABLE 1__________________________________________________________________________ ##STR29##Example Melting pointNo. L.sup.1 L.sup.2 L.sup.3 [.degree.C.]__________________________________________________________________________8 CH.sub.2CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9 NH.sub.2 H9 n-C.sub.3 H.sub.7 NH.sub.2 H 257-26710 n-C.sub.4 H.sub.9 NH.sub.2 H 182-19211 iso-C.sub.4 H.sub.9 NH.sub.2 H12 sec-C.sub.4 H.sub.9 NH.sub.2 H13 n-C.sub.5 H.sub.11 NH.sub.2 H14 Neo-C.sub.5 H.sub.11 NH.sub.2 H15 n-C.sub.6 H.sub.13 NH.sub.2 H16 n-C.sub.7 H.sub.15 NH.sub.2 H17 n-C.sub.8 H.sub.17 NH.sub.2 H18 n-C.sub.9 H.sub.19 NH.sub.2 H19 n-C.sub.10 H.sub.21 NH.sub.2 H20 n-C.sub.11 H.sub.23 NH.sub.2 H21 n-C.sub.12 H.sub.25 NH.sub.2 H22 n-C.sub.14 H.sub.29 NH.sub.2 H23 n-C.sub.15 H.sub.31 NH.sub.2 H24 n-C.sub.16 H.sub.33 NH.sub.2 H25 n-C.sub.17 H.sub.35 NH.sub.2 H26 n-C.sub.18 H.sub.37 NH.sub.2 H27 n-C.sub.19 H.sub.39 NH.sub.2 H28 n-C.sub.20 H.sub.41 NH.sub.2 H29 CH.sub.2 CCH NH.sub.2 H30 Cyclo-C.sub.3 H.sub.5 NH.sub.2 H31 Cyclo-C.sub.4 H.sub.7 NH.sub.2 H32 Cyclo-C.sub.5 H.sub.9 NH.sub.2 H33 Cyclo-C.sub.6 H.sub.11 NH.sub.2 H 30034 Cyclo-C.sub.7 H.sub.13 NH.sub.2 H35 Cyclo-C.sub.8 H.sub.15 NH.sub.2 H36 Cyclo-C.sub.9 H.sub.17 NH.sub.2 H37 Cyclo-C.sub.10 H.sub.19 NH.sub.2 H38 CH.sub.2 CH.sub.2 OH NH.sub.2 H 245-25039 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 NH.sub.2 H40 CH.sub.2 CH.sub.2 NH.sub.2 NH.sub.2 H41 CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2 NH.sub.2 H42 CH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2 NH.sub.2 H43 CH.sub.2 CH.sub.2 SCH.sub.3 NH.sub.2 H44 CH.sub.2 CH.sub. 2 SC.sub.2 H.sub.5 NH.sub.2 H45 (CH.sub.2).sub.3 OH NH.sub.2 H46 (CH.sub.2).sub.3 OCH.sub.3 NH.sub.2 H47 (CH.sub.2).sub.3 OC.sub.2 H.sub.5 NH.sub.2 H48 (CH.sub.2).sub.3 NH.sub.2 NH.sub.2 H49 (CH.sub.2).sub.3 N(CH.sub.3).sub.2 NH.sub.2 H50 (CH.sub.2).sub.3 N(C.sub.2 H.sub.5).sub.2 NH.sub.2 H51 (CH.sub.2).sub.3 SCH.sub.3 NH.sub.2 H52 (CH.sub.2).sub.3 SC.sub.2 H.sub.5 NH.sub.2 H53 CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 H 236-23854 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 H 230-23255 CH(CH.sub.3)C.sub.6 H.sub.5 NH.sub.2 H56 CH(C.sub.6 H.sub.5).sub.2 NH.sub.2 H57 C.sub.6 H.sub.4 -(2)-OH NH.sub.2 H58 C.sub.6 H.sub.4 -(3)-OH NH.sub.2 H59 C.sub.6 H.sub.4 -(4)-OH NH.sub.2 H60 C.sub.6 H.sub.4 -(2)-OCH.sub.3 NH.sub.2 H61 C.sub.6 H.sub.4 -(3)-OCH.sub.3 NH.sub.2 H 23462 C.sub.6 H.sub.4 -(4)-OCH.sub.3 NH.sub.2 H 27063 C.sub.6 H.sub.4 -(2)-OC.sub.2 H.sub.5 NH.sub.2 H64 C.sub.6 H.sub.4 -(3)-OC.sub.2 H.sub.5 NH.sub.2 H65 C.sub.6 H.sub.4 -(4)-OC.sub.2 H.sub.5 NH.sub.2 H66 C.sub.6 H.sub.4 -(2)-Cl NH.sub.2 H67 C.sub.6 H.sub.4 -(3)-Cl NH.sub.2 H68 C.sub.6 H.sub.4 -(4)-Cl NH.sub.2 H69 C.sub.6 H.sub.4 -(2)-NO.sub.2 NH.sub.2 H70 C.sub.6 H.sub.4 -(3)-NO.sub.2 NH.sub.2 H71 C.sub.6 H.sub.4 -(4)-NO.sub.2 NH.sub.2 H72 C.sub.6 H.sub.4 -(2)-NH.sub.2 NH.sub.2 H73 C.sub.6 H.sub.4 -(3)-NH.sub.2 NH.sub.2 H74 C.sub.6 H.sub.4 -(4)-NH.sub.2 NH.sub.2 H75 C.sub.6 H.sub.4 -(2)-CH.sub.3 NH.sub.2 H76 C.sub.6 H.sub.4 -(3)-CH.sub.3 NH.sub.2 H77 C.sub.6 H.sub.4 -(4)-CH.sub.3 NH.sub.2 H78 C.sub.6 H.sub.4 -(2)-C.sub.2 H.sub.5 NH.sub.2 H79 C.sub.6 H.sub.4 -(3)-C.sub.2 H.sub.5 NH.sub.2 H80 C.sub.6 H.sub.4 -(4)-C.sub.2 H.sub.5 NH.sub.2 H81 C.sub.6 H.sub.4 -(2)-CN NH.sub.2 H82 C.sub.6 H.sub.4 -(3)-CN NH.sub.2 H83 C.sub.6 H.sub.4 -(4)-CN NH.sub.2 H84 C.sub.6 H.sub.4 -(2)-COOCH.sub.3 NH.sub.2 H85 C.sub.6 H.sub.4 -(3)-COOCH.sub.3 NH.sub.2 H86 C.sub.6 H.sub.4 -(4)-COOCH.sub.3 NH.sub.2 H87 Pyrid-2-yl NH.sub.2 H88 Pyrid-3-yl NH.sub.2 H 30089 Pyrid-4-yl NH.sub.2 H90 (CH.sub.2).sub.2C.sub.6 H.sub.3 -(3)-Cl(2)-CH.sub.3 NH.sub.2 H 27091 (CH.sub.2).sub.2C.sub.6 H.sub.3 -(3,4)-(OCH.sub.3).sub.2 NH.sub.2 H 220-22592 (CH.sub.2).sub.2C.sub.6 H.sub.4 -(2)-Cl NH.sub.2 H above 27093 C.sub.6 H.sub.3 -(3,4)-Cl.sub.2 NH.sub.2 H above 27094 CH.sub.2COOCH.sub.3 NH.sub.2 H above 27095 CH.sub.2COOC.sub.2 H.sub.5 NH.sub.2 H96 NH.sub.2 NH.sub.2 H 280-28597 N(CH.sub.3).sub.2 NH.sub.2 H98 N(C.sub.2 H.sub.5).sub.2 NH.sub.2 H99 H N(CH.sub.3).sub.2 H 228-235100 H N(C.sub.2 H.sub.5).sub.2 H 119-123101 H N(n-C.sub.3 H.sub.7).sub.2 2 H102 H N(n-C.sub.4 H.sub.9).sub.2 2 H103 H ##STR30## H 245-249104 H ##STR31## H 267-269105 H ##STR32## H106 H ##STR33## H 280-284107 H ##STR34## H108 H ##STR35## H109 CH.sub.3 NH.sub.2 CH.sub.3 298110 C.sub.2 H.sub.5 NH.sub.2 CH.sub.3111 iso-C.sub.3 H.sub.7 NH.sub.2 CH.sub.3112 CH.sub.2 CHCH.sub.2 NH.sub.2 CH.sub.3113 Cyclo-C.sub.6 H.sub.11 NH.sub.2 CH.sub.3114 CH.sub.2 CH.sub.2 OH NH.sub.2 CH.sub.3115 CH.sub.2 CH.sub.2 OCH.sub.3 NH.sub.2 CH.sub.3116 CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CH.sub.3117 C.sub.6 H.sub.5 NH.sub.2 CH.sub.3118 C.sub.6 H.sub.4 -(4)-OCH.sub.3 NH.sub.2 CH.sub.3119 C.sub.6 H.sub.4 -(2)-CH.sub.3 NH.sub.2 CH.sub.3120 Pyrid-3-yl NH.sub.2 CH.sub.3121 NH.sub.2 NH.sub.2 CH.sub.3122 H N(CH.sub.3).sub.2 CH.sub.3123 H N(C.sub.2 H.sub.5).sub.2 CH.sub.3124 H ##STR36## CH.sub.3125 H ##STR37## CH.sub.3126 CH.sub.3 NH.sub.2 C.sub.6 H.sub.5127 C.sub.2 H.sub.5 NH.sub.2 C.sub.6 H.sub.5128 iso-C.sub.3 H.sub.7 NH.sub.2 C.sub.6 H.sub.5129 CH.sub.2 CHCH.sub.2 NH.sub.2 C.sub.6 H.sub.5130 CH.sub.2 CH.sub.2 OH NH.sub.2 C.sub.6 H.sub.5131 CH.sub.2 CH.sub.2 OCH.sub.3 NH.sub.2 C.sub.6 H.sub.5132 CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 C.sub.6 H.sub.5133 C.sub.6 H.sub.5 NH.sub.2 C.sub.6 H.sub.5134 C.sub.6 H.sub.4 -(4)-OCH.sub.3 NH.sub.2 C.sub.6 H.sub.5135 C.sub.6 H.sub.4 -(4)-CN NH.sub.2 C.sub.6 H.sub.5136 NH.sub.2 NH.sub.2 C.sub.6 H.sub.5137 H N(CH.sub.3).sub.2 C.sub.6 H.sub.5138 H N(C.sub.2 H.sub.5).sub.2 C.sub.6 H.sub.5139 H ##STR38## C.sub.6 H.sub.5140 H ##STR39## C.sub.6 H.sub.5141 (CH.sub.2).sub.3OCH.sub.2 C.sub.6 H.sub.5 NH.sub.2 H 149142 (CH.sub.2).sub.3O(CH.sub.2).sub.2OC.sub.6 H.sub.5 NH.sub.2 H 132__________________________________________________________________________
EXAMPLE 143
4-Chloro-3-cyano-2-dimethylformamidino-5-formyl-1-methylpyrrole
364 ml of phosphoryl chloride (POCl.sub.3) were added dropwise at 0.degree. to 5.degree. C. to 1.5 1 of DMF. After one hour at 0.degree. to 5.degree. C., a solution of 137 g of 2-amino-3-cyano-1-methylpyrrolin-4-one (Example 1) in 1.5 1 of DMF was added dropwise to the reaction mixture (exothermic reaction with temperature rising to 40.degree. C.). After the mixture had been stirred at 100.degree. C. for 4 hours, it was cooled to room temperature, hydrolyzed with 5 l of water and adjusted to pH 8 to 9 with 50% concentrated sodium hydroxide solution. The beige-colored precipitate was filtered off with suction and dried in an oven at 50.degree. C. 180 g (75% of theory) of the compound of the formula ##STR40## of melting point 150.degree. to 152.degree. C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.
