Novel Organo-Substituted Cyclophosphazenes via Reaction of a Monohydro Cyclophosphazene and Acetyl Chloride.
A new olefin-substituted tetrachlorocyclotri-lambda(5)-phosphazene (NPCl(2))(2)NP(i)Pr{C[OC(O)Me]=CH(2)} (4) and an unique bicyclo-lambda(5)-triphosphazene [(NPCl(2))(2)NP(i)Pr](2)C(OH)Me (5) have been prepared from the reaction of MeC(O)Cl and (NPCl(2))(2)NP(i)PrH in the presence of Et(3)N. Exclusive formation of 4 could be achieved by using an excess of both Et(3)N and MeC(O)Cl. The phosphazene rings in 5 are bridged by one carbon atom. The presence of this C(OH)Me bridge induces an asymmetric environment which renders the isopropyl ligands no longer equivalent under NMR conditions. Crystals of 4 are monoclinic, space group P2(1)/n, with a = 13.158(1) Å, b = 9.555(1) Å, c = 14.859(1) Å, beta = 115.502(6) degrees, V = 1686.1(3) Å(3), and Z = 4. Crystals of 5 are monoclinic, space group P2(1)/c, with a = 13.255(2) Å, b = 12.050(2) Å, c = 16.280(2) Å, beta = 98.91(1) degrees, V = 2568.8(7) Å(3), and Z = 4.
Bosscher
G.
G
Department of Polymer Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands.
Meetsma
A.
A
van De Grampel
J. C.
JC