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Diphenyl phosphorochloridate is used to prepare cyclohexyl-amidophosphoric acid diphenyl ester by reacting with cyclohexylamine. It is also used in the synthesis of alfa-substituted beta-lactams, anhydrides, esters and thioesters. It is also employed in the conversion of aldoximes to nitriles. Further, it is used in the preparation and reaction of enol phosphates, guanosine-adenosine-5',5'-triphosphate, guanosine-cytidine-5',5'-triphosphate, guanosine-uridine-5',5'-triphosphate, diguanosine-5',5'-diphosphate and diguanosine-5',5'-triphosphate. In addition to this, it serves as a phosphorylating agent for the preparation of 2-deoxy-D-galactose-3 and -6 phosphoric acids.
Diphenylphosphate esters, formed with or without catalysis by DMAP, undergo a variety of transformations:
Hydrogenolysis of the phenyl groups yields the monophosphate ester of the alcohol. Glycosyl monophosphates have been prepared in this way. Alternatively, treatment of the glycosyl diphenyl phosphate with sodium azide in DMF provides a high yield route to glycosyl azides: Carbohydr. Res., 223, 169 (1992).
Diphenylphosphate has also been exploited as a good leaving group in the high yield conversion (equivalent to dehydration) of secondary alcohols to olefins by thermal elimination: Synthesis, 1300 (1995). For further information, see Triphenyl phosphate, L08130. Other conversions, generally in the presence of a base such as triethylamine, in which the equivalent of a dehydration step occurs are:
Aldoximes to nitriles at room temperature: J. Org. Chem., 34, 2805 (1969). Peptide coupling (see Appendix 6), via the mixed carboxyl phosphate anhydride: Chem. Ber., 94, 2644 (1961). Carboxylic acids to anhydrides: Synthesis, 219 (1981). ω-Hydroxy acids to macrolides, promoted by DMAP: J. Org. Chem., 47, 1612 (1982).
Lithium enolates give enol diphenylphosphates in which the phosphate moiety acts as a leaving group; e.g., ketone enol phosphates have been converted to the corresponding alkene by reaction with organocuprates: Tetrahedron Lett., 4405 (1976). With amides, internal displacement occurs; subsequent reaction with NaN3 gives azirines: Helv. Chim. Acta, 76, 2830 (1993):
See also Diphenylphosphonic azide, A12124.
Xu, Z. A review on the chemical synthesis of pyrophosphate bonds in bioactive nucleoside diphosphate analogs. Bioorg. Med. Chem. Lett. 2015, 25 (18), 3777-3783.
Marquick, A. L.; Montero, J. L.; Lebrun, A.; Barragan-Montero, V. Straightforward synthesis towards mono and bis-phosphonic acid functionalised beta-cyclodextrins. Tetrahedron 2015, 71 (10), 1616-1621.
Gefahrenhinweise (EU): H314-H318
Causes severe skin burns and eye damage. Causes serious eye damage.
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