Aa. Vanderhuizen et al., PREPARATION OF URETHANE AND UREA DERIVATIVES OF (NPCL2)3 - CRYSTAL-STRUCTURE OF A SPIROCYCLIC PHOSPHAZENE WITH A PHOSPHACYANURIC LOOP, Journal of the Chemical Society. Dalton transactions, (4), 1994, pp. 577-581
Reactions of (NPCl2)3 with NaNCO in the presence of aliphatic alcohols
have been investigated. Using an equimolar amount of NaNCO in refluxi
ng acetonitrile, high yields of mono(urethane) derivatives N3P3Cl5(NHC
O2R) were obtained. Disubstitution is mainly non-geminal. Reactions of
(NPCl2)3 with AgNCO and methanol in acetonitrile follow a quite diffe
rent pattern and lead to the formation of three products with basicall
y geminal structures, e.g. gem-N3P3Cl4(OR)(NHCO2R), gem-N3P3Cl4(NH-CO2
R)2, and a spiro derivative (NPCl2)2NP[N(CO2R)C(O)NHC(CH3)N]. The crys
tal structure of the last compound (R = CH3) has been determined. The
difference between the reaction pathways observed for NaNCO and AgNCO
is discussed in terms of S(N)2 and S(N)1 mechanisms, respectively. An
improved synthesis of (NPCl2)2NP(NH2)(NCO) and its reactions with alco
hols and amines are described.