EXAMPLE 144
4-Bromo-3-cyano-2-dimethylformamidino-5-formyl-1-methylpyrrole
172 g of phosphoryl bromide (POBr.sub.3) were added dropwise at 0.degree. to 10.degree. C. to 200 ml of DMF. The mixture was stirred for 5 minutes and then a further 100 ml of DMF were added. 27.4 g of 2-amino-3-cyano-1-methylpyrrolin-4-one (Example 1) were introduced a little at a time into the cooled mixture. After the exothermic reaction had subsided, the reaction solution was stirred at 70.degree. C. for 2 hours and then poured into 2 kg of ice-water. The suspension was stirred at room temperature for 8 hours. The precipitate was then filtered off with suction, washed and dried in an oven at 50.degree. C. 12.6 g (22%) of the compound of the formula ##STR41## of melting point 180.degree. to 184.degree. C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.
The compounds listed in Table 2 are obtained in a similar manner.
TABLE 2______________________________________ ##STR42##Example Melting pointNo. L.sup.1 L.sup.2 L.sup.3 [.degree.C.]______________________________________145 C.sub.2 H.sub.5 Cl CHO146 n-C.sub.3 H.sub.7 Cl CHO147 iso-C.sub.3 H.sub.7 Cl CHO 136-139148 n-C.sub.4 H.sub.9 Cl CHO149 iso-C.sub.4 H.sub.9 Cl CHO150 sec-C.sub.4 H.sub.9 Cl CHO151 n-C.sub.5 H.sub.11 Cl CHO152 Neo-C.sub.5 H.sub.11 Cl CHO153 n-C.sub.6 H.sub.13 Cl CHO154 n-C.sub.7 H.sub.15 Cl CHO155 n-C.sub.8 H.sub.17 Cl CHO156 n-C.sub.9 H.sub.19 Cl CHO157 n-C.sub.10 H.sub.21 Cl CHO158 n-C.sub.11 H.sub.23 Cl CHO159 n-C.sub.12 H.sub.25 Cl CHO160 n-C.sub.13 H.sub.27 Cl CHO161 n-C.sub.14 H.sub.29 Cl CHO162 n-C.sub.15 H.sub.31 Cl CHO163 n-C.sub. 16 H.sub.33 Cl CHO164 n-C.sub.17 H.sub.35 Cl CHO165 n-C.sub.18 H.sub.37 Cl CHO166 n-C.sub.19 H.sub.39 Cl CHO167 n-C.sub.20 H.sub.41 Cl CHO168 Cyclo-C.sub.3 H.sub.5 Cl CHO169 Cyclo-C.sub.4 H.sub.7 Cl CHO170 Cyclo-C.sub.5 H.sub.9 Cl CHO171 Cyclo-C.sub.6 H.sub.11 Cl CHO172 Cyclo-C.sub.7 H.sub.13 Cl CHO173 Cyclo-C.sub.8 H.sub.15 Cl CHO174 Cyclo-C.sub.9 H.sub.17 Cl CHO175 Cyclo-C.sub.10 H.sub.19 Cl CHO176 CH.sub.2 CH.sub.2 Cl Cl CHO 119-123177 CH.sub.2 CH.sub.2 OCH.sub.3 Cl CHO178 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 Cl CHO179 CH.sub.2 CH.sub.2 NCHN(CH.sub.3).sub.2 Cl CHO180 CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2 Cl CHO181 CH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2 Cl CHO182 CH.sub.2 CH.sub.2 SCH.sub.3 Cl CHO183 CH.sub.2 CH.sub.2 SC.sub.2 H.sub.5 Cl CHO184 (CH.sub.2).sub.3 Cl Cl CHO185 (CH.sub.2).sub.3 OCH.sub.3 Cl CHO186 (CH.sub.2).sub.3 OC.sub.2 H.sub.5 Cl CHO187 (CH.sub.2).sub.3 NCHN(CH.sub.3).sub.2 Cl CHO188 (CH.sub.2).sub.3 N(CH.sub.3).sub.2 Cl CHO189 (CH.sub.2).sub.3 N(C.sub.2 H.sub.5).sub.2 Cl CHO190 (CH.sub.2).sub.3 SCH.sub.3 Cl CHO191 (CH.sub.2).sub.3 SC.sub.2 H.sub.5 Cl CHO192 CH.sub.2 C.sub.6 H.sub.5 Cl CHO193 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 Cl CHO194 CH(CH.sub.3)C.sub.6 H.sub.5 Cl CHO195 CH(C.sub.6 H.sub.5).sub.2 Cl CHO196 C.sub.6 H.sub.5 Cl CHO 175-176197 C.sub.6 H.sub.4 -(2)-Cl Cl CHO198 C.sub.6 H.sub.4 -(3)-Cl Cl CHO199 C.sub.6 H.sub.4 -(4)-Cl Cl CHO200 C.sub.6 H.sub.4 -(2)-OCH.sub.3 Cl CHO201 C.sub.6 H.sub.4 -(3)-OCH.sub.3 Cl CHO 123-130202 C.sub.6 H.sub.4 -(4)-OCH.sub.3 Cl CHO 140-146203 C.sub.6 H.sub.4 -(2)-OC.sub.2 H.sub.5 Cl CHO204 C.sub.6 H.sub.4 -(3)-OC.sub.2 H.sub.5 Cl CHO205 C.sub.6 H.sub.4 -(4)-OC.sub.2 H.sub.5 Cl CHO206 C.sub.6 H.sub. 4 -(2)-NO.sub.2 Cl CHO207 C.sub.6 H.sub.4 -(3)-NO.sub.2 Cl CHO208 C.sub.6 H.sub.4 -(4)-NO.sub.2 Cl CHO209 CH.sub.2COOCH.sub.3 Cl CHO210 CH.sub.2COOC.sub.2 H.sub.5 Cl CHO211 NCHN(CH.sub.3).sub.2 Cl CHO 183212 N(CH.sub.3).sub.2 Cl CHO213 N(C.sub.2 H.sub.5).sub.2 Cl CHO214 C.sub.2 H.sub.5 Br CHO215 n-C.sub.3 H.sub.7 Br CHO216 iso-C.sub.3 H.sub.7 Br CHO217 n-C.sub.4 H.sub.9 Br CHO218 n-C.sub.13 H.sub.27 Br CHO219 Cyclo-C.sub.6 H.sub.11 Br CHO220 C.sub.6 H.sub.5 Br CHO221 C.sub.2 H.sub.4 Br Br CHO222 NCHN(CH.sub.3).sub.2 Br CHO223 N(CH.sub.3).sub.2 Br CHO224 N(C.sub.2 H.sub.5).sub.2 Br CHO225 CH.sub.3 Cl CH.sub.3226 C.sub.2 H.sub.5 Cl CH.sub.3227 iso-C.sub.3 H.sub.7 Cl CH.sub.3228 CH.sub.2 CHCH.sub.2 Cl CH.sub.3229 Cyclo-C.sub.6 H.sub.11 Cl CH.sub.3230 CH.sub.2 CH.sub.2 Cl Cl CH.sub.3231 CH.sub.2 CH.sub.2 OCH.sub.3 Cl CH.sub.3232 CH.sub.2 C.sub.6 H.sub.5 Cl CH.sub.3233 C.sub.6 H.sub.5 Cl CH.sub.3234 Pyrid-3-yl Cl CH.sub.3235 CH.sub.3 Br CH.sub.3236 C.sub.2 H.sub.5 Br CH.sub.3237 iso-C.sub.3 H.sub.7 Br CH.sub.3238 CH.sub.2 CHCH.sub.2 Br CH.sub.3239 Cyclo-C.sub.6 H.sub.11 Br CH.sub.3240 CH.sub.2 CH.sub.2 Br Br CH.sub.3241 CH.sub.2 CH.sub.2 OCH.sub.3 Br CH.sub.3242 CH.sub.2 C.sub.6 H.sub.5 Br CH.sub.3243 C.sub.6 H.sub.5 Br CH.sub.3244 Pyrid-3-yl Br CH.sub.3245 CH.sub.3 Cl C.sub.6 H.sub.5246 C.sub.2 H.sub.5 Cl C.sub.6 H.sub.5247 iso-C.sub.3 H.sub.7 Cl C.sub.6 H.sub.5248 CH.sub.2 CHCH.sub.2 Cl C.sub.6 H.sub.5249 Cyclo-C.sub.6 H.sub.11 Cl C.sub.6 H.sub.5250 CH.sub.2 CH.sub.2 Cl Cl C.sub.6 H.sub.5251 CH.sub.2 CH.sub.2 OCH.sub.3 Cl C.sub.6 H.sub.5252 CH.sub.2 C.sub.6 H.sub.5 Cl C.sub.6 H.sub.5253 C.sub.6 H.sub.5 Cl C.sub. 6 H.sub.5254 Pyrid-3-yl Cl C.sub.6 H.sub.5255 CH.sub.3 Br C.sub.6 H.sub.5256 C.sub.2 H.sub.5 Br C.sub.6 H.sub.5257 iso-C.sub.3 H.sub.7 Br C.sub.6 H.sub.5258 CH.sub.2 CHCH.sub.2 Br C.sub.6 H.sub.5259 Cyclo-C.sub.6 H.sub.11 Br C.sub.6 H.sub.5260 CH.sub.2 CH.sub.2 Br Br C.sub.6 H.sub.5261 CH.sub.2 CH.sub.2 OCH.sub.3 Br C.sub.6 H.sub.5262 CH.sub.2 C.sub.6 H.sub.5 Br C.sub.6 H.sub.5263 C.sub.6 H.sub.5 Br C.sub.6 H.sub.5264 Pyrid-3-yl Br C.sub.6 H.sub.5______________________________________
EXAMPLE 265
4-Chloro-3-cyano-2-dimethylformamidino-1-methylpyrrole
33 ml of phosphoryl chloride (POCl.sub.3) were added dropwise at 0.degree. to 5.degree. C. to 285 ml of DMF. After 1 hour at 0.degree. to 5.degree. C., 41.1 g of 2-amino-3-cyano-1-methylpyrrolin-4-one (Example 1) were added a little at a time to the reaction solution (exothermic reaction with temperature rising to 40.degree. C.). After the mixture had been stirred at 70.degree. C. for 1 hour it was cooled to room temperature, hydrolyzed with 1.5 l of water and adjusted to pH 7 with 240 g of sodium acetate. The precipitate was filtered off with suction and dried in an oven at 50.degree. C. 40.5 g (75% of theory) of the compound of the formula ##STR43## of melting point 88.degree. C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.
