Matthias Rehwald

Synthese neuartig substituierter Pyridazin-6(1H)-one

SummaryArylhydrazono acetamides1 react with chloroacetic acid chloride to give N-chloroacetyl derivatives2. Subsequent reaction with pyridines followed by ring closure yield 1-(4-amino-6-oxo-pyridazin-5-yl)-pyridinium chlorides3. Analogously, 1-(6-oxo-pyridazin-5-yl)-pyridinium chloride (5) and 6-oxo-5-pyridinio-pyridazin-4-olate (4) are formed from phenylhydrazono derivatives and pyridine. Treatment of3 and4 with hydrazinium hydrate gives 4,5-diamino-6-oxo-pyridazin-3-carbohydrazides6 and 5-amino-4-hydroxy-pyridazin-6(1H)-one (8). An analogous ring cleavage of3e and5 gives rise to 4,5-diamino- and 5-amino-pyridazin-6(1H)-ones7. On treatment of the pyridinium salts3 with caustic soda in water, nucleophilic addition of the amino group to the pyridinium ring takes place and stable dehydrated products9 are isolated.

New syntheses of 2,4-diaminopyrroles and aminopyrrolinones

SummaryOxazolin-2-ylidene-malononitriles3a–d, obtainable from thioketenaminals and α-halogen-ketones, react with primary and secondary amines to afford 2,4-diamino-pyrroles5a–h. Mercaptobenzen as nucleophilic agent gives the 4-amino-2-phenylthio-pyrrole5j. Analogously, cyano-(3,5-diphenyl-3H-oxazol-2-ylidene)-acetic acid methyl esters were prepared as intermediates for the synthesis of 2-amino-4-oxo-pyrrolines10a–d. The isomeric 4-amino-2-oxo-pyrrolines13a–d can be obtained from 4-amino-2-methoxy-pyrroles, which serves as proof for the position of substituents. The structures were investigated by1H and13C NMR spectroscopy.ZusammenfassungDie Oxazolin-2-yliden-malononitrile3a–d. die aus Thioketenaminalen und α-Halogenketonen erhalten wurden, reagieren mit primären und sekundären Aminen zu den 2,4-Diaminopyrrolen5a–h. Mercaptobenzol als nukleophiles Reagens liefert 4-Amino-2-phenylthiopyrrol (5j). Analog wurden Cyan-(3,5-diphenyl-3H-oxazol-2-yliden)-essigsäuremethylester als Zwischenprodukte für die Synthese der 2-Amino-4-oxo-pyrroline10a–d hergestellt. Die isomeren 4-Amino-2-oxo-pyrroline13a–d können aus den 4-Amino-2-methoxy-pyrrolen11a,b erhalten werden, was als Nachweis für die Position der Substituenten dient. Die Verbindungen wurden1H- und13C NMR-spektroskopisch untersucht.

Synthese von Hetaryl-pyridiniumsalzen und kondensierten 3-Amino-pyrid-2-onen

1-(3-Coumaryl)-pyridinium salts 3 and 1-(3-coumaryl)-tetrahydrothiophenium salts 5 were synthesized from 2-acylphenyl chloro- or bromoacetates 2. 2-Chloro-N1-(3,4-dimethoxyphenyl)-acetamide and substituted 2-chloro-N1-(2-thienyl)-acetamides 8 react with acetyl chloride and pyridine to yield the quinolinyl- and (thieno[2,3-b]pyridin-5-yl)-pyridinium salts 10. Fused thieno[2,3-b]pyridin-ones 19 were formed from N-chloroacetyl-2-aminothiophen-3-carbonitriles 16 with pyridine via Thorpe-Ziegler cyclization and followed by cyclodehydrogenation. In presence of pyridine alkyl 2-chloro-acetylaminobenzoates 21 yield 3-(1-pyridinio)-quinoline-4-olates 23. Zincke-cleavage of 10 and 23 with hydrazinium hydroxide leads to fused 3-amino-pyridine-2-ones 11 and 3-amino-4-hydroxy-quinoline-2-ones 24, respectively. Oxazoloquinolines 25 were synthesized from 24 with acetic anhydride.

Syntheses with pyridinium and sulfonium salts of acylated β-enaminonitriles

SummaryPyridinium and sulfonium salts2a–e which can be prepared from 3-amino-2-(α-haloacetyl)-crotonitriles and 3-amino-2-(α-halo-acetyl)-3-phenyl-acrylonitriles react with malononitrile in the presence of a base to 3-amino-2-pyridinio-phenolates3a,b and 3-amino-2-sulfonio-phenolates3c–e. In an analogous way, 3-amino-2-(diethyloxyphosphoryl)-phenol5a and 3-amino-2-(p-tolyl-sulfonyl)-phenol5b have been prepared. 2,3-Diamino-phenoles6a,b are formed from the pyridinium salts3a,b. The behaviour of the pyridinium salts2a,b towards heterocumulenes has been investigated. Cyanamide leads to the (2-amino-4-hydroxy-pyrid-3-yl)-pyridinium salt8c. Phenylisothiocyanate gives the 3-pyridinio-2-thioxo-pyridin-4-olates9a,b. Carbon disulfide gives rise to 3-pyridinio-2-thioxo-pyridin-4-olate10 or 3-pyridinio-2-thioxo-thiopyran-4-olate11, depending on the substituent at the 6-position. Phenylisocyanate reacts to the pyrimidin-2,4-dione12 with loss of N-methyl-pyridinium chloride. S-methylation of9a and cleavage of the pyridine moiety yields the 3-amino-2-methylthio-pyrid-4-one14. The structures were investigated by1H and13C NMR spectroscopy.ZusammenfassungPyridinium- und Sulfoniumsalze2a–e, die aus 3-Amino-2-(α-halo-acetyl)-crotonsäurenitril und 3-Amino-2-(α-halo-acetyl)-zimtsäurenitril hergestellt werden können, reagieren mit Malonsäuredinitril in Gegenwart einer Base zu 3-Amino-2-pyridinio-phenolaten3a,b und 3-Amino-2-sulfonio-phenolaten3c–e. In Analogie wurden 3-Amino-2-(diethyloxyphosphoryl)-phenol5a und 3-Amino-2-(p-tolyl-sulfonyl)-phenol5b erhalten. 2,3-Diamino-phenole6a,b werden aus den Pyridiniumsalzen3a,b gebildet. Das Verhalten der Pyridiniumsalze2a,b gegenüber Heterokumulenen ist untersucht worden. Cyanamid führt zum (2-Amino-4-hydroxy-pyrid-3-yl)-pyridiniumsalz8c. Phenylisothiocyanat liefert die 3-Pyridinio-2-thioxo-pyridin-4-olate9a,b. In Abhängigkeit vom Substituenten in der Position 6 entsteht bei der Reaktion mit Schwefelkohlenstoff ein 3-Pyridinio-2-thioxo-pyridin-4-olat10 oder ein 3-Pyridinio-2-thioxo-thiopyran-4-olat11. Phenylisocyanat reagiert zum Pyrimidin-2,4-dion12 unter Verlust von N-Methyl-pyridiniumchlorid. S-Methylierung von9a und Spaltung des Pyridiniumringes ergibt das 3-Amino-2-methylthio-pyrid-4-on14. Die Verbindungen wurden1H- und13C-NMR-spektroskopisch untersucht.