Dealkylation reactions of dialkylaminomethylferrocenes with cyclic chlorocarbaphosphazene, (ClCN)2(Cl2PN)
作者:N.Dastagiri Reddy、Anil J. Elias、Ashwani Vij
DOI:10.1016/s0022-328x(98)01095-x
日期:1999.5
Dialkylaminomethylferrocenes, FcCH(2)NRR' (NRR'=NMe2)(1), NEt2 (2), N(CH2CH=CH2)(2), (3), N(CH2CH2)(2)O (4), N(Me)(CH2Ph) (5) and N(Me)(c-C6H11) (6) (Fe = Ferrocenyl) were synthesized by the reaction of ferrocene with the corresponding diamines, RR'NCH2NRR'. The identity of 3 was further confirmed by X-ray structural analysis of its hydrochloride, FcCH(2)NH (CH2CH=CH2)(2)(+) Cl- (7). Reactions of compounds 1-6 were carried out with tetrachlorodicarbaphosphatriazene, (ClCN)(2)(Cl2PN) in diethylether medium at room temperature or in refluxing toluene. The amines 1, 2, 4, 5 and 6 were found to undergo a facile C-N bond cleavage at the bridging methylene group irrespective of the nature of substituents on the nitrogen. The cleaved dialkylamino groups were found to substitute regiospecifically at the ring carbon atoms of the carbaphosphazene, yielding the dialkylamino substituted carbaphosphazenes [(RR'N)CN](2),(Cl2PN) 8-12. The X-ray crystal structure of the substituted carbaphosphazene (Me2NCN)(2)(Cl2PN) 8 has also been determined. (C) 1999 Elsevier Science S.A. All rights reserved.