Diphenyl phosphorochloridate

A mixture of 56.8 g (0.21 mol) of diphenyl phosphorochloridate (Note 1), 16.3 g (0.25 mol) of sodium azide, and 300 mL of anhydrous acetone (Note 2) in a 500-mL round-bottomed flask fitted with a calcium chloride tube is stirred at 20-25°C for 21 hr. The lachrymatory mixture is filtered in a hood, and the filtrate is concentrated under reduced pressure. The residue is distilled through a short Vigreux column (Note 3). The yield of diphenyl phos-phorazidate, bp 134-136 C (0.2 ram), is 49-52 g (84-89 ) (Note 4). 

Diphenyl phosphorochloridate (diphenyl chiorophosphate), from Aldrich Chemical Company, Inc., was used after purification by distillation at 165-168 C (5 mm). 

Diphenyl phosphorochloridate Diphenyl chlorophosphate Phosphorochloridic acid, diphenyl ester (8,9) (2524-64-3)... 

Poly(methyl 3-(l-oxypyridinyl)siloxane) was synthesized and shown to have catalytic activity in transacylation reactions of carboxylic and phosphoric acid derivatives. 3-(Methyldichlorosilyl)pyridine (1) was made by metallation of 3-bromopyridine with n-BuLi followed by reaction with excess MeSiCl3. 1 was hydrolyzed in aqueous ammonia to give hydroxyl terminated poly(methyl 3-pyridinylsiloxane) (2) which was end-blocked to polymer 3 with (Me3Si)2NH and Me3SiCl. Polymer 3 was N-oxidized with m-ClC6H4C03H to give 4. Species 1-4 were characterized by IR and H NMR spectra. MS of 1 and thermal analysis (DSC and TGA) of 2-4 are discussed. 3-(Trimethylsilyl)-pyridine 1-oxide (6), l,3-dimethyl-l,3-bis-3-(l-oxypyridinyl) disiloxane (7) and 4 were effective catalysts for conversion of benzoyl chloride to benzoic anhydride in CH2Cl2/aqueous NaHCC>3 suspensions and for hydrolysis of diphenyl phosphorochloridate in aqueous NaHCC>3. The latter had a ti/2 of less than 10 min at 23°C. 

Hydrolysis of diphenyl phosphorochloridate (DPPC) in 2.0 M aqueous sodium carbonate is also believed to be a two-phase process. DPPC is quite insoluble in water and forms an insoluble second phase at the concentration employed (i.e. 0.10 M). It seems highly significant that the hydrophobic silicon-substituted pyridine 1-oxides (4,6,7) are much more effective catalysts than hydrophilic 8 and 9. In fact, 4 is clearly the most effective catalyst we have examined for this reaction (ti/2 < 10 min). Since derivatives of phosphoric acids are known to undergo substitution reactions via nucleophilic addition-elimination sequences 1201 (Equation 5), we believe that the initial step in hydrolysis of DPPC occurs in the organic phase. Moreover, the... 

When the monosodium salts of uracil and similar pyrimidines react with diphenyl phosphorochloridate, phosphorylation takes place on oxygen unless other suitable nucleophilic centres are present and free.69 The reaction between the sodium salt of a 1,3-dicarbonyl compound and diethyl phosphorochloridothionate yields the Z-vinylphosphorothionate if the tetrabutylammonium salt is employed, the product has E geometry. This phenomenon has been interpreted in terms of the shape of the... 

If 8-mercaptoadenosine-2, 3/-cyclic phosphate is treated with a phosphateactivating agent, e.g. diphenyl phosphorochloridate or tetraphenyl pyrophosphate, an oligomer is formed in which each phosphate is esterified by the 2 - and 3 -hydroxy-groups of one nucleoside residue and the 5 -hydroxy-group of the next. On... 

The etiolate intermediate, generated by the addition of higher-order cyanocuprates to enones, has been trapped with several electrophiles. Thus the addition of trimethylsilyl chloride, diethyl or diphenyl phosphorochloridate and iV-phenyltrifluoro methane-sulphonamide affords the corresponding vinyl silyl ethers, vinyl phosphates and vinyltri-flates. " ... 

The reagent is prepared by reaction of diphenyl phosphorochloridate w ith sodium aride in acetone (92% yield). It decomposes at 200° and should he protected from light and moisture.1... 

Diphenyl phosphorochloridate can be used, but it is more sensitive to moisture than 1. 

Furthermore, this phosphorylation reaction could be applied not only to the glycosyl position but also to other hydroxyl groups. When compound 38 (Figure 11) was treated with butyl-lithium and diphenyl phosphorochloridate as above, a syrupy 4-phosphate 39 was obtained whose structure was unequivocally confirmed by 3oOMHz -NMR. A quartet signal of H-4 (6 4.70ppm,... 

Diphenyl phosphorazidate, 222 Diphenyl phosphorochloridate, 223 Diphenylselenium bis(trifluoro)acetate, 223-224... 

To obtain model compounds for the study of inositol phosphates, Kil-gour and Ballou180 treated di-O-isopropylidenepinitol (LXIV) and di-O-isopropylidene-Zeyo-inositol (XXVIII) with diphenyl phosphorochloridate. For the latter, the result was surprising instead of the expected mono-or di-phosphate, a cyclic phosphate (LXXIX) was obtained. In it, the phosphate group is attached to two irans-hydroxyl groups, like the third iso-propylidene group in tri-O-isopropylidene-fevo-inositol (see p. 149). This... 

---