EXAMPLE 266
4-Bromo-3-cyano-2-dimethylformamidino-1-methylpyrrole
70 g of phosphoryl bromide (POBr.sub.3) were added dropwise at 0.degree. to 10.degree. C. to 190 ml of DMF. After one hour at 0.degree. to 5.degree. C., 27 g of 2-amino-3-cyano-1-methylpyrrolin-4-one (Example 1) were added a little at a time to the reaction solution (exothermic reaction with temperature rising to 30.degree. C.). After the mixture had been stirred at 80.degree. C. for 1 hour it was cooled to room temperature, hydrolyzed with 1.5 l of water and adjusted to pH 7 with 160 g of sodium acetate. The precipitate was filtered off with suction and dried in an oven at 50.degree. C. 22.5 g (44% of theory) of the compound of the formula ##STR44## were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.
The compounds listed in the following Table 3 are obtained in a similar manner.
TABLE 3______________________________________ ##STR45##Example Melting pointNo. L.sup.1 L.sup.2 [.degree.C.]______________________________________267 C.sub.2 H.sub.5 Cl268 n-C.sub.3 H.sub.7 Cl269 iso-C.sub.3 H.sub.7 Cl270 n-C.sub.4 H.sub.9 Cl271 iso-C.sub.4 H.sub.9 Cl272 sec-C.sub.4 H.sub.9 Cl273 n-C.sub.5 H.sub.11 Cl274 Neo-C.sub.5 H.sub.11 Cl275 n-C.sub.6 H.sub.13 Cl276 n-C.sub.7 H.sub.15 Cl277 n-C.sub.8 H.sub.17 Cl278 n-C.sub.9 H.sub.19 Cl279 n-C.sub.10 H.sub.21 Cl280 n-C.sub.11 H.sub.23 Cl281 n-C.sub.12 H.sub.25 Cl282 n-C.sub.13 H.sub.27 Cl283 n-C.sub.14 H.sub.29 Cl284 n-C.sub.15 H.sub.31 Cl285 n-C.sub.16 H.sub.33 Cl286 n-C.sub.17 H.sub.35 Cl287 n-C.sub.18 H.sub.37 Cl288 n-C.sub.19 H.sub.39 Cl289 n-C.sub.20 H.sub. 41 Cl290 Cyclo-C.sub.3 H.sub.5 Cl291 Cyclo-C.sub.4 H.sub.7 Cl292 Cyclo-C.sub.5 H.sub.9 Cl293 Cyclo-C.sub.6 H.sub.11 Cl294 Cyclo-C.sub.7 H.sub.13 Cl295 Cyclo-C.sub.8 H.sub.15 Cl296 Cyclo-C.sub.9 H.sub.17 Cl297 Cyclo-C.sub.10 H.sub.19 Cl298 CH.sub.2 CH.sub.2 Cl Cl299 CH.sub.2 CH.sub.2 OCH.sub.3 Cl300 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 Cl301 CH.sub.2 CH.sub.2 NCHN(CH.sub.3).sub.2 Cl302 CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2 Cl303 CH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2 Cl304 CH.sub.2 CH.sub.2 SCH.sub.3 Cl305 CH.sub.2 CH.sub.2 SC.sub.2 H.sub.5 Cl306 (CH.sub.2).sub.3 Cl Cl307 (CH.sub.2).sub.3 OCH.sub.3 Cl308 (CH.sub.2).sub.3 OC.sub.2 H.sub.5 Cl309 (CH.sub.2).sub.3 NCHN(CH.sub.3).sub.2 Cl310 (CH.sub.2).sub.3 N(CH.sub.3).sub.2 Cl311 (CH.sub.2).sub.3 N(C.sub.2 H.sub.5).sub.2 Cl312 (CH.sub.2).sub.3 SCH.sub.3 Cl313 (CH.sub.2).sub.3 SC.sub. 2 H.sub.5 Cl314 CH.sub.2 C.sub.6 H.sub.5 Cl315 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 Cl316 CH(CH.sub.3)C.sub.6 H.sub.5 Cl317 CH(C.sub.6 H.sub.5).sub.2 Cl318 C.sub.6 H.sub.5 Cl319 C.sub.6 H.sub.4 -(2)-Cl Cl320 C.sub.6 H.sub.4 -(3)-Cl Cl321 C.sub.6 H.sub.4 -(4)-Cl Cl322 C.sub.6 H.sub.4 -(2)-OCH.sub.3 Cl323 C.sub.6 H.sub.4 -(3)-OCH.sub.3 Cl324 C.sub.6 H.sub.4 -(4)-OCH.sub.3 Cl325 C.sub.6 H.sub.4 -(2)-OC.sub.2 H.sub.5 Cl326 C.sub.6 H.sub.4 -(3)-OC.sub.2 H.sub.5 Cl327 C.sub.6 H.sub.4 -(4)-OC.sub.2 H.sub.5 Cl328 C.sub.6 H.sub.4 -(2)-NO.sub.2 Cl329 C.sub.6 H.sub.4 -(3)-NO.sub.2 Cl330 C.sub.6 H.sub.4 -(4)-NO.sub.2 Cl331 CH.sub.2COOCH.sub.3 Cl332 CH.sub.2COOC.sub.2 H.sub.5 Cl333 NCHN(CH.sub.3).sub.2 Cl334 N(CH.sub.3).sub.2 Cl335 N(C.sub.2 H.sub.5).sub.2 Cl336 C.sub.2 H.sub.5 Br337 iso-C.sub.3 H.sub.7 Br338 Cyclo-C.sub.6 H.sub.11 Br339 CH.sub.2 CH.sub.2 Br Br340 CH.sub.2 C.sub.6 H.sub.5 Br341 C.sub.6 H.sub.5 Br342 NCHN(CH.sub.3).sub.2 Br343 N(CH.sub.3).sub.2 Br344 N(C.sub.2 H.sub.5).sub.2 Br______________________________________
EXAMPLE 345
2-Amino-4-chloro-3-cyano-5-formyl-1-methylpyrrole
84.8 g of 4-chloro-3-cyano-2-dimethylformamidino-5-formyl-1-methylpyrrole (Example 143) were dissolved in 50 ml of water and 150 ml of ethanol. To this was added a solution of 15 g of KOH in 150 ml of ethanol, and the mixture was refluxed for 10 minutes. It was then poured into 1 kg of ice-water, the pH was adjusted to 7 with concentrated formic acid, and the precipitate was filtered off with suction, washed and dried in an oven at 50.degree. C. 60.2 g (92% of theory) of the compound of the formula ##STR46## of melting point 282.degree. to 285.degree. C. are obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.
The compounds listed in Table 4 are obtained in a similar manner to Example 345.
TABLE 4______________________________________ ##STR47##Example Melting pointNo. L.sup.1 L.sup.2 L.sup.3 [.degree.C.]______________________________________346 C.sub.2 H.sub.5 Cl CHO347 n-C.sub.3 H.sub.7 Cl CHO348 iso-C.sub.3 H.sub.7 Cl CHO 180-195349 n-C.sub.4 H.sub.9 Cl CHO350 iso-C.sub.4 H.sub.9 Cl CHO351 sec-C.sub.4 H.sub.9 Cl CHO352 n-C.sub.5 H.sub.11 Cl CHO353 Neo-C.sub.5 H.sub.11 Cl CHO354 n-C.sub.6 H.sub.13 Cl CHO355 n-C.sub.7 H.sub.15 Cl CHO356 n-C.sub.8 H.sub.17 Cl CHO357 n-C.sub.9 H.sub.19 Cl CHO358 n-C.sub.10 H.sub.21 Cl CHO359 n-C.sub.11 H.sub.23 Cl CHO360 n-C.sub.12 H.sub.25 Cl CHO361 n-C.sub.13 H.sub.27 Cl CHO362 n-C.sub.14 H.sub.29 Cl CHO363 n-C.sub.15 H.sub.31 Cl CHO364 n-C.sub.16 H.sub.33 Cl CHO365 n-C.sub.17 H.sub.35 Cl CHO366 n-C.sub.18 H.sub.37 Cl CHO367 n-C.sub.19 H.sub.39 Cl CHO368 n-C.sub.20 H.sub.41 Cl CHO369 Cyclo-C.sub.3 H.sub.5 Cl CHO370 Cyclo-C.sub.4 H.sub.7 Cl CHO371 Cyclo-C.sub.5 H.sub.9 Cl CHO372 Cyclo-C.sub.6 H.sub.11 Cl CHO373 Cyclo-C.sub.7 H.sub.13 Cl CHO374 Cyclo-C.sub.8 H.sub.15 Cl CHO375 Cyclo-C.sub.9 H.sub.17 Cl CHO376 Cyclo-C.sub.10 H.sub.19 Cl CHO377 CH.sub.2 CH.sub.2 Cl Cl CHO378 CH.sub.2 CH.sub.2 OCH.sub.3 Cl CHO379 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 Cl CHO380 CH.sub.2 CH.sub.2 NH.sub.2 Cl CHO381 CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2 Cl CHO382 CH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2 Cl CHO383 CH.sub.2 CH.sub.2 SCH.sub.3 Cl CHO384 CH.sub.2 CH.sub.2 SC.sub.2 H.sub.5 Cl CHO385 (CH.sub.2).sub.3 Cl Cl CHO386 (CH.sub.2).sub.3 OCH.sub.3 Cl CHO387 (CH.sub.2).sub.3 OC.sub.2 H.sub.5 Cl CHO388 (CH.sub.2).sub.3 NH.sub.2 Cl CHO389 (CH.sub.2).sub.3 N(CH.sub.3).sub.2 Cl CHO390 (CH.sub.2).sub.3 N(C.sub.2 H.sub.5).sub.2 Cl CHO391 (CH.sub.2).sub.3 SCH.sub.3 Cl CHO392 (CH.sub.2).sub.3 SC.sub.2 H.sub.5 Cl CHO393 CH.sub.2 C.sub.6 H.sub.5 Cl CHO394 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 Cl CHO395 CH(CH.sub.3)C.sub.6 H.sub.5 Cl CHO396 CH(C.sub.6 H.sub.5).sub.2 Cl CHO397 C.sub.6 H.sub.5 Cl CHO 220-226398 C.sub.6 H.sub.4 -(2)-Cl Cl CHO399 C.sub.6 H.sub.4 -(3)-Cl Cl CHO400 C.sub.6 H.sub.4 -(4)-Cl Cl CHO401 C.sub.6 H.sub.4 -(2)-OCH.sub.3 Cl CHO402 C.sub.6 H.sub.4 -(3)-OCH.sub.3 Cl CHO 123-130403 C.sub.6 H.sub.4 -(4)-OCH.sub.3 Cl CHO 140-146404 C.sub.6 H.sub.4 -(2)-OC.sub.2 