Über P–P-haltige cyclische Verbindungen. II

On P? P Containing Cyclic Compounds. II. Reaction of N,N'-dimethylthiourea with phenyl dichlorophosphane yields 1.4-dimethyl-2. 3-diphenyl-1.4.2.3-diazadiphospholidine-5-thione-2-sulfide ( II ). The compound is characterized by its nmr, vibration and mass spectra as well as the results of an X-ray structural analysis. Byproduct of the reaction is N-(N,N'-dimethylcarbamimidoyl)-N,N'-dimethyl thiourea hydrochloride ( III ), which crystallizes with pyridinium chloride. Molecular and crystal structure are reported. With methyl dichlorophosphane N,N'-dimethylthiourea forms 1.2.3.4-tetramethyl-1.4.2.3-diazadiphospholidine-5-thione-2-sulfide ( IV ), which is characterized by its nmr and vibration spectra.     

NMR-Untersuchungen an Methylphosphoniumchlorid

N.M.R. Investigation of Methylphosphonium Chloride The n.m.r. spectra of [CH₃PH₃]Cl in aqueous hydrochloric acid as solvent and of [OP(CH₃) (OCH₂CH₂Cl)OCH₂? ]₂ in C₆D₆ und CD₂Cl₂ are described. ³¹P n.m.r. resonances with a line width at half height of 55 Hz are found for the H₂O? HCl solutions of [CH₃PH₃]Cl in the solid state at 183 K.     

Über Trichlorphosphazo-Verbindungen aus Nitrilen. III. Die Reaktion zwischen Acrylnitril und PCl3

On Trichlorophosphazo Compounds from Nitriles. III. The Reaction between Acrylonitrile and PCl₃. The reaction of PCl₃ with acrylonitrile at higher temperatures gives CH₂Cl? CCl₂? CCl₂? N? PCl₃ ( II ). On pyrolysis of (II), CH₂Cl? CCl₂? CN (IV) is form- ed. Treatment of (II) with SO, results in CHzCL? CCl₂? CCl?N-P(0)Cl₂ ( III ). At lower temperatures and/or in the presence of PCl₃, acrylonitrile reacts with PCl₃ to give the cis/ trans isomers VIa and VIb .     

Diazadiphosphetidine. VIII. Weitere Diazadiphosphetidin-oxide und ein -oxid-sulfid

Diazadiphosphetidines. VIII. Further Diazadiphosphetidine Oxides and an Oxide Sulfide Synthesis and properties of 1,3-dimethyl-2-phenyl-4-diethylamino-1,3,2,4-diazadiphosphetidine-2-oxide ( II ), 1,3-dimethyl-2-diethylamino-4-phenyl-1,3,2,4-diazadiphosphetidine-2-sulfide-4-oxide ( III ), and 1,3-dimethyl-2,4-diphenyl-1,3,2,4-diazadiphosphetidine-2,4-dioxide ( V ) are reported.     

Radical and radiation-induced grafting of some synthetic high polymers within the temperature range of their glass transition

The temperature dependence of radiation-induced grafting onto poly(ethylene terephthalate), polyamides, polyacrylonitrile, and polypropylene has been investigated for several monomers. In all cases a maximum grafting yield is obtained when the reaction is performed in the temperature range of the glass transition T_g of the polymer used. This maximum yield does not only appear with radiation-induced simultaneous grafting. It also appears when the graft polymerization is induced by pre-irradiation or even by thermal decomposition of organic peroxides. It is assumed that the pronounced maximum of the reactivity at T_g is obtained because in the glassy state below T_g the radicals formed cannot react due to a reduced diffusion of the monomer, whereas above T_g the number of radicals available for polymerization will be reduced with increasing temperature.     

Über die Reaktion von Phosphorpentachlorid mit BF3 · NH3

Phosphorus pentachloride reacts with BF₃ · NH₃ to give [Cl₃P?N? PCl₃][BCl₄](Va). Mechanism of formation and chemical behaviour to SO₂ and H₂S are described, followed by a presentation and discussion of the ³¹P, ¹⁹F, and ¹¹B NMR spectra of the adducts formed by P₂NOCl₅ and BF₃, BCl₃, and PF₅, respectively.     

Synthese und NMR-Spektren von λ5-Diphospheten Die Struktur des 2,4-Diphenyl-1,1,3,3-tetrakis(diethylamino)-1λ5,3λ5-diphosphets

Synthesis and NMR Spectra of λ⁵-Diphosphets. Structure of 2,4-Diphenyl-1,1,3,3-tetrakis (diethylamino)-1λ⁵, 3λ⁵-diphosphete Preparation, properties, and n.m.r. spectra of C₂H₅PF₂[N(C₂H₅)₂]₂, CH₂?PF[N(C₂H₅)₂]₂, and the diphosphetes {RC?P[N(C₂H₅)₂]₂}₂ (R) ? H ( 5a ), CH₃ [( 5b )] are described. The λ⁵-diphosphete {HC?P(NR₂)₂}₂ (R ? CH₃) reacts with BF₃ · O(C₂H₅)₂ to give which is transformed into by n-C₄H₉Li. The crystal and molecular structure of 2,4-diphenyl-1,3,3-tetrakis(diethylamino)-1λ⁵,3λ⁵-diphosphete 2 are reported and discussed.     

Thermolyse von Phosphor(V)-Schwefel(VI)-nitridhalogeniden

Thermolysis of Phosphorus(V) Sulfur(VI) Nitride Halides Thermolysis of compounds of the type R₂PCl = N–SO₂X (R = Cl, CH₃, C₆H₅; X = F, Cl) results in the formation of the compounds R₂P(O)Cl and [NS(O)X]_n. Pyrolysis of the title compounds with longer chains yields, among others, the cyclic compounds III and IX. IX is also one of the decomposition products of a sulfamide derivative (XXI). Finally the thermal behaviour of carbon containing phosphorus(V) sulfur(VI) nitride chlorides has been investigated.     

On the chiral anomaly in non-Riemannian spacetimes

Thetranslation Chern-Simons type three-formcoframe∧torsion on a Riemann-Cartan spacetime is related (by differentiation) to the Nieh-Yan fourform. Following Chandia and Zanelli, two spaces with nontrivial translational Chern-Simons forms are discussed. We then demonstrate, first within the classical Einstein-Cartan-Dirac theory and second in the quantum heat kernel approach to the Dirac operator, how the Nieh-Yan form surfaces in both contexts, in contrast to what has been assumed previously.     

Knot wormholes in geometrodynamics?

The familiar wormhole model of geometrodynamics is extended to allow for knotted embeddings of the initial hypersurface. It is shown that topology change is not only a means to modify the connectivity of the space, but also the knot invariants of its embedding. In a probabilistic framework the process of wormhole scattering can be expressed by creation and annihilation operators acting on the wave function of quantum geometrodynamics. Implications concerning Wheeler's exciton model of elementary particles, thef-gravity approach to hadronic matter, and interrelations with Jehle's flux quantization program are discussed.Work supported by a grant of the Studienstiftung des deutschen Volkes and in part by National Science Foundation grant No. GP 30799 X to Princeton University.