Phosphorus(V) Acid Esters of Oximes

Deoxy‐nitrosugars. 11th Communication. Reactions of 1‐C‐nitroglycosyl halides and 1‐C‐nitroglycosyl sulfones with dialkyl‐phosphite anions: Nucleophilic attack vs. single‐electron transfer

“…for CI4H26N0&' (383.33): C 43.86, H 6.83, N 3.65, P 8.08; found: C 43.57, H 6.89, N 3.40, P 8.20. (28…”

“…Compound 8 was also obtained from 7 by treatment with trimethyl phosphite (cf. [28]). The 'H-NMR spectrum (CDCl,) of 8 (foam) showed the presence of (E)-and (Z)-8 (ratio 1 :9, based on the integral of H-C(2)).…”

“…of NaPO(OMe), gave mainly the 0 -amino phosphate 17 (45 YO). This phosphate was also obtained by treatment of 16 with trimethyl phosphite (88 %), or by treatment of the hydroximo-lactone 11 with dimethyl phosphorochloridate (43 YO) [28]; 17 was readily transesterified with NaOEt to 11 (84%).…”

Dialkyl (1-Hydroxyiminoalkyl)phosphonates from 1-Bromo-1-nitroalkanes and Trialkyl Phosphites

“…We envisaged a new method for the synthesis of α-aminophosphonates that comprises the Arbuzov reaction of 1-halo-1-nitroalkanes with trialkyl phosphites and reduction of the resulting α-nitroalkylphosphonates. There have been reports on the reaction of 1-halo-1-nitroalkanes with trialkyl phosphites; − however, the results are neither conclusive nor consistent. Thus, Allen reported that 1-halo-1-nitroalkanes reacted with trialkyl phosphites to form alkyl halides and oxime esters of the corresponding pentavalent phosphorus acids, whereas Stirling et al reported that the reaction of bromonitromethane with triethyl phosphite gave triethyl phosphate and hydrogen cyanide .…”

“…There have been reports on the reaction of 1-halo-1-nitroalkanes with trialkyl phosphites; − however, the results are neither conclusive nor consistent. Thus, Allen reported that 1-halo-1-nitroalkanes reacted with trialkyl phosphites to form alkyl halides and oxime esters of the corresponding pentavalent phosphorus acids, whereas Stirling et al reported that the reaction of bromonitromethane with triethyl phosphite gave triethyl phosphate and hydrogen cyanide . On the other hand, Donnelly et al found that 1-bromo-1-phenylnitromethane reacted with 2 molar equiv of triethyl phosphite to afford benzonitrile as the major product, together with phenylnitromethane, ethyl bromide, and triethyl phosphate .…”