H.sub.5 Cl CHO405 C.sub.6 H.sub.4 -(3)-OC.sub.2 H.sub.5 Cl CHO406 C.sub.6 H.sub.4 -(4)-OC.sub.2 H.sub.5 Cl CHO407 C.sub.6 H.sub.4 -(2)-NO.sub.2 Cl CHO408 C.sub.6 H.sub.4 -(3)-NO.sub.2 Cl CHO409 C.sub. 6 H.sub.4 -(4)-NO.sub.2 Cl CHO410 CH.sub.2COOCH.sub.3 Cl CHO411 CH.sub.2COOC.sub.2 H.sub.5 Cl CHO412 NH.sub.2 Cl CHO413 N(CH.sub.3).sub.2 Cl CHO414 N(C.sub.2 H.sub.5).sub.2 Cl CHO415 CH.sub.3 Br CHO416 C.sub.2 H.sub.5 Br CHO417 n-C.sub.3 H.sub.7 Br CHO418 iso-C.sub.3 H.sub.7 Br CHO419 n-C.sub.4 H.sub.9 Br CHO420 n-C.sub.13 H.sub.17 Br CHO421 Cyclo-C.sub.6 H.sub.11 Br CHO422 C.sub.6 H.sub.5 Br CHO423 C.sub.2 H.sub.4 Br Br CHO424 NH.sub.2 Br CHO425 N(CH.sub.3).sub.2 Br CHO426 N(C.sub.2 H.sub.5).sub.2 Br CHO427 CH.sub.3 Cl CH.sub.3428 C.sub.2 H.sub.5 Cl CH.sub.3429 n-C.sub.3 H.sub.7 Cl CH.sub.3430 iso-C.sub.3 H.sub.7 Cl CH.sub.3431 n-C.sub.4 H.sub.9 Cl CH.sub.3432 n-C.sub.13 H.sub.17 Cl CH.sub.3433 Cyclo-C.sub.6 H.sub.11 Cl CH.sub.3434 C.sub.6 H.sub.5 Cl CH.sub.3435 C.sub.2 H.sub.4 Br Cl CH.sub.3436 NH.sub. 2 Cl CH.sub.3437 N(CH.sub.3).sub.2 Cl CH.sub.3438 N(C.sub.2 H.sub.5).sub.2 Cl CH.sub.3439 CH.sub.3 Br CH.sub.3440 C.sub.2 H.sub.5 Br CH.sub.3441 n-C.sub.3 H.sub.7 Br CH.sub.3442 iso-C.sub.3 H.sub.7 Br CH.sub.3443 n-C.sub.4 H.sub.9 Br CH.sub.3444 n-C.sub.13 H.sub.17 Br CH.sub.3445 Cyclo-C.sub.6 H.sub.11 Br CH.sub.3446 C.sub.6 H.sub.5 Br CH.sub.3447 C.sub.2 H.sub.4 Br Br CH.sub.3448 NH.sub.2 Br CH.sub.3449 N(CH.sub.3).sub.2 Br CH.sub.3450 N(C.sub.2 H.sub.5).sub.2 Br CH.sub.3451 CH.sub.3 Cl C.sub.6 H.sub.5452 C.sub.2 H.sub.5 Cl C.sub.6 H.sub.5453 n-C.sub.3 H.sub.7 Cl C.sub.6 H.sub.5454 iso-C.sub.3 H.sub.7 Cl C.sub.6 H.sub.5455 n-C.sub.4 H.sub.9 Cl C.sub.6 H.sub.5456 n-C.sub.13 H.sub.17 Cl C.sub.6 H.sub.5457 Cyclo-C.sub.6 H.sub.11 Cl C.sub.6 H.sub.5458 C.sub.6 H.sub.5 Cl C.sub.6 H.sub.5459 C.sub.2 H.sub.4 Br Cl C.sub.6 H.sub.5460 NH.sub.2 Cl C.sub.6 H.sub.5461 N(CH.sub.3).sub.2 Cl C.sub.6 H.sub.5462 N(C.sub.2 H.sub.5).sub.2 Cl C.sub.6 H.sub.5463 CH.sub.3 Br C.sub.6 H.sub.5464 C.sub.2 H.sub.5 Br C.sub.6 H.sub.5465 n-C.sub.3 H.sub.7 Br C.sub.6 H.sub.5466 iso-C.sub.3 H.sub.7 Br C.sub.6 H.sub.5467 n-C.sub.4 H.sub.9 Br C.sub.6 H.sub.5468 n-C.sub.13 H.sub.17 Br C.sub.6 H.sub.5469 Cyclo-C.sub.6 H.sub.11 Br C.sub.6 H.sub.5470 C.sub.6 H.sub.5 Br C.sub.6 H.sub.5471 C.sub.2 H.sub.4 Br Br C.sub.6 H.sub.5472 NH.sub.2 Br C.sub.6 H.sub.5473 N(CH.sub.3).sub.2 Br C.sub.6 H.sub.5474 N(C.sub.2 H.sub.5).sub.2 Br C.sub.6 H.sub.5475 CH.sub.3 Cl H476 C.sub.2 H.sub.5 Cl H477 n-C.sub.3 H.sub.7 Cl H478 iso-C.sub.3 H.sub.7 Cl H479 n-C.sub.4 H.sub.9 Cl H480 n-C.sub.13 H.sub.17 Cl H481 Cyclo-C.sub.6 H.sub.11 Cl H482 C.sub.6 H.sub.5 Cl H483 C.sub.2 H.sub.4 Br Cl H484 NH.sub.2 Cl H485 N(CH.sub.3).sub.2 Cl H486 N(C.sub.2 H.sub.5).sub.2 Cl H487 CH.sub.3 Br H488 C.sub.2 H.sub.5 Br H489 n-C.sub.3 H.sub.7 Br H490 iso-C.sub.3 H.sub.7 Br H491 n-C.sub.4 H.sub.9 Br H492 n-C.sub.13 H.sub.17 Br H493 Cyclo-C.sub.6 H.sub.11 Br H494 C.sub.6 H.sub.5 Br H495 C.sub.2 H.sub.4 Br Br H496 NH.sub.2 Br H497 N(CH.sub.3).sub.2 Br H498 N(C.sub.2 H.sub.5).sub.2 Br H______________________________________
EXAMPLE 499
2-Amino-4-chloro-5-formyl-1-methylpyrrole-3-carboxamide
9.54 g of 4-chloro-3-cyano-2-dimethylformamidino-5-formyl-1-methylpyrrole (Example 143) were refluxed in 100 ml of 5% by weight aqueous sodium hydroxide solution for one hour. After cooling, the precipitate was filtered off with suction, washed and dried. 4.00 g (50% of theory) of the compound of the formula ##STR48## of melting point 217.degree. C. (decomposition) were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are constituent with the structural formula.
The compounds listed in Table 5 are obtained in a similar manner to Example 499.
TABLE 5______________________________________ ##STR49##Example Melting pointNo. L.sup.1 L.sup.2 L.sup.3 [.degree.C.]______________________________________500 C.sub.2 H.sub.5 Cl CHO501 n-C.sub.3 H.sub.7 Cl CHO502 iso-C.sub.3 H.sub.7 Cl CHO503 n-C.sub.4 H.sub.9 Cl CHO504 iso-C.sub.4 H.sub.9 Cl CHO505 sec-C.sub.4 H.sub.9 Cl CHO506 n-C.sub.5 H.sub.11 Cl CHO507 Neo-C.sub.5 H.sub.11 Cl CHO508 n-C.sub.6 H.sub.13 Cl CHO509 n-C.sub.7 H.sub.15 Cl CHO510 n-C.sub.8 H.sub.17 Cl CHO511 n-C.sub.9 H.sub.19 Cl CHO512 n-C.sub.10 H.sub.21 Cl CHO513 n-C.sub.11 H.sub.23 Cl CHO514 n-C.sub.12 H.sub.25 Cl CHO515 n-C.sub.13 H.sub.27 Cl CHO516 n-C.sub.14 H.sub.29 Cl CHO517 n-C.sub.15 H.sub.31 Cl CHO518 n-C.sub.16 H.sub.33 Cl CHO519 n-C.sub.17 H.sub. 35 Cl CHO520 n-C.sub.18 H.sub.37 Cl CHO521 n-C.sub.19 H.sub.39 Cl CHO522 n-C.sub.20 H.sub.41 Cl CHO523 Cyclo-C.sub.3 H.sub.5 Cl CHO524 Cyclo-C.sub.4 H.sub.7 Cl CHO525 Cyclo-C.sub.5 H.sub.9 Cl CHO526 Cyclo-C.sub.6 H.sub.11 Cl CHO527 Cyclo-C.sub.7 H.sub.13 Cl CHO528 Cyclo-C.sub.8 H.sub.15 Cl CHO529 Cyclo-C.sub.9 H.sub.17 Cl CHO530 Cyclo-C.sub.10 H.sub.19 Cl CHO531 CH.sub.2 CH.sub.2 Cl Cl CHO532 CH.sub.2 CH.sub.2 OCH.sub.3 Cl CHO533 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 Cl CHO534 CH.sub.2 CH.sub.2 NH.sub.2 Cl CHO535 CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2 Cl CHO536 CH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2 Cl CHO537 CH.sub.2 CH.sub.2 SCH.sub.3 Cl CHO538 CH.sub.2 CH.sub.2 SC.sub.2 H.sub.5 Cl CHO539 (CH.sub.2).sub.3 Cl Cl CHO540 (CH.sub.2).sub.3 OCH.sub.3 Cl CHO541 (CH.sub.2).sub.3 OC.sub.2 H.sub.5 Cl CHO542 (CH.sub.2).sub.3 NH.sub.2 Cl CHO543 (CH.sub. 2).sub.3 N(CH.sub.3).sub.2 Cl CHO544 (CH.sub.2).sub.3 N(C.sub.2 H.sub.5).sub.2 Cl CHO545 (CH.sub.2).sub.3 SCH.sub.3 Cl CHO546 (CH.sub.2).sub.3 SC.sub.2 H.sub.5 Cl CHO547 CH.sub.2 C.sub.6 H.sub.5 Cl CHO548 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 Cl CHO549 CH(CH.sub.3)C.sub.6 H.sub.5 Cl CHO550 CH(C.sub.6 H.sub.5).sub.2 Cl CHO551 C.sub.6 H.sub.5 Cl CHO552 C.sub.6 H.sub.4 -(2)-Cl Cl CHO553 C.sub.6 H.sub.4 -(3)-Cl Cl CHO554 C.sub.6 H.sub.4 -(4)-Cl Cl CHO555 C.sub.6 H.sub.4 -(2)-OCH.sub.3 Cl CHO556 C.sub.6 H.sub.4 -(3)-OCH.sub.3 Cl CHO557 C.sub.6 H.sub.4 -(4)-OCH.sub.3 Cl CHO558 C.sub.6 H.sub.4 -(2)-OC.sub.2 H.sub.5 Cl CHO559 C.sub.6 H.sub.4 -(3)-OC.sub.2 H.sub.5 Cl CHO560 C.sub.6 H.sub.4 -(4)-OC.sub.2 H.sub.5 Cl CHO561 C.sub.6 H.sub.4 -(2)-NO.sub.2 Cl CHO562 C.sub.6 H.sub.4 -(3)-NO.sub.2 Cl CHO563 C.sub.6 H.sub.4 -(4)-NO.sub.2 Cl CHO564 CH.sub. 2COOCH.sub.3 Cl CHO565 CH.sub.2COOC.sub.2 H.sub.5 Cl CHO566 NH.sub.2 Cl CHO567 N(CH.sub.3).sub.2 Cl CHO568 N(C.sub.2 H.sub.5).sub.2 Cl CHO569 CH.sub.3 Br CHO570 C.sub.2 H.sub.5 Br CHO571 n-C.sub.3 H.sub.7 Br CHO572 iso-C.sub.3 H.sub.7 Br CHO573 n-C.sub.4 H.sub.9 Br CHO574 n-C.sub.13 H.sub.17 Br CHO575 Cyclo-C.sub.6 H.sub.11 Br CHO576 C.sub.6 H.sub.5 Br CHO577 C.sub.2 H.sub.4 