18357-17-0Relevant articles and documents
METHOXY-CATALYSED REARRANGEMENT OF N- TO O-(DIPHENYLPHOSPHINYL)HYDROXYLAMINE
Harger, Martin J. P.
, p. 3115 - 3116 (1983)
In methanol Ph2P(O)NHOH undergoes rapid NaOMe-catalysed rearrangement to Ph2P(O)ONH2 which is subsequently converted into Ph2P(O)ONa and Ph2P(O)OMe.
Peroxyhydrolysis of nerve agent VX and model compounds and related nucleophilic reactions
Yang, Yu-Chu,Berg, Frederic J.,Szafraniec, Linda L.,Beaudry, William T.,Bunton, Clifford A.,Kumar, Anurag
, p. 607 - 613 (2007/10/03)
The exceedingly toxic agent VX [O-ethyl S-(diisopropylaminoethyl) methylphosphonothioate], 1a, and the midly toxic model compound O,S-diethyl methylphosphonothioate, 1b, react with HO- to give parallel P-S and P-O bond cleavages; the P-O cleavage of VX produces relatively unreactive but very toxic anionic phosphonothioate. Peroxyhydrolysis of 1a,b with HO2- involves quantitative P-S cleavage at rates 30-40 times that with HO giving the corresponding phosphonate and sulfonate ions and disulfide as nontoxic products. In reaction of 1b with HO2- in H218O, oxygen in these final products is not derived from water and HO2- exclusively displaces the thiolate ion at phosphorus. Reaction of 1b with HSO5- gives the same products, but via oxidatively promoted attack of H218O on phosphorus. Kinetic and isotopic labelling results on reactions of 1a,b and a range of related compounds with HO2-, HO- and RO and an oximate ion are interpreted in terms of concerted SN2(P) reactions rather than stepwise reactions with formation of a trigonal bipyramidal (TBP) intermediate. Product selectivity depends on the relative basicities of the anionic nucleophile and the leaving anions.
ZUR KENNTNIS DES NATRIUMDIPHENYLPHOSPHINOFORMIATS Ph2PCOONa
Diemert, Klaus,Hahn, Thomas,Kuchen, Wilhelm
, p. 287 - 294 (2007/10/02)
Ph2PCOONa 2, prepared from Ph2PNa and CO2, is readily hydrolyzed in protic media with formation of Ph2PH and CO2.Hydrolysis is much slower in NaOH and small quantities of Ph2P(O)O- and HCOO- are additionally formed.Reactions of 2 with RI in stoichiometrical amounts gave tertiary phosphines Ph2PR (R=Me, Et) while the phosphonium compound I resulted from 2 and MeI in excess.Ph2PCOOMe, Ph2PCOOSiMe3 or Ph2PCSSNa were obtained from 2 and (MeO)2SO2, Me3SiCl or CS2.Ph2P(O)ONa and Ph2P(S)SNa were isolated when 2 was reacted with O2 or S8 in benzene.
N,O-bis(diphenylphosphinoyl)hydroxylamine base-induced rearrangement to a phosphonamidic-phosphinic mixed anhydride
Harger
, p. 1451 - 1454 (2007/10/02)
The hydroxylamine derivative Ph2P(O)NHOP(O)Ph2 rearranges on treatment with Bu(t)OK-Bu(t)OH; the product contains two dissimilar P atoms (δ(p) 24.2 and 7.9, J(pp) 34 Hz) and is rapidly hydrolysed to a phosphonamidate and a phosphinate, consistent with it being the mixed anhydride Ph(PhNH)P(O)OP(O)Ph2.
THE STEREOCHEMICALLY CONTROLLED HORNER-WITTIG ROUTE TO UNSATURATED ACIDS: THE BAEYER-VILLIGER REARRANGEMENT OF α-(1-Ph2PO-ALKYL)-CYCLOHEXANONES
Levin, Daniel,Warren, Stuart
, p. 2265 - 2266 (2007/10/02)
Lithiated alkyl diphenylphosphine oxides attack cyclic epoxides with high stereoselectivity: Baeyer-Villiger rearrangement of the derived ketones gives Horner-Wittig intermediates for the synthesis of Z unsaturated acids
