PHOSPHONIC ACIDS AND ESTERS .19. SYNHTESES OF SUBSTITUTED PHENYL- AND ARYLPHOSPHONATES BY PHOTOINITIATED ARYLATION OF TRIALKYL PHOSPHITES

The syntheses of a variety of nuclear substituted (methyl, ethyl, methoxy, hydroxy, amino, formyl) phenylphosphonates 3 and other aryl-(1-naphthyl-, 2-thienyl-, 2-furyl-) phosphonates have been carried out by the low temperature ultraviolet photolyses of the corresponding aryl iodides in excess trialkyl (methyl or ethyl) phosphite 1. The process constitutes an experimentally simple one-step procedure for the synthesis of these compounds in good yield. The nitroiodobenzenes are the only class of compounds examined which failed to yield the corresponding 3; photolyses of these compounds in the presence of 1 resulted in deoxygenation to yield the corresponding phosphate and, presumably, an electron-deficient nitrogen intermediate. Infrared and proton magnetic resonance data are presented for certain 3, particularly para-substituted compounds and those structures capable of exhibiting intra- or intermolecular hydrogen bonds. © 1968, American Chemical Society. All rights reserved.