Oxime phosphates

Carbamyl phosphonates (Phosphorylimino)esters Phosphoryloximes Oxime phosphates 15... 

Phosphoric acid 2,2-dihalogenovinyl esters s. 11,173 Oxime phosphates G NOPO(OR)2... 

Dutch State Mines (Stamicarbon). Vapor-phase, catalytic hydrogenation of phenol to cyclohexanone over palladium on alumina, Hcensed by Stamicarbon, the engineering subsidiary of DSM, gives a 95% yield at high conversion plus an additional 3% by dehydrogenation of coproduct cyclohexanol over a copper catalyst. Cyclohexane oxidation, an alternative route to cyclohexanone, is used in the United States and in Asia by DSM. A cyclohexane vapor-cloud explosion occurred in 1975 at a co-owned DSM plant in Flixborough, UK (12) the plant was rebuilt but later closed. In addition to the conventional Raschig process for hydroxylamine, DSM has developed a hydroxylamine phosphate—oxime (HPO) process for cyclohexanone oxime no by-product ammonium sulfate is produced. Catalytic ammonia oxidation is followed by absorption of NO in a buffered aqueous phosphoric acid... 

The lipophilicity of this phosphate protective group helps in the chromatographic purification of oligonucleotides. It is removed by the oximate method. ... 

Martynov, I.V., Yu.L. Kruglyak, and S.I. Malekin. "Carbonyl Halide Oxime /S-Chloroalkyl Fluoro-phosphates," Soviet Patent 241433, April 18, 1969 (In Russian). 

HPO [Hydroxylamine phosphate oxime] A process for making caprolactam, an intermediate in the manufacture of polyamides. It differs from related processes, such as HSO, in producing less of the ammonium sulfate by-product. Developed by DSM Research, The Netherlands, operated by DSM Polymers and Hydrocarbons, and offered for license by Stamicarbon. 

The effect is not limited to C-O bonds. It is observed also for the N-OX bonds of oxime derivatives (see below) and for P-OX bond lengths in two series of phosphate esters. The P-OX bond lengths also show sensitivities to pXHox which parallel their reactivities (Jones and Kirby, 1984). 

The O-substitution products of oximes can be readily cleaved to give the corresponding alcohols. The (Ph-Pybox) Ir catalyst worked well at low temperatures with allyl phosphates as substrates (Scheme 9.36) [40, 63]. The selectivities depended heavily on the base used for activation of the oxime with, again, the best results being obtained with Ba(0H)2-H20. Only arylallyl phosphates have been reported as substrates. 

An efficient synthesis of 2Ff-azirines 6 substituted with a phosphate group is described. Its key step is an alkaloid catalyzed Neber reaction of -ketoxime tosylates 5 (equation 3) . Similarly, azirines containing an ester group in position 2 were obtained from tosy-lated oximes . A novel approach to substituted 2Ff-azirines using benzotriazole (Bt) methodology was recently presented. The reaction of benzotriazole oxime tosylates formed from the oxime 7 and TsCl with aqueous KOH yielded 2-(benzotriazol-l-yl)-2H-azirines. 

Synthetic studies for the discovery of effective antidotes for cholinesterase inhibitors are continuing . Various reactivity studies of oximates with different functional organophosphorus compounds, such as phosphinates, phosphonates, phosphates and thiono analogues (shown in Scheme 5), have been reported . ... 

Kondritzer et al.1 8 administered I, 2-PAM lactate, 2-PAM dihydrogen phosphate, II, 2-PAM I, and III to human subjects as aqueous solutions. The subjects were primed with 400 ml of water during the hour before they drank the solution of oxime and drank 100 ml of water during each of 5 consecutive hours after taking the oxime. The peak plasma concentrations of oxime occurred at about 2 h after drinking of a solution of 2-PAM 1 that contained a mean dose of 71.4 mg/kg, at about 2.5 h when the dose was increased to 114.3 mg/kg, and at about 3 h when the dose was Increased further to 142.9 mg/kg. 

---