J. C. Van De Grampel

Synthesis of phosphazene-substituted polysiloxanes

Phosphazene-substituted polysiloxanes have been synthesized via a hydrosilylation reaction of allyl derivatives of cyclophosphazenes with polymethylhydrosiloxanes. It turned out that a proper choice of both the spacer between the phosphazene group and the double bond and the position of the phosphazene group at the spacer is important for the preparation of soluble polysiloxanes with a high content of phosphazene units.

Inorganic ring systems of physiological importance. Part III: Structure and cytostatic activity in vitro of aziridino cyclophospha(thia)zenes

Abstract The testing for cytostatic activity of a series of 36 aziridino derivatives of (NPCl 2 ) 3 and (NPCl 2 ) 2 NSOCl gives similar results in two different in vitro screening systems. Evaluation of the dose causing 50 per cent inhibition of colony formation (ID50) in mouse leukaemia L1210 cells and the lowest active dose (LAD) established for the radiosensitive mouse lymphoma L5178Y leads to an insight into activating and deactivating structural requirements. The presence of aziridino (N(CH 2 ) 2 ) groups with their alkylating ability and electron releasing substituents is essential for effective tumour growth inhibition. Hydrolytic instability results in loss of gravity.

Structures of inorganic rings as antitumor agents. I. Structure of the two allotropic varieties of 1,3,3,5,5-penta(1-aziridinyl)-1λ6,2,4,6,3,5-thiatriazadiphosphorine 1-oxide, (NPaz2)2-(NSOaz)

The two allotropic varieties of the title compound N3P2SO(NC2H4) 5 have been studied; they are respectively named SOaz(I) and SOaz(II). SOaz(I) crystallizes in the orthorhombic system, space group P2~2~2~, with a - 8.972 (1), b = 23.547 (2), c = 8.028 (1) A, and Z = 4, V = 1696 A 3, d m = 1.40 (5), d x = 1.419 Mg m -3,/t(Mo Ka) = 0.39 mm -~, m.p. = 357 K. SOaz(II) is monoclinic, P2~/c, with a -- 15.614(4), b -- 14.151(6), c = 16.310(6) A, fl = 114.7 (1) °, and Z = 8, V = 3274 A 3, d m = 1.45 (5), d x = 1.471 Mg m -3,/~(Mo Kct) = 0.41 mm -l, m.p. = 376 K. Both structures have been determined using direct methods and refined to conventional R factors of 0.051 [SOaz(I)] and 0.035 [SOaz(II)] for 1492 and 2242 reflections respectively. SOaz(I) contains one type of N3PzSO(NC2H4) 5 molecule, and SOaz(II) two types, A and B; these three different types of molecule exhibit drastic changes in their conformation. This last fact is explained by the possible rotation around the (P-N) and (S-N) bonds which link the aziridinyl groups to the six-membered ring N3P2S.

Synthesis of siloxanes containing acid-sensitive side groups

Abstract New siloxanes with acid-sensitive substituents have been synthesized by means of hydrosilylation, starting from methylhydrosiloxanes. Details of the preparation and characterization are reported. p -t-Butoxycarbonyloxystyrene, p -t-butoxystyrene and t-butyl methacrylate turned out to be excellent reagents in these experiments. 1 H, 13 C and 29 Si nuclear magnetic resonance techniques were used for characterization. The ratio between α and β addition appears to be strongly dependent on the substituents at the vinyl group of the organic moieties.

Derivatives of cis-NPCL2(NSOCl)2 and (NPCl2)2NSOCl. Part VIII. Dimethylamino Derivatives of cis-NPCI2(NSOCl)2

Abstract Cis -NPCl 2 (NSOCl) 2 (I) reacts with dimethylamine in a molar ratio of 1:2 to give four isomeric monosubstituted compounds N 3 PS 2 O 2 Cl 3 NMe 2 ; the position of the substituent depends strongly on the solvent. The second reaction step leads to three isomeric bis(dimethylamino) derivatives. Furthermore, two trisubstituted and two tetrasubstituted derivatives are described. Structures are assigned on the basis of 1 H NMR spectra. A suggestion for the substitution mechanism of the first step is offered. The 31 P NMR spectra of the secondary-amino derivatives of the ring systems (NPCl 2 ) 3 , (NPCl 2 ) 2 NSOCl and NPCl 2 (NSOCl) 2 , known up to now, are compared.

