Direct phosphonylation of mono- and dihalogenoanilines

The Pd(0)-catalyzed coupling reaction of diethyl phosphite to bromoaniline precursors or derivatives could not be realized at the ortho-position. On the other hand, the photoactivated substitution with diethyl phosphite anion was readily applied to unprotected mono- and dihalogenoanilines; the ortho-substitution was more rapid than the para, but side-products resulting from dehalogenation reactions were also formed. New fluorophosphonoanilines 8 and diphosphonoanilines 9 have been prepared.