Manfred Klade

Dicyanmethylenpyrazolinone und deren Bedeutung als Chromophor. Synthesen mit Nitrilen, 80. Mitt.

Abstract1-Phenyl-2-pyrazolin-5-ones1 a–e react with tetracyanoethylene forming the corresponding dicyanomethylenepyrazolin-5-ones2 a–e. The products are deeply coloured with absorption bands between 550 and 650 nm, but low ε-values and negative solvatochromic effect. By amine-HCN exchange reaction with anilines the red-coloured phenylamino-cyanomethylene-pyrazolinones3–6 are obtained.15N- and13C-NMR-data of2 and quantum-chemical calculations (INDO/S-CI) reveal the extreme polarization and chromophoric properties of the described dicyanomethylene-pyrazolinones.

Thermisch und photochemisch induzierte bildung von polymethinen aus N-alkylaminophenyl-pyrazolinon-malononitrilen. synthesen mit nitrilen, LXXXI

Abstract 4-Dicyanomethylene-3-methyl-1-phenyl-2-pyrazolin-5-one and 3-amino-4-dicyanomethylene-1-phenyl-2-pyrazolin-5-one react with N-alkylanilines to give colourless adducts. By heating or by photolysis elimination of cyanide leads to deeply coloured N-alkylaminophenyl-cyanomethylene-pyrazo-linones, to be classified as heptamethines with absorption maxima from 525 to 560 nm.

Über Dicyanmethylen-aminoindene, Indano-pyridazine und Indano-pyridine. Synthesen mit Nitrilen, 83. Mitt.

Summary1-Dicyanomethylene-3-indanone (1) shows a remarkable reactivity of the carbonyl- and the methylene-function towards nucleophiles. With anilines and phenylhydrazine, resp., the deep-red colored pentamethinecyanines2 and3 are formed, azocoupling leads to indano-pyridazines4. With diphenylformamidines anilinomethylene-indanones5 are obtained in a primary reaction, followed by ring closure and Dimroth-rearrangement to indano-pyridines6.13C- and15N-NMR-spectrocopy is used for confirmation of the structures.

Ein Beitrag zur Chemie des 2,3-Dihydro-3-oxo-benzo[b]thiophen-1,1-dioxids Synthesen mit Nitrilen, 86. Mitt.

Summary2,3-Dihydro-3-oxo-benzo[b]thiophen-1,1-dioxide (1) reacts as CH-acidic component with amidines of orthoesters and anilines resp. to give the anilinomethylene derivates3, 4, and5. With triethyl orthoformiate the hydroxymethylene-compound7 is obtained. Anilino- and phenylhydrazino derivates8 and9 prove the carbonyl activity of1, azo-coupling leads to10, whereas treatment of1 with sulfur and malononitrile yields the benzo[b]thieno[2,3-d]thiophenes11. Introduction of substituents with active NH-functions in position 2 of the dicyanomethylene-product2, such as azocoupling, reaction with phenyl isocyanate and formation of enamines, leads to ring closure reactions between a nitrile and the NH-group. Thereby the phenyl-benzo[4,5]thieno[2,3-c]pyridazines12, the phenyl-1H-benzo[4,5]thieno[2,3-c]pyridines13 and the phenylamino-benzo[4,5]thieno[2,3-c]pyridines14 are obtained.13C and15N-NMR spectroscopy was used as proof of the ring closure reactions.