Polymerabwandlung und Synthese mit Sulfenylderivaten. 5. Mitt. Addukte mit cis-1,4-Polybutadien

Ohne Zusammenfassung     

A theoretical approach to the role of transfer reactions in the thermal decomposition of polymers

The relative importance of intermolecular and intramolecular transfers is investigated in the thermal degradation of polymers, in particular polystyrene.It is indicated that any mechanism for the pyrolysis behaviour of this polymer must include both modes of transfer. The model is offered as a diagnostic tool for mechanistic investigations of the thermal decompositions of polymers.     

"GaI": a versatile reagent for the synthetic chemist

The current renaissance in main group chemistry has been fuelled by the remarkable array of fundamentally interesting yet synthetically applicable low oxidation state p-block compounds that have appeared over the last decade. Their syntheses generally require the ready availability of low oxidation state element halide precursors. In the case of gallium this is provided by the simple to prepare reagent, "GaI", which since it was first reported in 1990, has been utilised in areas as varied as organic synthesis and gallium cluster construction. This article tracks the history of this extraordinary material and highlights its synthetic diversity; hopefully allowing the reader to envisage its application to aspects of their own research fields.     

High-power optical parametric chirped-pulse amplifier system with a 1.55 microm signal and a 1.064 microm pump

We have designed and built a chirped-pulse parametric-amplifier system that utilizes a 10 Hz, 300 ps, Nd:YAG pump laser system; a 1.575 microm fiber oscillator and amplifier as the signal source; and rubidium titanyl phosphate and potassium titanyl arsenate nonlinear crystals. We obtained 260 fs, 30 mJ pulses centered at 1.550 microm, representing a gain of > 10(9) and a peak power of 100 GW. To our knowledge, these are the highest energy and peak power pulses ever produced in the 1.5-2.0 microm region     

Time-resolved measurements of self-focusing pulses in air

The spatial, spectral, and temporal properties of self-focusing 798-nm 100-fs pulses in air are experimentally measured with high-resolution, single-shot techniques at a set propagation distance of 10.91 m. The data, obtained with an initially collimated Gaussian beam, show significant evolution of spatial narrowing as well as temporal and spectral changes at intensities lower than those required for significant ionization of air.     

Design and synthesis of a diverse morpholine template library

Efficient and general procedures have been developed for the solution-phase preparation of substituted morpholine derivatives, and a library has been produced around generic structure 1. This library was designed with proprietary modeling software for use as a general screening library. The 30 R1 reagents were phenols, and the 275 R2 reagents were taken from five different reagent classes, giving a variety of product classes in the final library of 8250 potential products. All of the library members were generated from a common intermediate, mesylate (5), which was synthesized efficiently, in bulk, in three steps from N-benzylethanolamine (2). High-throughput chemistry using robotics was carried out to produce the 7907 library members, which were individually characterized by reversed-phase LC/MS analysis.     

Generation of azines by the reaction of a nucleophilic carbene with diazoalkanes: a synthetic and crystallographic study

Reactions of the nucleophilic carbene 1,3-dimesityl-imidazol-2-ylidene (1) with diazofluorene, diphenyldiazomethane, and azidotrimethylsilane were examined. Specifically, carbene 1 reacts with diazofluorene and diphenyldiazomethane to give addition products (azines: 3 and 4, respectively). Compounds 3 and 4 were further characterized in the solid-state by single-crystal X-ray crystallographic studies. [3 (a = 9.7936(6) A, b = 10.0529(7) A, c = 16.251(1) A, alpha = 75.765(1) degrees, beta = 79.711(1) degrees, gamma = 64.321(1) degrees, Z = 2, space group P1); 4 (a = 11.681(3) A, b = 11.861(4) A, c = 21.186(3) A, alpha = 90 degrees, beta = 97.05(2) degrees, gamma = 90 degrees, Z = 4, space group P2(1)/n)]. The structural parameters of 3 and 4 are discussed with reference to previously characterized symmetrical and unsymmetrical azines. Structural data suggest that charge separation is possible in 3.     

High-spin structure of N\simeq Z nuclei around the A = 72 region

High-spin states have been studied in ⁷²Kr and ⁷²Br using the ⁴⁰Ca + ⁴⁰Ca and ³⁶Ar + ⁴⁰Ca reactions at 164 and 145 MeV, respectively. The properties and configurations of the high-spin bands observed have been interpreted using unpaired cranked Nilsson-Strutinsky (CNS), and for ⁷²Kr, paired cranked relativistic Hartree-Bogoliubov (CRHB) calculations. In ⁷²Kr a new band has been identified that has the properties expected for the doubly aligned S-band configuration. In ⁷²Br the previously known bands have been extended to higher spin. This has lead to a re-interpretation of the configurations.Received: 31 October 2002, Published online: 24 February 2004PACS: 21.10.Re Collective levels - 23.20.Lv transitions and level energies - 27.50. + e