Br Br CHO578 NH.sub.2 Br CHO579 N(CH.sub.3).sub.2 Br CHO580 N(C.sub.2 H.sub.5).sub.2 Br CHO581 CH.sub.3 Cl CH.sub.3582 C.sub.2 H.sub.5 Cl CH.sub.3583 n-C.sub.3 H.sub.7 Cl CH.sub.3584 iso-C.sub.3 H.sub.7 Cl CH.sub.3585 n-C.sub.4 H.sub.9 Cl CH.sub.3586 n-C.sub.13 H.sub.17 Cl CH.sub.3587 Cyclo-C.sub.6 H.sub.11 Cl CH.sub.3588 C.sub.6 H.sub.5 Cl CH.sub.3589 C.sub.2 H.sub.4 Cl Cl CH.sub.3590 NH.sub.2 Cl CH.sub.3591 N(CH.sub.3).sub.2 Cl CH.sub.3592 N(C.sub.2 H.sub.5).sub.2 Cl CH.sub.3593 CH.sub.3 Br CH.sub.3594 C.sub.2 H.sub.5 Br CH.sub.3595 n-C.sub.3 H.sub.7 Br CH.sub.3596 iso-C.sub.3 H.sub.7 Br CH.sub.3597 n-C.sub.4 H.sub.9 Br CH.sub.3598 n-C.sub.13 H.sub.17 Br CH.sub.3599 Cyclo-C.sub.6 H.sub.11 Br CH.sub.3600 C.sub.6 H.sub.5 Br CH.sub.3601 C.sub.2 H.sub.4 Br Br CH.sub.3602 NH.sub.2 Br CH.sub.3603 N(CH.sub.3).sub.2 Br CH.sub.3604 N(C.sub.2 H.sub.5).sub.2 Br CH.sub.3605 CH.sub.3 Cl C.sub.6 H.sub.5606 C.sub.2 H.sub.5 Cl C.sub.6 H.sub.5607 n-C.sub.3 H.sub.7 Cl C.sub.6 H.sub.5608 iso-C.sub.3 H.sub.7 Cl C.sub.6 H.sub.5609 n-C.sub.4 H.sub.9 Cl C.sub.6 H.sub.5610 n-C.sub.13 H.sub.17 Cl C.sub.6 H.sub.5611 Cyclo-C.sub.6 H.sub.11 Cl C.sub.6 H.sub.5612 C.sub.6 H.sub.5 Cl C.sub.6 H.sub.5613 C.sub.2 H.sub.4 Cl Cl C.sub.6 H.sub.5614 NH.sub.2 Cl C.sub.6 H.sub.5615 N(CH.sub.3).sub.2 Cl C.sub.6 H.sub.5616 N(C.sub.2 H.sub.5).sub.2 Cl C.sub.6 H.sub.5617 CH.sub.3 Br C.sub.6 H.sub.5618 C.sub.2 H.sub.5 Br C.sub.6 H.sub.5619 n-C.sub.3 H.sub.7 Br C.sub.6 H.sub.5620 iso-C.sub.3 H.sub.7 Br C.sub.6 H.sub.5621 n-C.sub.4 H.sub.9 Br C.sub.6 H.sub.5622 n-C.sub.13 H.sub.17 Br C.sub.6 H.sub.5623 Cyclo-C.sub.6 H.sub.11 Br C.sub.6 H.sub.5624 C.sub.6 H.sub.5 Br C.sub.6 H.sub.5625 C.sub.2 H.sub.4 Br Br C.sub.6 H.sub.5626 NH.sub.2 Br C.sub.6 H.sub.5627 N(CH.sub.3).sub.2 Br C.sub.6 H.sub.5628 N(C.sub.2 H.sub.5).sub.2 Br C.sub.6 H.sub.5629 CH.sub.3 Cl H630 C.sub.2 H.sub.5 Cl H631 n-C.sub.3 H.sub.7 Cl H632 iso-C.sub.3 H.sub.7 Cl H633 n-C.sub.4 H.sub.9 Cl H634 n-C.sub.13 H.sub.17 Cl H635 Cyclo-C.sub.6 H.sub.11 Cl H636 C.sub.6 H.sub.5 Cl H637 C.sub.2 H.sub.4 OH Cl H638 NH.sub.2 Cl H639 N(CH.sub.3).sub.2 Cl H640 N(C.sub.2 H.sub.5).sub.2 Cl H641 CH.sub.3 Br H642 C.sub.2 H.sub.5 Br H643 n-C.sub.3 H.sub.7 Br H644 iso-C.sub.3 H.sub.7 Br H645 n-C.sub.4 H.sub.9 Br H646 n-C.sub.13 H.sub.17 Br H647 Cyclo-C.sub.6 H.sub.11 Br H648 C.sub.6 H.sub.5 Br H649 C.sub.2 H.sub.4 Br Br H650 NH.sub.2 Br H651 N(CH.sub.3).sub.2 Br H652 N(C.sub.2 H.sub.5).sub.2 Br H______________________________________
EXAMPLE 653
4-Chloro-3-cyano-2-dimethylformamidino-1-methylpyrrole-5-carbaldehyde oxime
7.2 g of 4-chloro-3-cyano-2-dimethylformamidino-5formyl-1-methylpyrrole (Example 143), 4.2 g of hydroxylammonium chloride and 5.1 g of sodium bicarbonate were refluxed in 100 ml of ethanol/water (1:1) for 3 hours. After cooling, 0.5 l of water was added, and the precipitate was filtered off with suction, washed and dried. 5.5 g of the compound of the formula ##STR50## of melting point 220.degree. to 220.degree. C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.
The compounds listed in Table 6 are obtained in a similar manner to Example 653.
TABLE 6______________________________________ ##STR51##Example Melting pointNo. L.sup.1 L.sup.2 [.degree.C.]______________________________________654 C.sub.2 H.sub.5 Cl655 n-C.sub.3 H.sub.7 Cl656 iso-C.sub.3 H.sub.7 Cl657 n-C.sub.4 H.sub.9 Cl658 iso-C.sub.4 H.sub.9 Cl659 sec-C.sub.4 H.sub.9 Cl660 n-C.sub.5 H.sub.11 Cl661 Neo-C.sub.5 H.sub.11 Cl662 n-C.sub.6 H.sub.13 Cl663 n-C.sub.7 H.sub.15 Cl664 n-C.sub.8 H.sub.17 Cl665 n-C.sub.9 H.sub.19 Cl666 n-C.sub.10 H.sub.21 Cl667 n-C.sub.11 H.sub.23 Cl668 n-C.sub.12 H.sub.25 Cl669 n-C.sub.13 H.sub.27 Cl670 n-C.sub.14 H.sub.29 Cl671 n-C.sub.15 H.sub.31 Cl672 n-C.sub.16 H.sub.33 Cl673 n-C.sub.17 H.sub.35 Cl674 n-C.sub.18 H.sub.37 Cl675 n-C.sub.19 H.sub.39 Cl676 n-C.sub.20 H.sub. 41 Cl677 Cyclo-C.sub.3 H.sub.5 Cl678 Cyclo-C.sub.4 H.sub.7 Cl679 Cyclo-C.sub.5 H.sub.9 Cl680 Cyclo-C.sub.6 H.sub.11 Cl681 Cyclo-C.sub.7 H.sub.13 Cl682 Cyclo-C.sub.8 H.sub.15 Cl683 Cyclo-C.sub.9 H.sub.17 Cl684 Cyclo-C.sub.10 H.sub.19 Cl685 CH.sub.2 CH.sub.2 Cl Cl686 CH.sub.2 CH.sub.2 OCH.sub.3 Cl687 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 Cl688 CH.sub.2 CH.sub.2 NCHN(CH.sub.3).sub.2 Cl689 CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2 Cl690 CH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2 Cl691 CH.sub.2 CH.sub.2 SCH.sub.3 Cl692 CH.sub.2 CH.sub.2 SC.sub.2 H.sub.5 Cl693 (CH.sub.2).sub.3 Cl Cl694 (CH.sub.2).sub.3 OCH.sub.3 Cl695 (CH.sub.2).sub.3 OC.sub.2 H.sub.5 Cl696 (CH.sub.2).sub.3 NCHN(CH.sub.3).sub.2 Cl697 (CH.sub.2).sub.3 N(CH.sub.3).sub.2 Cl698 (CH.sub.2).sub.3 N(C.sub.2 H.sub.5).sub.2 Cl699 (CH.sub.2).sub.3 SCH.sub.3 Cl700 (CH.sub.2).sub.3 SC.sub. 2 H.sub.5 Cl701 CH.sub.2 C.sub.6 H.sub.5 Cl702 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 Cl703 CH(CH.sub.3)C.sub.6 H.sub.5 Cl704 CH(C.sub.6 H.sub.5).sub.2 Cl705 C.sub.6 H.sub.5 Cl706 C.sub.6 H.sub.4 -(2)-Cl Cl707 C.sub.6 H.sub.4 -(3)-Cl Cl708 C.sub.6 H.sub.4 -(4)-Cl Cl709 C.sub.6 H.sub.4 -(2)-OCH.sub.3 Cl710 C.sub.6 H.sub.4 -(3)-OCH.sub.3 Cl711 C.sub.6 H.sub.4 -(4)-OCH.sub.3 Cl712 C.sub.6 H.sub.4 -(2)-OC.sub.2 H.sub.5 Cl713 C.sub.6 H.sub.4 -(3)-OC.sub.2 H.sub.5 Cl714 C.sub.6 H.sub.4 -(4)-OC.sub.2 H.sub.5 Cl715 C.sub.6 H.sub.4 -(2)-NO.sub.2 Cl716 C.sub.6 H.sub.4 -(3)-NO.sub.2 Cl717 C.sub.6 H.sub.4 -(4)-NO.sub.2 Cl718 CH.sub.2COOCH.sub.3 Cl719 CH.sub.2COOC.sub.2 H.sub.5 Cl720 NCHN(CH.sub.3).sub.2 Cl721 N(CH.sub.3).sub.2 Cl722 N(C.sub.2 H.sub.5).sub.2 Cl723 CH.sub.3 Br724 C.sub.2 H.sub.5 Br725 n-C.sub.3 H.sub.7 Br726 iso-C.sub.3 H.sub.7 Br727 CH.sub.2 CH.sub.2 NH.sub.2 Br728 CH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2 Br729 Cyclo-C.sub.6 H.sub.11 Br730 C.sub.6 H.sub.5 Br731 C.sub.2 H.sub.4 Br Br732 NH.sub.2 Br733 N(CH.sub.3).sub.2 Br734 N(C.sub.2 H.sub.5).sub.2 Br______________________________________
EXAMPLE 735
2-Acetylamino-4-chloro-3,5-dicyano-1-metylpyrrole
5.0 g of 4-chloro-b 3-cyano-2-dimethylformamidino-1-metylpyrrole-5-carbaldehyde oxime (Example 653) were refluxed in 40 ml of acetic anhydride for 15 hours. After addition of 100 ml of water the reaction mixture was refluxed for a further 10 minutes and then poured into 300 g of ice. The mixture was adjusted to pH 5 with 50% concentrated sodium hydroxide solution, and the precipitate was left to stand at room temperature for two hours and then filtered off with suction, washed and dried. 2.2 g (47% of theory) of the compound of the formula ##STR52## of melting point 180.degree. to 182.degree. C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.
