Hexachlorocyclotriphosphazatriene reacts with aniline to give mono, 2,2-bis-, 2,4-bis-, 2,2,4-tris-, 2,2,4,4-tetrakis-. and hexakis-anilino-derivatives, N3P3C16-n(NHPh), (n = 1, 2, 2, 3,4, or 6). The predominantly geminal reaction pattern was established by basicity measurements. and by the preparation of anilinodimethylaminocyclotriphosphazatrienes, and measurements of their l H n.m.r. spectra.
HEXACHLOROCYCLOTRIPHOSPHAZATRIENE (I) reacts withamines in organic solvents to give aminocyclotriphosphazatrienes and amine hydrochlorides.2 It is shown here that reactions with aniline take place by a predominantly geminal pattern, to give derivatives of composition N,P,Cl,-,(NHPh),A mixture containing all six derivatives in addition to oily decomposition products is usually obtained. Relatively weak nucleophiles, e.g., phenoxide and aniline, are less selective than stronger nucleophiles, e.g., aliphatic a m i n e ~, ~~~ which give rise to more powerful electron-supplying substituents.The monoanilinopentachloro-derivative ( 11) is isolated comparatively easily by column adsorption chromatography. The nongeminal-bisanilinotetrachloro-(IV) and geminal-trisanilinotrichloro-(V) derivatives are obtained in particularly low yields. A small-scale reaction of the monoanilinopentachloro-derivative ( 11) with 2 moles of aniline was shown by t.1.c. to give a mixture of all the higher derivatives ( 111)-(VII). Similar reactions of the geminal-bisanilinotetrachloroderivative (111) give only the geminal-tetrakisanilinodichloro-(VI) and hexakisanilino-(VII) derivatives. The nongeminal-bisanilinotetrachloro-derivative (IV) gives also the geminal-trisanilinotrichloro-derivative.The anilinochloro-derivatives react with an excess of dimethylamine in benzene or chloroform when heated in a sealed tube, to give anilinodimethylamino-derivatives. The reactions of hexachlorocyclotriphosphazatriene (I) with dimethylamine have been investigated extensively, and the structures of the chlorodimethylaminocyclotriphosphazatrienes have been establi~hed.~., Their reactions with aniline to give anilinodimethylamino-derivatives are also reported here.
