ChemInform Abstract: REACTION OF CHLOROMETHYLDIBENZYLPHOSPHINE OXIDE WITH SOME NUCLEOPHILIC AGENTS

Abstract

".1‐ horverbindungen Die Umsetzung des Chlormethyl‐dibenzyl‐phosphinoxids mit einigen nucleophilen Agentien.

Reactions of N-phenyl α-halogenophosphonamidates with alkoxide: migration of the anilino group from phosphorus to the α carbon atom

“…The 1-chloroethylphosphonamidate (5) was prepared from the corresponding phosphonic dichloride (4) by treatment first with methanol-triethylamine (1 mol equiv. ), then with aniline (Scheme 1).…”

Synthetic Applications of Dialkyl (Chloromethyl)phosphonates and N,N,N‘,N‘-Tetraalkyl(chloromethyl)phosphonic Diamides

“…A novel rearrangement involving an intramolecular substitution of the chlorine atom by an aromatic amine has recently been described. When the unsymmetrical phosphonic diamide 61 is treated with alkoxide, loss of a proton from the anilino group leads to the synthesis of 63 via a highly reactive three membered ring intermediate 62 (Scheme ) 105a…”

“…This reaction has been extended to chloro phosphonamidates in which the N -phenyl group has been replaced by N -alkyl. In this case the reaction can give two products: by P−N cleavage of the three membered ring to give an α-amino phosphonate or by P−C cleavage to give a phosphoramidate. 105b,c

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Evidence for cyclic azaphosphiridine oxide intermediates in the methoxide-induced rearrangements of N-alkyl α-chlorophosphonamidates: formation of phosphoramidates as well as α-aminophosphonates

“…When the a-chlorophosphonic diamide (1) is heated with RONa-ROH in dimethylformamide the phenylamino group migrates from phosphorus to the a-carbon atom and the CCanilino compound (2; R = Me, Et, or Ph) is obtained in good yield (5(r_S0%). 2 Comparable behaviour has recently been observed with N-phenyl a-chlorophosphonamidates, including the more highly alkylated substrates (3; R = H) and (3; R = Me),3 suggesting that this type of rearrangement has considerable generality and synthetic potential.…”