83206-21-7Relevant academic research and scientific papers
CARBON-PHOSPHORUS HETEROCYCLES. REACTIONS OF THE ENAMINE 1-(1,2,3,6-TETRAHYDRO-1-PHENYL-4-PHOSPHORINYL)PYRROLIDINE P-SULFIDE WITH ACTIVATED ALKENES AND ACID ANHYDRIDES.
Rampal, Jang B.,Berlin, K. Darrell,Satyamurthy, Nagichettiar
, p. 179 - 188 (2007/10/02)
The enamine of 1-phenyl-4-phosphorinanone-1-sulfide has been prepared for the first time from the ketone and pyrrolidine in benzene.Crude enamine could be cyanoethylated at carbon.Hydrolysis of the product followed by treatment of the nitrile with aqueous KOH gave the corresponding carboxylic acid.Reduction of this keto acid with NaBH4 in alkaline medium gave the expected carbinol which lactonized spontaneously.Independent synthesis of the keto acid was achieved by adding methyl acrylate to the crude enamine followed by hydrolysis.The crude enamine also reacted with methyl vinyl ketone in dry benzene.Suprisingly, the product was a bicyclic unsaturated ketone which apparently formed via and aldol type condensation (intramolecular) during the hidrolysis of the enamine reaction mixture (hidrolysis was effected with H2O/CH3CO2H/NaO2CCH3).Interestingly, the crude enamine did not react with mesityl oxide or 1-acetyl-1-cyclohexenbe as only starting material and a polymeric substance could be obtained.Freshly distilled acetic anhydride or propionic anhydride did react with the crude enamine to give a solid product in each instance in modest yields.NMR analysis indicated a high population of the enol form in each example.Reaction of the acetyl derivative with hydrazine gave a phosphorinopyrazole and with hydroxylamine a mixture of phosphorinoisoxazoles.These are the first members of these heterocyclic families to be reported.Characterization via 1H, 13C and 31P NMR analysis is also recorded for all compounds.
