Nucleophilic Substitution of 2,2-Bis(arylthio)-4,4,6,6-tetrachlorocyclotriphosphazene with Ammonia, Phenoxide, and Thiophenoxide

Nucleophilic substitution of hexachlorocyclotriphosphazene (HCCP) with arylthiol gave 2,2-bis(arylthio)-4,4,6,6-tetrachlorocyclotriphosphazene.Aminolysis of 2,2,4,4 -tet erachl oro -6,6-bi s(4-m ethoxyphenylt hio )cyclotriphosphazene with gaseous ammonia gave gem-disubstituted 2,2-diamino-4,4-dichloro-6,6-bis(4-methoxyphenylthio)cyclotriphosphazene in Et2O and tetrasubstituted 2,2,4,4-tetraamino-6,6-bis(4-methoxyphenylthio)cyclotriphosphazene in acetonitrile, respectively.The reaction of 2,2,4,4-teterachloro-6,6-bis(4-methoxyphenylthio)cyclotriphosphazene w i t h 4 -c h l o r o p h e n o l g a v e a m i x t u r e o f g e m -d i s u b s t i t u t e d 2,2-dichloro-4,4-bis(4-chlorophenoxy)-6,6-bis(4-methoxyphenylthio)cyclotriphosphazene and tetrasubstituted 2,2,4,4-tetrakis(4-chlorophenoxy)-6,6-bis(4methoxyphenylthio)cyclotriphosphazene, whose ratio depended on the reaction solvent.On the other hand, in reaction of 2,2-bis(arylthio)-4,4,6,6-tetrachlorocyclotriphosphazene with another arylthiol, ArS-groups were scrambled. INTRODUCTIOINCyclotriphosphazenes, P3N3X6, has a six-membered flat ring, in which three nitrogen and three phosphorus atoms are connected alternately, and two substituents X are placed on the each phosphorus atom upper side and lower side of the ring (Figure 1).