The compounds listed in Table 7 are obtained in a similar manner to Example 735.
TABLE 7______________________________________ ##STR53##Example Melting pointNo. L.sup.1 L.sup.2 [.degree.C.]______________________________________736 C.sub.2 H.sub.5 Cl737 n-C.sub.3 H.sub.7 Cl738 iso-C.sub.3 H.sub.7 Cl739 n-C.sub.4 H.sub.9 Cl740 iso-C.sub.4 H.sub.9 Cl741 sec-C.sub.4 H.sub.9 Cl742 n-C.sub.5 H.sub.11 Cl743 Neo-C.sub.5 H.sub.11 Cl744 n-C.sub.6 H.sub.13 Cl745 n-C.sub.7 H.sub.15 Cl746 n-C.sub.8 H.sub.17 Cl747 n-C.sub.9 H.sub.19 Cl748 n-C.sub.10 H.sub.21 Cl749 n-C.sub.11 H.sub.23 Cl750 n-C.sub.12 H.sub.25 Cl751 n-C.sub.13 H.sub.27 Cl752 n-C.sub.14 H.sub.29 Cl753 n-C.sub.15 H.sub.31 Cl754 n-C.sub.16 H.sub.33 Cl755 n-C.sub.17 H.sub.35 Cl756 n-C.sub.18 H.sub.37 Cl757 n-C.sub.19 H.sub.39 Cl758 n-C.sub.20 H.sub.41 Cl759 Cyclo-C.sub.3 H.sub.5 Cl760 Cyclo-C.sub.4 H.sub.7 Cl761 Cyclo-C.sub.5 H.sub.9 Cl762 Cyclo-C.sub.6 H.sub.11 Cl763 Cyclo-C.sub.7 H.sub.13 Cl764 Cyclo-C.sub.8 H.sub.15 Cl765 Cyclo-C.sub.9 H.sub.17 Cl766 Cyclo-C.sub.10 H.sub.19 Cl767 CH.sub.2 CH.sub.2 Cl Cl768 CH.sub.2 CH.sub.2 OCH.sub.3 Cl769 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 Cl770 CH.sub.2 CH.sub.2 NCHN(CH.sub.3).sub.2 Cl771 CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2 Cl772 CH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2 Cl773 CH.sub.2 CH.sub.2 SCH.sub.3 Cl774 CH.sub.2 CH.sub.2 SC.sub.2 H.sub.5 Cl775 (CH.sub.2).sub.3 Cl Cl776 (CH.sub.2).sub.3 OCH.sub.3 Cl777 (CH.sub.2).sub.3 OC.sub.2 H.sub.5 Cl778 (CH.sub.2).sub.3 NCHN(CH.sub.3).sub.2 Cl779 (CH.sub.2).sub.3 N(CH.sub.3).sub.2 Cl780 (CH.sub.2).sub.3 N(C.sub.2 H.sub.5).sub.2 Cl781 (CH.sub.2).sub.3 SCH.sub.3 Cl782 (CH.sub.2).sub.3 SC.sub.2 H.sub.5 Cl783 CH.sub.2 C.sub.6 H.sub.5 Cl784 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 Cl785 CH(CH.sub.3)C.sub.6 H.sub.5 Cl786 CH(C.sub.6 H.sub.5).sub.2 Cl787 C.sub.6 H.sub.5 Cl788 C.sub.6 H.sub.4 -(2)-Cl Cl789 C.sub.6 H.sub.4 -(3)-Cl Cl790 C.sub.6 H.sub.4 -(4)-Cl Cl791 C.sub.6 H.sub.4 -(2)-OCH.sub.3 Cl792 C.sub.6 H.sub.4 -(3)-OCH.sub.3 Cl793 C.sub.6 H.sub.4 -(4)-OCH.sub.3 Cl794 C.sub.6 H.sub.4 -(2)-OC.sub.2 H.sub.5 Cl795 C.sub.6 H.sub.4 -(3)-OC.sub.2 H.sub.5 Cl796 C.sub.6 H.sub.4 -(4)-OC.sub.2 H.sub.5 Cl797 C.sub.6 H.sub.4 -(2)-NO.sub.2 Cl798 C.sub.6 H.sub.4 -(3)-NO.sub.2 Cl799 C.sub.6 H.sub.4 -(4)-NO.sub.2 Cl800 CH.sub.2COOCH.sub.3 Cl801 CH.sub.2COOC.sub.2 H.sub.5 Cl802 NCHN(CH.sub.3).sub.2 Cl803 N(CH.sub.3).sub.2 Cl804 N(C.sub.2 H.sub.5).sub.2 Cl805 CH.sub.3 Br806 C.sub.2 H.sub.5 Br807 n-C.sub.3 H.sub.7 Br808 iso-C.sub.3 H.sub.7 Br809 n-C.sub.4 H.sub.9 Br810 n-C.sub.13 H.sub.17 Br811 Cyclo-C.sub.6 H.sub.11 Br812 C.sub.6 H.sub.5 Br813 C.sub.2 H.sub.4 Br Br814 N(CH.sub.3).sub.2 Br815 N(C.sub.2 H.sub.5).sub.2 Br______________________________________
EXAMPLE 816
4-chloro-3,5-dicyano-2-dimethylformamidino-1-methylpyrrole
4.8 g of 4-chloro-3-cyano-2-dimethylformamidino-5-formyl-1-methylpyrrole (Example 143) and 1.8 g of copper(I) cyanide in 50 ml of DMF were refluxed for 5 days. The reaction mixture was cooled and then filtered, and 200 ml of water were added to the filtrate. The precipitate was filtered off with suction, washed and dried. 1.4 g (30% of theory) of the compound of the formula ##STR54## of melting point 180.degree. to 184.degree. C. were obtained The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.
The compounds listed in Table 8 are obtained in a similar manner to Example 816.
TABLE 8______________________________________ ##STR55##Example Melting pointNo. L.sup.1 L.sup.2 [.degree.C.]______________________________________816 CH.sub.3 Cl817 C.sub.2 H.sub.5 Cl818 n-C.sub.3 H.sub.7 Cl819 iso-C.sub.3 H.sub.7 Cl820 n-C.sub.4 H.sub.9 Cl821 iso-C.sub.4 H.sub.9 Cl822 sec-C.sub.4 H.sub.9 Cl823 n-C.sub.5 H.sub.11 Cl824 Neo-C.sub.5 H.sub.11 Cl825 n-C.sub.6 H.sub.13 Cl826 n-C.sub.7 H.sub.15 Cl827 n-C.sub.8 H.sub.17 Cl828 n-C.sub.9 H.sub.19 Cl829 n-C.sub.10 H.sub.21 Cl830 n-C.sub.11 H.sub.23 Cl831 n-C.sub.12 H.sub.25 Cl832 n-C.sub.13 H.sub.27 Cl833 n-C.sub.14 H.sub.29 Cl834 n-C.sub.15 H.sub.31 Cl835 n-C.sub.16 H.sub.33 Cl836 n-C.sub.17 H.sub.35 Cl837 n-C.sub.18 H.sub.37 Cl838 n-C.sub.19 H.sub.39 Cl839 n-C.sub.20 H.sub.41 Cl840 Cyclo-C.sub.3 H.sub.5 Cl841 Cyclo-C.sub.4 H.sub.7 Cl842 Cyclo-C.sub.5 H.sub.9 Cl843 Cyclo-C.sub.6 H.sub.11 Cl844 Cyclo-C.sub.7 H.sub.13 Cl845 Cyclo-C.sub.8 H.sub.15 Cl846 Cyclo-C.sub.9 H.sub.17 Cl847 Cyclo-C.sub.10 H.sub.19 Cl848 CH.sub.2C.sub.6 H.sub.5 Cl849 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 Cl850 CH(CH.sub.3).sub.2 C.sub.6 H.sub.5 Cl851 CH(C.sub.6 H.sub.5).sub.2 Cl852 C.sub.6 H.sub.5 Cl______________________________________
EXAMPLE 853
5-Acetyl-2-acetylamino-4-acetyloxy-3-cyano-1-methylpyrrole
4.11 g of 2-amino-3-cyano-1-methylpyrrolin-4-one (Example 1) and 4.92 g of sodium acetate were refluxed in 50 ml of acetic anhydride for one hour. 150 ml of water were added and the mixture was then boiled for a further 30 minutes and then cooled to room temperature. The precipitate was filtered off with suction, washed and dried. 6.7 g (85% of theory) of the compound of the formula ##STR56## of melting point 140.degree. to 141.degree. C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.