NOVEL PHOSPHAZENE-SUBSTITUTED SILOXANES AND SILANES

Abstract Cyclophosphazene-substituted siloxanes and silanes are prepared by the method of hydrosilylation, starting from allylderivatized cyclophosphazenes and hydrosiloxanes or hydrosilanes in the presence of a platinum catalyst. Steric and electronic effects govern the course of the reaction.

Structure of the tetrabutylammonium salt of 2,4,4,6,6-pentachloro-1,3,5,2λ5,4λ5,6λ5-triazatriphosphorinine 2-oxide

[N(C4H9)4][N3P3C150], Mr--- 570.67, monoclinic, P2Jc, a=10.184(2), b=18.072(3), c = 16.448 (2) A, fl = 106.88 (2) °, V= 2896-8 (9) A 3, Z = 4, Dx = 1.308 g cm -3, A(Mo K~) = 0-71073 A, /z = 6-8 cm-i, F(000) = 1192, T = 298 K, RF = 0.082, wR = 0.069 for 2089 unique observed reflections with I >_ 1.5tr(/) and 263 parameters. The inorganic ring skeleton is nearly flat, tending somewhat to a crown conformation. The P--N bond lengths (mean values) are: N--P(OC1) 1.606 (5) A and N--P(C12) 1.540 (5), 1.58 (1) A.

Novel alkenyl substituted cyclophosphazenes for the synthesis of thermally stable polymers

ABSTRACT. The synthesis of some new alkenyl substituted tetrachlorocyclophosphazenes is discussed. The reaction of acetyl chloride with a hydridocyclophosphazene yielded a vinylacetate derivative or a carbon-bridged bicyclophosphazene. Elimination reactions with (NPCl2)2NP(iPr)C(CH3)2OSO2CH3 yielded a propene derivative and an ANSA compound. X-ray structures of the bicyclophosphazene and ANSA compound are presented. The vinylacetate and propene derivatives did not homopolymerize under radical conditions. Copolymerization with styrene resulted in polymers with a maximum incorporation of 17 mol% for the vinylacetate derivative and 18 mol% for the propene derivative. In TGA studies high char yields up to 64 wt% were observed for the homo- and copolymers of the vinylbenzyl substituted tetrachlorocyclophosphazene. XPS studies showed the residue to contain P, N and C.

Synthesis and characterization of silicon-containing graft copolymers

Poly(4-t-butoxycarbonyloxystyrene)-g-poly(dimethylsiloxane) and poly(t-butylmethacrylate)-g-poly(dimethylsiloxane) with various chemical compositions were synthesized via free radical polymerization of 4-t-butoxycarbonyloxystyrene (TBCS) or t-butylmethacrylate (TBMA) with silicone macromers. These macromers were prepared by anionic ring-opening polymerization of hexamethylcyclotrisiloxane (D3) and subsequent termination with a chlorosilane compound having a methacrylate functionality. The morphology of the graft copolymer systems was investigated by DSC and TEM.

Structure of 2,2';4,4'-bis(p-phenylenedioxy)bis(2,4,6,6-tetrachloro-1,3,5,2λ5,4λ5,6λ5-triazatriphosphorine)

C a2HsClsN604Pr, M r = 769.70, monoclinic, P2Jc, a = 8.959 (1), b = 18.666 (2), c= 17.124 (1)/~, t= 102.01 (1) °, V=2800.9 (6)/~3, Z=4, Dx= 1.825 g cm -a, 2(Mo Kh-) = 0.71073 A,/t = 11.8 cm -a, F(000) = 1520, T= 130K, R = 0.026 for 4629 observed reflections with I> 2.50(/). Molecules of the title compound consist of two, nearly parallel [angle 11.03 (5)°], NaP 3 rings linked to each other by two non-geminal p-phenylenedioxy units. The angles between the inorganic and organic rings vary from 84.15 (7) to 89-80 (7) °. Endocyclic parameters are: P-N = 1.579 (1), C-C = 1.379 (2)A (mean values); N-P-N varies from 116.4(1) to 119.5(1) °, PN--P = 120.9 (1), C--C--C(O) = 118.8 (1), C-C(O)- C-122.4 (2) ° (mean values). The phenylene ring [C(1)-C(6)] is rotated around the C(1)-C(4) axis by short intermolecular contacts.