Derivatives of cis‐NPCl2(NSOCl)2 and (NPCl2)2NSOCl Part III. Butylamino derivatives of cis‐NPCl2(NSOCl)2

Reaction of cis-NPCl2(NSOCl)2 with n-butylamine (molar ratio 1:2) in acetonitrile leads to a mono(amino) derivative, NPCl(NHBu) (NSOCl)2. Under the same experimental conditions sec-butylamine gives a mixture of about equal amounts of NPCl(NH-s-Bu) (NSOCl)2 and NPCl2NSOClNSO(NH-s-Bu), while tert-butylamine yields mainly NPCl2NSOClNSO(NH-t-Bu). The increasing tendency towards substitution at a sulfur atom can be ascribed to an increasing steric hindrance towards the formation of an 5N1 transition state with five coordinated phosphorus. The reaction of NPCl(NHBu) (NSOCl)2 with n-butylamine (molar ratio 1:2) gives a geminal bis(n-butylamino) derivative, which on fluorination yields NP(NHBu)2(NSOF)2. The 31P- and 19F NMR spectra of the compounds prepared are discussed.