Novel aminophosphonothiophene derivatives from β-keto-δ-carbethoxyphosphonates and phosphineoxides
摘要:
The reaction of -keto--carbethoxyphosphonates and phosphineoxides with active methylene nitriles leads to the corresponding phosphonoalkylidenes. Treatment of these compounds with sulfur, under the classical Gewald reaction conditions, gives a ca. 1:1 mixture of novel aminophosphonothiophene derivatives 3 and 3'. In order to improve the regioselectivity of the reaction, novel conditions have been developed for the Gewald condensation, in which we used an inorganic base NaH in THF as the solvent. These conditions afforded exclusively the 3-regioisomer in good yield. [image omitted].
Unusual Course of the Reaction of Lawesson’s Reagent with β-Phosphoryl- β’-carbethoxyhydrazones: First Synthesis of 5-Mercapto-3-(methylthiophosphoryl) pyrazoles
作者:Emna Chebil、Soufiane Touil
DOI:10.2174/157017812801264764
日期:2012.5.1
It is well known that Lawesson’s reagent (LR) reacts with hydrazone derivatives at 80 °C to yield 3-thioxo- 1,2,3-diazaphospholine derivatives. We show, in the present investigation, that the reaction of LR with β- phosphoryl-β’-carbethoxyhydrazones under the same conditions, took an entirely different course and gave a new type of pyrazole derivatives, the 5-mercapto-3-(methylthiophosphoryl)pyrazoles