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.     

A simple cobalt catalyst system for the efficient and regioselective cyclotrimerisation of alkynes

The intermolecular cyclotrimerisation of terminal and internal alkynes can be catalysed by simple cobalt complexes such as a CoBr2(diimine) under mild reaction conditions when treated with zinc and zinc iodide with high regioselectivity in excellent yields.     

Synthesis and antimalarial effects of 5,6-dichloro-2-[(4-||4-(diethylamino)-i-methylbutyl] amino||-6-methyl-2-pyrirnidinyl)amino] benzimidazole and related benzimidazoles and lH-imidazo[4,5-b] pyridines

A group of fifty-five 2-[(4-11[(dialkylamino)alkyI]amino11-6-methyl-2-pyrimidinyl)amino]-benzimidazoles (VII) was synthesized in 3-88% yield by the condensation of the requisite 2-[(2-benzimidazolyl)amino]-4-chloro-6-methylpyrimidine (VI) with the appropriate polyamine in ethanol-hydrochloric acid or neat with excess amine containing potassium iodide. The 2-[(2-benzimidazolyl)amino]-6-methyl-4-pyrirnidinol precursors (V), obtained in 11-51% yield by cyclization of 2-(cyanoamino)-4-hydroxy-6-methylpyrimidine with a suitably substituted o-phenylenediamine, were chlorinated with phosphorus oxychloride to give the intermediate 2-[(2-benzimidazolyl)amino]-4-chloro-6-rnethylpyrimidines (VI) (27-99%). Oxidation of 5,6-dichloro-2-[(4-11[4-(diethylamino)-l-methylbutyl] amino 11-6-methyl-2-pyrimidinyl) amino ]benzimidazole ( 29 ) with m-chloroperbenzoic acid gave the distal N⁴'-oxide ( 31 ) (19%). Fusion of 2,3-uiaminopyridine with 2-(cyanoamino)-4-hydroxy-6-methylpyrimidine provided 2-[(4-hydroxy-6-tnethyl-2-pyrimidinyl)amino]-lH-imitlazo[4,5-b]pyrimidine (VIII) (30%), which upon chlori-nation with phosphorus oxychloride (63%) followed by amination with i N, N-diethylethylene-diamine afforded 2-(4-11[2-(diethylamino)ethyl] amino 11-6-methyl-2-pyrimidinyl)-lH-imidazo [4,5-b]pyridine (X) (8%). Thirty-eight of the novel 2-[(4-amino-6-methyl-2-pyrimidinyl)amino]-benzimidazoles possessed “curative” activity against Plasmodium berghei at single subcutaneous doses ranging from 20.640 mg./kg. Orally, thirty-one compounds exhibited suppressive activity against P. berghei comparable with or superior to the reference drugs 1-(p-chlorophenyl)-3-(4-11[2-(diethylarnino)ethyl]amino 11-6-methyl-2-pyrimidinyl)guanidine (I) and quinine hydrochloride, while twelve of them were 5 to 28 times as potent as I and quinine hydrochloride. Eight compounds also displayed strong suppressive activity against P. gallinaceum in chicks. 5,6-Dichloro-2-[(4-112-(diethylamino)ethyl]amino11-6-methyl-2-pyrimidinyl] benzimidazole (18) showed marked activity against a cycloguanil-resistant line of P. berghei, and the most promising member of the series, namely 5,6-dichloro-2-[(4-11[4-(diethylamino)-l-methylbutyl]amino11-6-methyl-2-pyrimidinyl)amino]benzimidazole ( 29 ) (Q = 28), was designated for preclinical toxico-logical studies and clinical trial. Structure-activity relationships are discussed.     

Commutative free loop space models at large primes

Let p be a prime number and a natural number. If E is a r-connected finite CW-complex of dimension at most pr, then E is an example of a p -Anick space. For p > 2 we construct a commutative cochain algebra over that is an -model of the free loop space on a p-Anick space, i.e., its cohomology algebra is isomorphic to the mod p cohomology of the free loop space. For p-Anick spaces that are p-formal, such as spheres and projective spaces, we define an even simpler commutative free loop space model that applies for all primes p. We then use the simplified model to compute the cohomology algebras of a number of free loop spaces explicitly. Received: 23 June 1999; in final form: 8 September 2000 // Published online: 7 April 2003     

Intrinsic strength of silicon crystals in pure- and combined-mode fracture without precrack

Measurement of the critical fracture strength of single-crystal silicon was carried out by contact-free laser-based excitation and detection of nonlinear surface acoustic wave (SAW) pulses. The three crystallographic geometries Si(112)111[over ], Si(112)1[over ]1[over ]1, and Si(110)11[over ]1 were examined. A comparison of the optically detected SAW transients and numerically calculated stress-strain fields allowed an estimate of the intrinsic mechanical strength without using an artificial precrack. Depending on the geometry, the critical strength varied between 5 and 7 GPa.     

Generalized hydrodynamics of systems of Brownian particles

A generalized hydrodynamic theory is developed for systems of interacting Brownian particles on the basis of a Fokker-Planck equation. General results are derived for correlation functions, frequency- and wave-vector dependent transport coefficients. Explicit expressions for moments, cumulants and the hydrodynamic limits of the transport coefficients are given. For the special cases of overdamped systems with and without hydrodynamic interaction the general results are simplified. As an example for the application of this approach the system of charged spherical polystyrene spheres in aqueous solution is treated in detail. The generalized transport functions are evaluated in mode-mode coupling approximation and detailed numerical results are presented for various collective and single-particle properties. Finally, the relationship to a corresponding Smoluchowski approach is discussed.     

Zur quantitativen Auswertung von Mikro-Autoradiogrammen mit dem Densitron

Die vorliegende Arbeit beschāftigt sich mit der Answertung von Autoradiogrammen inhomogen markierter mikroskopischer Strukturen am Densitron. Dazu fertigten wir von herkömmlichen Stripping-Filmen (z. B. ORW O K 106) Mikro-Stufengraukeile an und bestimmten die Schwärzung S_ijeder Stufe photometrisch. Graukeile geeigneten Schwärzungsumfangs dienten dann zur Einstellung der Farbtrigger des Densitrons, so daß sich die bei dieser Einstellung gemessenen Farbflächen F_i des jeweiligen Objektes bestimmten Schwärzungswerten zuordnen ließen.

Als Modellobjekte verwendelen wir erstens Autoradiogramme von ³H-Thymidin-markierten Tumorzellen. Vergleichsmessungen an unterschiedlich lange exponierten, sonst aber identischen Präparaten ergaben eine gute Reproduzierbarkeit der Meßergebnisse. Als zweites Testobjekt dienlen Autoradiogramme einer nur schwach markierten Struktur im Gehirn von Fröschen. Die an diesem Grenzfall erhaltenen Ergebnisse werden mit Meßwerten verglichen, die vom gleichen Objekt mittels Scanning-Photometrie an einem. Mikroskop-Photometer SMP 01 (OPTON, Oberkoches, BRD) gewonnen wurden.