The compounds listed in Table 9 are obtained in a similar manner to Example 853
TABLE 9__________________________________________________________________________ ##STR57##Example Melting pointNo. L.sup.1 L.sup.2 L.sup.3 [.degree.C.]__________________________________________________________________________853 CH.sub.3 COCH.sub.3 CH.sub.3854 C.sub.2 H.sub.5 COCH.sub.3 CH.sub.3855 n-C.sub.3 H.sub.7 COCH.sub.3 CH.sub.3856 iso-C.sub.3 H.sub.7 COCH.sub.3 CH.sub.3857 n-C.sub.4 H.sub.9 COCH.sub.3 CH.sub.3858 iso-C.sub.4 H.sub.9 COCH.sub.3 CH.sub.3859 sec-C.sub.4 H.sub.9 COCH.sub.3 CH.sub.3860 n-C.sub.5 H.sub.11 COCH.sub.3 CH.sub.3861 Neo-C.sub.5 H.sub.11 COCH.sub.3 CH.sub.3862 n-C.sub.6 H.sub.13 COCH.sub.3 CH.sub.3863 n-C.sub.7 H.sub.15 COCH.sub.3 CH.sub.3864 n-C.sub.8 H.sub.17 COCH.sub.3 CH.sub.3865 n-C.sub.9 H.sub.19 COCH.sub.3 CH.sub.3866 n-C.sub.10 H.sub.21 COCH.sub.3 CH.sub.3867 n-C.sub.11 H.sub. 23 COCH.sub.3 CH.sub.3868 n-C.sub.12 H.sub.25 COCH.sub.3 CH.sub.3869 n-C.sub.13 H.sub.27 COCH.sub.3 CH.sub.3870 n-C.sub.14 H.sub.29 COCH.sub.3 CH.sub.3871 n-C.sub.15 H.sub.31 COCH.sub.3 CH.sub.3872 n-C.sub.16 H.sub.33 COCH.sub.3 CH.sub.3873 n-C.sub.17 H.sub.35 COCH.sub.3 CH.sub.3874 n-C.sub.18 H.sub.37 COCH.sub.3 CH.sub.3875 n-C.sub.19 H.sub.39 COCH.sub.3 CH.sub.3876 n-C.sub.20 H.sub.41 COCH.sub.3 CH.sub.3877 CH.sub.2 CHCH.sub.2 COCH.sub.3 CH.sub.3878 CH.sub.2 OCH COCH.sub.3 CH.sub.3879 Cyclo-C.sub.3 H.sub.5 COCH.sub.3 CH.sub.3880 Cyclo-C.sub.4 H.sub.7 COCH.sub.3 CH.sub.3881 Cyclo-C.sub.6 H.sub.11 COCH.sub.3 CH.sub.3882 Cyclo-C.sub.7 H.sub.13 COCH.sub.3 CH.sub.3883 Cyclo-C.sub.8 H.sub.15 COCH.sub.3 CH.sub.3884 Cyclo-C.sub.9 H.sub.17 COCH.sub.3 CH.sub.3885 Cyclo-C.sub.10 H.sub.19 COCH.sub.3 CH.sub.3886 CH.sub.2 CH.sub.2 OCOCH.sub.3 COCH.sub.3 CH.sub.3887 CH.sub.2 CH.sub.2 OCH.sub.3 COCH.sub.3 CH.sub.3888 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 COCH.sub.3 CH.sub.3889 CH.sub.2 CH.sub.2 NHCOCH.sub.3 COCH.sub.3 CH.sub.3890 CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2 COCH.sub.3 CH.sub.3891 CH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2 COCH.sub.3 CH.sub.3892 CH.sub.2 CH.sub.2 SCH.sub.3 COCH.sub.3 CH.sub.3893 CH.sub.2 CH.sub.2 SC.sub.2 H.sub.5 COCH.sub.3 CH.sub.3894 (CH.sub.2).sub.3 OCOCH.sub.3 COCH.sub.3 CH.sub.3895 (CH.sub.2).sub.3 OCH.sub.3 COCH.sub.3 CH.sub.3896 (CH.sub.2).sub.3 OC.sub.2 H.sub.5 COCH.sub.3 CH.sub.3897 (CH.sub.2).sub.3 NHCOCH.sub.3 COCH.sub.3 CH.sub.3898 (CH.sub.2).sub.3 N(CH.sub.3).sub.2 COCH.sub.3 CH.sub.3899 (CH.sub.2).sub.3 N(C.sub.2 H.sub.5).sub.2 COCH.sub.3 CH.sub.3900 (CH.sub.2).sub.3 SCH.sub.3 COCH.sub.3 CH.sub.3901 (CH.sub.2).sub.3 SC.sub.2 H.sub.5 COCH.sub.3 CH.sub.3902 CH.sub.2 C.sub.6 H.sub.5 COCH.sub.3 CH.sub.3903 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 COCH.sub.3 CH.sub.3904 CH(CH.sub.3 )C.sub.6 H.sub.5 COCH.sub.3 CH.sub.3905 CH(C.sub.6 H.sub.5).sub.2 COCH.sub.3 CH.sub.3906 C.sub.6 H.sub.5 COCH.sub.3 CH.sub.3907 C.sub.6 H.sub.4 -(2)-Cl COCH.sub.3 CH.sub.3908 C.sub.6 H.sub.4 -(3)-Cl COCH.sub.3 CH.sub.3909 C.sub.6 H.sub.4 -(4)-Cl COCH.sub.3 CH.sub.3910 C.sub.6 H.sub.4 -(2)-NO.sub.2 COCH.sub.3 CH.sub.3911 C.sub.6 H.sub.4 -(3)-NO.sub.2 COCH.sub.3 CH.sub.3912 C.sub.6 H.sub.4 -(4)-NO.sub.2 COCH.sub.3 CH.sub.3913 C.sub.6 H.sub.4 -(2)-CN COCH.sub.3 CH.sub.3914 C.sub.6 H.sub.4 -(3)-CN COCH.sub.3 CH.sub.3915 C.sub.6 H.sub.4 -(4)-CN COCH.sub.3 CH.sub.3916 C.sub.6 H.sub.4 -(2)-COOCH.sub.3 COCH.sub.3 CH.sub.3917 C.sub.6 H.sub.4 -(3)-COOCH.sub.3 COCH.sub.3 CH.sub.3918 C.sub.6 H.sub.4 -(4)-COOCH.sub.3 COCH.sub.3 CH.sub.3919 Pyrid-2-yl COCH.sub.3 CH.sub.3920 Pyrid-3-yl COCH.sub.3 CH.sub.3921 Pyrid-4-yl COCH.sub.3 CH.sub.3922 CH.sub.2COOCH.sub.3 COCH.sub.3 CH.sub.3923 CH.sub.2COOC.sub.2 H.sub.5 COCH.sub.3 CH.sub.3924 NHCOCH.sub.3 COCH.sub.3 CH.sub.3925 N(CH.sub.3).sub.2 COCH.sub.3 CH.sub.3926 N(C.sub.2 H.sub.5).sub.2 COCH.sub.3 CH.sub.3927 CH.sub.3 CH.sub.3 CH.sub.3928 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3929 iso-C.sub.3 H.sub.7 CH.sub.3 CH.sub.3930 CH.sub.2 CHCH.sub.2 CH.sub.3 CH.sub.3931 Cyclo-C.sub.6 H.sub.11 CH.sub.3 CH.sub.3932 CH.sub.2 CH.sub.2 OCOCH.sub.3 CH.sub.3 CH.sub.3933 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.3 CH.sub.3934 C.sub.6 H.sub.5 CH.sub.3 CH.sub.3935 Pyrid-3-yl CH.sub.3 CH.sub.3936 NHCOCH.sub.3 CH.sub.3 CH.sub.3937 CH.sub.3 C.sub.6 H.sub.5 CH.sub.3938 C.sub.2 H.sub.5 C.sub.6 H.sub.5 CH.sub.3939 iso-C.sub.3 H.sub.7 C.sub.6 H.sub.5 CH.sub.3940 CH.sub.2 CHCH.sub.2 C.sub.6 H.sub.5 CH.sub.3941 CH.sub.2 CH.sub.2 OCOCH.sub.3 C.sub.6 H.sub.5 CH.sub.3942 CH.sub.2 CH.sub.2 OCH.sub.3 C.sub.6 H.sub.5 CH.sub.3943 C.sub.6 H.sub.5 C.sub.6 H.sub.5 CH.sub.3944 C.sub.6 H.sub.4 -(4)-CN C.sub.6 H.sub.5 CH.sub.3945 NHCOCH.sub.3 C.sub.6 H.sub.5 CH.sub.3946 (CH.sub.2).sub.3OCH.sub.2 C.sub.6 H.sub.5 COCH.sub.3 CH.sub.3947 (CH.sub.2).sub.3O(CH.sub.2).sub.2OC.sub.6 H.sub.5 COCH.sub.3 CH.sub.3948 CH.sub.3 COCH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2949 CH.sub.3 COC.sub.6 H.sub.5 C.sub.6 H.sub.5950 CH.sub.3 CO-n-C.sub.6 H.sub.13 n-C.sub.6 H.sub.13__________________________________________________________________________
EXAMPLE 951
4.1 g of 2-amino-3-cyano-1-methylpyrrolin-4-one (Example 1), 4.2 g of hydroxylammonium chloride and 5.1 g of sodium bicarbonate are refluxed in 100 ml of H.sub.2 O/ethanol (1:1) for 3 hours. The mixture was cooled to room temperature and then diluted with H.sub.2 O, and the precipitate was filtered off with suction. 4.2 g (83% of theory) of the compound of the formula ##STR58## of melting point >260.degree. C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.
The compounds listed in the following Table 10 are obtained in a similar manner
TABLE 10__________________________________________________________________________ ##STR59##Example Melting pointNo. L.sup.1 L.sup.2 L.sup.3 [.degree.C.]__________________________________________________________________________952 C.sub.2 H.sub.5 NH.sub.2 H953 n-C.sub.3 H.sub.7 NH.sub.2 H954 iso-C.sub.3 H.sub.7 NH.sub.2 H955 n-C.sub.4 H.sub.9 NH.sub.2 H956 iso-C.sub.4 H.sub.9 NH.sub.2 H957 sec-C.sub.4 H.sub.9 NH.sub.2 H958 n-C.sub.5 H.sub.11 NH.sub.2 H959 Neo-C.sub.5 H.sub.11 NH.sub.2 H960 n-C.sub.6 H.sub.13 NH.sub.2 H961 n-C.sub.7 H.sub.15 NH.sub.2 H962 n-C.sub.8 H.sub.17 NH.sub.2 H963 n-C.sub.9 H.sub.19 NH.sub.2 H964 n-C.sub.10 H.sub.21 NH.sub.2 H965 n-C.sub.11 H.sub.23 NH.sub.2 H966 n-C.sub.12 H.sub.25 NH.sub.2 H967 n-C.sub.13 H.sub.27 NH.sub.2 H968 n-C.sub.14 H.sub. 29 NH.sub.2 H969 n-C.sub.15 H.sub.31 NH.sub.2 H970 n-C.sub.16 H.sub.33 NH.sub.2 H971 n-C.sub.17 H.sub.35 NH.sub.2 H972 n-C.sub.18 H.sub.37 NH.sub.2 H973 n-C.sub.19 H.sub.39 NH.sub.2 H974 n-C.sub.20 H.sub.41 NH.sub.2 H975 CH.sub.2 CHCH.sub.2 NH.sub.2 H976 CH.sub.2 CCH NH.sub.2 H977 Cyclo-C.sub.3 H.sub.5 NH.sub.2 H978 Cyclo-C.sub.4 H.sub.7 NH.sub.2 H979 Cyclo-C.sub.5 H.sub.9 NH.sub.2 H980 Cyclo-C.sub.6 H.sub.11 NH.sub.2 H981 Cyclo-C.sub.7 H.sub.13 NH.sub.2 H982 Cyclo-C.sub.8 H.sub.15 NH.sub.2 H983 Cyclo-C.sub.9 H.sub.17 NH.sub.2 H984 Cyclo-C.sub.10 H.sub.19 NH.sub.2 H985 CH.sub.2 CH.sub.2 OH NH.sub.2 H986 CH.sub.2 CH.sub.2 OCH.sub.3 NH.sub.2 H987 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 NH.sub.2 H988 CH.sub.2 CH.sub.2 NH.sub.2 