ChemInform Abstract: OXIDATIVE HERST. VON 1,2‐DINITRO‐ALKENEN UND 1,4‐DINITRO‐1,3‐ALKADIENEN

Abstract

1,2‐Dinitro‐alkane wie 1,2‐Dinitro‐äthan, 2,3‐Dinitro‐butan oder 1,2‐Diphenyl‐l ,2‐dinitro‐äthan (I) können in Äther bei ‐60°C bis ‐20°C mit Brom zu Dinitro‐äthylen, ‐buten bzw. ‐transstilben (II) oxidiert werden (Ausbeute 22 ‐ 27%; für Dinitrostilben 6%).

Reactions of δ-functionalized α-nitrodienes with N-mono- and N,S-binucleophiles

“…UV spectrum (CHCl 3 ): λ max 325 nm (log ε 4.38). 1 2-[(1E,3E)-4-Nitrobuta-1,3-dien-1-ylsulfanyl]-aniline (X). o-Aminobenzenethiol, 0.15 g (1.1 mmol), was added at 0°C to a solution of 0.15 g (1 mmol) of dinitrodiene III in 15 ml of methanol, the mixture was kept for 1 h, and the precipitate was filtered off.…”

“…The results of reactions of 1,4-dinitrodienes with aromatic amines and thiols are determined by nucleophilic attack at the middle or terminal carbon atom of the diene system [1,2]. In the present communication we report the results of our study on reactions of 1-nitro-4-arylsulfonyldienes I and II with aromatic amines and of 1,4-dinitro-and 1-nitro-4-sulfanyldienes III-V with N,S-binucleophiles.…”

“…We found that, unlike dinitrodienes III and IV which give rise to addition products [1], reactions of 1-nitro-4-sulfonyldienes I and II with aromatic amines followed nucleophilic vinylic substitution pattern, and the products were 1-arylamino-4-nitrodienes VI-VIII formed via replacement of the sulfonyl group. Less reactive 1-(4-chlorophenylsulfanyl)-2,3-dimethyl-4-nitrobuta-1,3-diene (V) failed to react with aniline under similar conditions; however, by heating compound V with toluidine hydrochloride we obtained bissubstitution product IX which was identical to that obtained in the reaction with sodium p-chlorobenzenethiolate.…”

Synthesis and Structure of 1-Nitro-4-benzothiazolylsulfanyl- and -sulfonyldienes

“…Ia and Ib were obtained by oxidative bromination of corresponding 1,4-dinitro-2-butenes disodium salts along the known procedure [7].…”