68280-30-8Relevant academic research and scientific papers
Stereochemistry and Reactions of Aziridinylphosphinothionates Derived from Amino Acids
Hirashima, Akinori,Eto, Morifusa
, p. 829 - 838 (2007/10/02)
Aziridinylphosphinothionates were prepared from optically active ethyl hydrogen phenylphosphonothionates and 1-bromo-2-alkanamines derived from leucine or valine.The aziridine ring was opened by the action of some nucleophiles.Refluxing the aziridinylphosphinethionates in acetone with sodium iodide caused hydrolysis accompanied by the rearrangement of the sulfur atom to give β-mercaptoethylphosphonamidates.The reaction mechanism was discussed eith stereochemical considerations.The insecticidal activity of the products was also examined.
SILICON-PHOSPHORUS ANALOGIES. PARTICIPATION OF EXTERNAL NUCLEOPHILES TO ACTIVATED PROCESSES OF RACEMIZATION AND HYDROLYSIS OF CHLOROPHOSPHONO DERIVATIVES
Corriu, R. J. P.,Lanneau, G. F.,Leclercq, D.
, p. 1617 - 1626 (2007/10/02)
Kinetic and stereochemical studies show nucleophilic assistance by dimethylformamide (DMF), dimethylacetamide (DMA), hexamethylphosphotriamide (HMPT) and N-methylimidazole (NMI) in racemization and solvolysis of menthylchloro(phenyl)phosphonate, 1a, and O-ethylchloro(phenyl)thiophosphonate, 2.Similar orders of nucleophilic reactivity (Nu = NMI >> HMPT > DMF> DMA), and identical rate laws (vrac = k 2 and vH2O = k') are consistent with a common mechanism, governed by entropy (-60 u.e/= -40 u.e.).Analogies between reaction mechanisms at silicon and phosphorus are clearly evidenced.A two step process, involving rate-determining attack on a pentacoordinate complex is discussed.