NH.sub.2 H989 CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2 NH.sub.2 H990 CH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2 NH.sub.2 H991 CH.sub.2 CH.sub.2 SCH.sub.3 NH.sub.2 H992 CH.sub.2 CH.sub.2 SC.sub.2 H.sub.5 NH.sub.2 H993 (CH.sub.2).sub.3 OH NH.sub.2 H994 (CH.sub.2).sub.3 OCH.sub.3 NH.sub.2 H995 (CH.sub.2).sub.3 OC.sub.2 H.sub.5 NH.sub.2 H996 (CH.sub.2).sub.3 NH.sub.2 NH.sub.2 H997 (CH.sub.2).sub.3 N(CH.sub.3).sub.2 NH.sub.2 H998 (CH.sub.2).sub.3 N(C.sub.2 H.sub.5).sub.2 NH.sub.2 H999 (CH.sub.2).sub.3 SCH.sub.3 NH.sub.2 H1000 (CH.sub.2).sub.3 SC.sub.2 H.sub.5 NH.sub.2 H1001 CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 H 205 (dec)1002 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 H 190 (dec)1003 CH(CH.sub.3)C.sub.6 H.sub.5 NH.sub.2 H1004 CH(C.sub.6 H.sub.5).sub.2 NH.sub.2 H1005 C.sub.6 H.sub.5 NH.sub.2 H 210 (dec)1006 C.sub.6 H.sub.4 -(2)-OH NH.sub.2 H1007 C.sub.6 H.sub.4 -(3)-OH NH.sub.2 H1008 C.sub.6 H.sub.4 -(4)-OH NH.sub.2 H1009 C.sub.6 H.sub.4 -(2)-OCH.sub.3 NH.sub.2 H1010 C.sub.6 H.sub.4 -(3)-OCH.sub.3 NH.sub.2 H 240 (dec)1011 C.sub.6 H.sub.4 -(4)-OCH.sub.3 NH.sub.2 H 220 (dec)1012 C.sub.6 H.sub.4 -(2)-OC.sub.2 H.sub.5 NH.sub.2 H1013 C.sub.6 H.sub.4 -(3)-OC.sub.2 H.sub.5 NH.sub.2 H1014 C.sub.6 H.sub.4 -(4)-OC.sub.2 H.sub.5 NH.sub.2 H1015 C.sub.6 H.sub.4 -(2)-Cl NH.sub.2 H1016 C.sub.6 H.sub.4 -(3)-Cl NH.sub.2 H1017 C.sub.6 H.sub.4 -(4)-Cl NH.sub.2 H1018 C.sub.6 H.sub.4 -(2)-NO.sub.2 NH.sub.2 H1019 C.sub.6 H.sub.4 -(3)-NO.sub.2 NH.sub.2 H1020 C.sub.6 H.sub.4 -(4)-NO.sub.2 NH.sub.2 H1021 C.sub.6 H.sub.4 -(2)-NH.sub.2 NH.sub.2 H1022 C.sub.6 H.sub.4 -(3)-NH.sub.2 NH.sub.2 H1023 C.sub.6 H.sub.4 -(4)-NH.sub.2 NH.sub.2 H1024 C.sub.6 H.sub.4 -(2)-CH.sub.3 NH.sub.2 H 190 (dec)1025 C.sub.6 H.sub.4 -(3)-CH.sub.3 NH.sub.2 H1026 C.sub.6 H.sub.4 -(4)-CH.sub.3 NH.sub.2 H1027 C.sub.6 H.sub.4 -(2)-C.sub.2 H.sub. 5 NH.sub.2 H1028 C.sub.6 H.sub.4 -(3)-C.sub.2 H.sub.5 NH.sub.2 H1029 C.sub.6 H.sub.4 -(4)-C.sub.2 H.sub.5 NH.sub.2 H1030 C.sub.6 H.sub.4 -(2)-CN NH.sub.2 H1031 C.sub.6 H.sub.4 -(3)-CN NH.sub.2 H1032 C.sub.6 H.sub.4 -(4)-CN NH.sub.2 H1033 C.sub.6 H.sub.4 -(2)-COOCH.sub.3 NH.sub.2 H1034 C.sub.6 H.sub.4 -(3)-COOCH.sub.3 NH.sub.2 H1035 C.sub.6 H.sub.4 -(4)-COOCH.sub.3 NH.sub.2 H1036 Pyrid-2-yl NH.sub.2 H1037 Pyrid-3-yl NH.sub.2 H1038 Pyrid-4-yl NH.sub.2 H1039 (CH.sub.2).sub.2C.sub.6 H.sub.3 -(3)-Cl-(2)-CH.sub.3 NH.sub.2 H1040 (CH.sub.2).sub.2C.sub.6 H.sub.4 -(3,4)-(OCH.sub.3).sub.2 NH.sub.2 H1041 (CH.sub.2).sub.2C.sub.6 H.sub.3 -(2)-Cl NH.sub.2 H1042 C.sub.6 H.sub.3 -(3,4)-Cl.sub.2 NH.sub.2 H1043 CH.sub.2COOCH.sub.3 NH.sub.2 H1044 CH.sub.2COOC.sub.2 H.sub.5 NH.sub.2 H1045 NH.sub.2 NH.sub.2 H1046 N(CH.sub.3).sub.2 NH.sub.2 H1047 N(C.sub.2 H.sub.5).sub.2 NH.sub.2 H1048 H N(CH.sub.3).sub. 2 H1049 H N(C.sub.2 H.sub.5).sub.2 H1050 H N(n-C.sub.3 H.sub.7).sub.2 H1051 H N(n-C.sub.4 H.sub.9).sub.2 H1052 H ##STR60## H1053 H ##STR61## H1054 H ##STR62## H1055 H ##STR63## H1056 H ##STR64## H1057 H ##STR65## H1058 CH.sub.3 NH.sub.2 CH.sub.31059 C.sub.2 H.sub.5 NH.sub.2 CH.sub.31060 iso-C.sub.3 H.sub.7 NH.sub.2 CH.sub.31061 CH.sub.2 CHCH.sub.2 NH.sub.2 CH.sub.31062 Cyclo-C.sub.6 H.sub.11 NH.sub.2 CH.sub.31063 CH.sub.2 CH.sub.2 OH NH.sub.2 CH.sub.31064 CH.sub.2 CH.sub.2 OCH.sub.3 NH.sub.2 CH.sub.31065 CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 CH.sub.31066 C.sub.6 H.sub.5 NH.sub.2 CH.sub. 31067 C.sub.6 H.sub.4 -(4)-OCH.sub.3 NH.sub.2 CH.sub.31068 C.sub.6 H.sub.4 -(2)-CH.sub.3 NH.sub.2 CH.sub.31069 (3)-Pyridyl NH.sub.2 CH.sub.31070 NH.sub.2 NH.sub.2 CH.sub.31071 H N(CH.sub.3).sub.2 CH.sub.31072 H N(C.sub.2 H.sub.5).sub.2 CH.sub.31073 H ##STR66## CH.sub.31074 H ##STR67## CH.sub.31075 CH.sub.3 NH.sub.2 C.sub.6 H.sub.51076 C.sub.2 H.sub.5 NH.sub.2 C.sub.6 H.sub.51077 iso-C.sub.3 H.sub.7 NH.sub.2 C.sub.6 H.sub.51078 CH.sub.2 CHCH.sub.2 NH.sub.2 C.sub.6 H.sub.51079 CH.sub.2 CH.sub.2 OH NH.sub.2 C.sub.6 H.sub.51080 CH.sub.2 CH.sub.2 OCH.sub.3 NH.sub.2 C.sub.6 H.sub.51081 CH.sub.2 C.sub.6 H.sub.5 NH.sub.2 C.sub.6 H.sub.51082 C.sub.6 H.sub.5 NH.sub.2 C.sub.6 H.sub.51083 C.sub.6 H.sub.4 -(4)-OCH.sub.3 NH.sub.2 C.sub.6 H.sub.51084 C.sub.6 H.sub.4 -(4)-CN NH.sub.2 C.sub.6 H.sub.51085 NH.sub.2 NH.sub.2 C.sub.6 H.sub.51086 H N(CH.sub.3).sub.2 C.sub.6 H.sub.51087 H N(C.sub.2 H.sub.5).sub.2 C.sub.6 H.sub.51088 H ##STR68## C.sub.6 H.sub.51089 H ##STR69## C.sub.6 H.sub.51090 (CH.sub.2).sub.3OCH.sub.2 C.sub.6 H.sub.5 NH.sub.2 H1091 (CH.sub.2).sub.3O(CH.sub.2).sub.2OC.sub.6 H.sub.5 NH.sub.2 H__________________________________________________________________________
EXAMPLE 1092
10.0 g of 3-chloro-4-cyano-5-dimethylformamidino-2-formyl-1-methylpyrrole and 6.1 g of Meldrum's acid were stirred in 100 ml of dimethylformamide and 1 ml of piperidine at 50.degree. C. for 15 hours. 200 ml of water were added and the precipitate was filtered off with suction and dried. 5.2 g (34% of theory) of the compound of the formula ##STR70## of melting point 199.degree. C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.
EXAMPLE 1093
6.6 g of malononitrile were dissolved in 200 ml of n-propanol. To this were added 5 g of sodium acetate and 11.9 g of 4-chloro-3-cyano-2-dimethylformamidino-5-formyl-1-methylpyrrole and the mixture was stirred at room temperature for 8 hours. The precipitate was filtered off with suction, washed with n-propanol and dried. 13.2 g (92% of theory) of the compound of the formula ##STR71## of melting point 180.degree. C. were obtained. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the structural formula.
The compounds listed in the following Table 11 are obtained in a similar manner.
TABLE 11__________________________________________________________________________ ##STR72##Example Melting pointNo. L.sup.1 L.sup.2 L.sup.3 [.degree.C.]__________________________________________________________________________1094 CH.sub.3 CHC(COOCH.sub.3).sub.2 NCHN(CH.sub.3).sub.2 1751095 C.sub.2 H.sub.5 CHC(COOCH.sub.3).sub.2 NCHN(CH.sub.3).sub.21096 C.sub.6 H.sub.5 CHC(COOC.sub.2 H.sub.5).sub.2 NCHN(CH.sub.3).sub.21097 CH(CH.sub.3).sub.2 CHC(COOC.sub.2 H.sub.5).sub.2 NH.sub.21098 C.sub.2 H.sub.5 CHC(CN).sub.2 NCHN(CH.sub.3).sub.21099 n-C.sub.4 H.sub.9 CHC(CN).sub.2 NCHN(CH.sub.3).sub.21100 CH.sub.3 CHC(COOCH.sub.3)(CN) NCHN(CH.sub.3).sub.21101 C.sub.6 H.sub.5 CHC(COOC.sub.2 H.sub.5)(CN) NH.sub.21102 C.sub.6 H.sub.5 CH.sub.2 CHC(COOCH.sub.3)(CN) NCHN(CH.sub.3).sub.21103 C.sub.6 H.sub.5 CHC(COOCH.sub.3)(CN) NH.sub.21104 CH.sub.3 ##STR73## NCHN(CH.sub.3).sub.21105 C.sub.2 H.sub.5 ##STR74## NH.sub.21106 CH.sub.3 CHC(CONHCH.sub.3)(CN) NCHN(CH.sub.3).sub.21107 C.sub.6 H.sub.5 CHC(COCH.sub.3)(CN) NH.sub.21108 Cyclo-C.sub.6 H.sub.11 CHC(COC.sub.6 H.sub.5)(CN) NCHN(CH.sub.3).sub.21109 CH.sub.3 CHC(C.sub.6 H.sub.5)(CN) NCHN(CH.sub.3).sub.21110 CH(CH.sub.3).sub.2 ##STR75## NCHN(CH.sub.3).sub.21111 CH.sub.3 ##STR76## NH.sub.21112 CH(CH.sub.3).sub.2 ##STR77## NH.sub.21113 CH.sub.3 CHCHNO.sub.2 NCHN(CH.sub.3).sub.21114 CH(CH.sub.3).sub.2 CHC(CH.sub.3)NO.sub.2 NCHN(CH.sub.3).sub.2__________________________________________________________________________

Pyrrole derivatives useful as diazo and coupling components

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