Silicon-Containing Polymers Derived from Mono and Disubstituted Cyclophosphazenes

Two classes of silicon-containing polymers are described, one in which phosphazene rings are part of the polymer backbone, the other where phosphazene rings are present as pendant groups. X-ray structures of some monomeric precursors and reaction products are shown

Fluorinated cyclothiaphosphazenes:Synthesis, structure and reactivity

Reaction of chlorocyclothiaphosphazenes NPCl2(NSOX)(2) (X = Cl, Ph) and (NPCl2)(2)NSOX (X = Cl, F, Ph) with KSO2F in bulk leads to fluorination at the phosphorus centers. The substitution reaction follows a geminal pattern. Reactions of trans-NPF2(NSOPh)(2) with Grignard reagents RMgX (R = Me, (t)Bu) show substitution of fluorine by alkyl groups to be a slow process. The more reactive PhMgBr gives an acceptable reaction rate and good yields. Organolithium reagents offer organo-substituted cyclothiaphosphazenes in low to moderate yields, depending on the reagent used. Crystals of cis-NPF2(NSOPh)(2) are monoclinic, space group P2(1)/n, with a = 13.665(7) Angstrom, b = 10.676(1) Angstrom, c = 9.897(3) Angstrom, beta = 90.55(3)degrees, V = 1443.8(9) Angstrom(3), and Z = 4. The final R and wR values are 0.034 and 0.043, respectively. The PN and SN bond lengths vary from 1.571(2) to 1.590(2) Angstrom

Structures of inorganic rings as antitumor agents

(NPAz2)2NSOF, C8H16FN7OP2S, Mr = 339.3, monoclinic, a = 10.506(2), b = 16.964(3), c = 8.506(1)Å, γ = 98.77(1)°. Z = 4, Dc = 1.508 g.cm-3, space group P21/b, 2606 unique reflections, R = 0.053; (NPAz2)2 NSOPh, C14H21N7OP2S, Mr = 397.4, orthorhombic, a = 8.043(2), b = 15.116(1), c = 15.763(6)Å, Z = 4, Dc = 1.377 g.cm-3, space group P212121, 1686 unique reflections, R = 0.025. Monochromatic MoKa1 radiation (λ = 0.70926 Å) was used. The structures were solved by the direct methods. Conformations of aziridinyl wings in both structures are compared with situations in other aziridinocyclophosphazenes and in (NPAz2)2NSOAz with the aim of understanding the variable antitumour activity within the series and of designing better drugs yet

The Application of Phosphazene Containing Polymers as Negative Resists in Microlithography

New terpolymers containing phosphazene, epoxy and silicon moieties have been synthesized which were used as negative resists in microlithography. In addition to synthesis and characterization, lithographic properties are discussed

Preparation of urethane and urea derivatives of (NPCl2)3: Crystal structure of a spirocyclic phosphazene with a phosphacyanuric loop

Reactions of (NPCl2)3 with NaNCO in the presence of aliphatic alcohols have been investigated. Using an equimolar amount of NaNCO in refluxing acetonitrile, high yields of mono(urethane) derivatives N3P3Cl5(NHCO2R) were obtained. Disubstitution is mainly non-geminal. Reactions of (NPCl2)3 with AgNCO and methanol in acetonitrile follow a quite different pattern and lead to the formation of three products with basically geminal structures, e.g. gem-N3P3Cl4(OR)(NHCO2R), gem-N3P3Cl4(NH-CO2R)2, and a spiro derivative (NPCl2)2NP[N(CO2R)C(O)NHC(CH3)N]. The crystal structure of the last compound (R = CH3) has been determined. The difference between the reaction pathways observed for NaNCO and AgNCO is discussed in terms of S(N)2 and S(N)1 mechanisms, respectively. An improved synthesis of (NPCl2)2NP(NH2)(NCO) and its reactions with alcohols and amines are described

Polymerization of Organo-Substituted Silanes by Hydroslylation

Polymerization of unsaturated organo-substituted silanes by catalytic hydrosilylation leads to both polymeric and cyclic carbosilanes