Ring opening of bicyclic tertiary amines with cyclic chlorocarbaphosphazenes: reactions of (ClCN)(2)(Cl2PN) with 1,4-diazabicyclo[2.2,2]octane and quinuclidine

Reactions of bicyclic tertiary amines, 1,4-diazabicyclo[2.2.2]octane (DABCO ) and quinuclidine, have been carried out with tetrachlorocyclodicarbaphosp hatriazene, (ClCN)(2)(Cl2PN), and with (ClCN)(2)(Cl2PN) together with anoth er acyclic tertiary amine. Reaction of an acyclic tertiary amine [NEt3, N(n -Pr)(3), NEt(i-Pr)(2) or Me2NCH2NMe2] with the chlorocarbaphosphazene follo wed by DABCO in 1 : 1 : 1 molar ratio proceeds with cleavage of a C-N bond of both tertiary amines. The cleaved alkyl group of DABCO remains as an alk yl chloride on the product molecule. The 4-(2-chloroethyl)piperazino deriva tives of carbaphosphazenes, (R2NCN)[ClCH2CH2N(CH2CH2)(2)NCN](Cl2PN) [R2N = NEt2 1, N(n-Pr), 2, NEt(i-Pr) 3 or NMe2 4] were isolated, purified and char acterized by spectral and analytical methods. Reaction of (ClCN)(2)(Cl2PN) with two moles of DABCO gave the compound [ClCH2CH2N(CH2CH2)(2)NCN](2)(Cl2P N) 5. The 4-(2-chloroethyl)piperidino compound [ClCH2CH2CH(CH2CH2)(2)NCN](2 )(Cl2PN) 6 was obtained in the reaction of (ClCN)(2)(Cl2PN) with two moles of quinuclidine, while (Me2NCN)[ClCH2CH2CH(CH2CH2)(2)NCN](Cl2PN) 7 is the p roduct in its reaction with Me2NCH2NMe2 and quinuclidine in 1 : 1 : 1 molar ratio. The crystal structure of compound 4 has been determined and shows d ifferences in the exocyclic N-C bond distances of the piperazino group in i ts bonding to the 2-chloroethyl and carbaphosphazene moieties.