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951.
Starting from the para‐phenylenediamine derivative HN(SiMe3)‐C6H4‐NH(SiMe3), a lithiation and subsequent borylation give [(MeO)2B]N(SiMe3)‐C6H4‐N(SiMe3)[B(OMe)2] ( 1 ), the hydridation of which yields Li2[(H3B)N(SiMe3)‐C6H4‐N(SiMe3)(BH3)] ( 2 ). Applying ZrCl4 upon 2 initiates a condensation to give the title compound [‐N(SiMe3)‐p‐C6H4‐N(SiMe3)‐BH‐]2, a hetero[3, 3]paracyclophane with two N‐B‐N chains that connect the para‐phenylene units. The product 3 crystallizes in the orthorhombic space group P212121. 相似文献
952.
Osamu Sangen Singo Masuda Hidehiko Nakano Kazusige Yamana Kenichi Sasaki Naoki Ikeda 《Journal of polymer science. Part A, Polymer chemistry》1992,30(6):1171-1175
A new synthetic pathway of A–B–A tri-block copolyether which is composed of a hydrophilic poly(oxyethylene) unit as an A part and a hydrophobic poly(oxy-2-methyl-trimethylene) unit as a B part is proposed. Telechelic α-tosyl-ω-tosyloxypoly(oxy-2-methyl-trimethylene) derived from tosylation of poly(oxy-2-methyl-trimethylene glycol) (PMTG) was allowed to react with poly(ethylene glycol) (PEG) in the presence of sodium hydroxide. Tg of the resulting A–B–A tri-block copolyether (PEMG) (M?n = 1600) was ?72°C and its specific gravity [D415] was 1.055. 相似文献
953.
Kuno Wagner Kurt Findeisen Walter Schfer Werner Dietrich 《Angewandte Chemie (International ed. in English)》1981,20(10):819-830
Research in the field of low-molecular weight, oligomeric and polymeric α,ω-diisocyanatocarbodiimides and -polycarbodiimides has been fruitful, not only in connection with these compounds themselves, but also—as so often happens in chemistry—with quite different problems. Novel synthetic methods, discoveries concerning the properties of low-molecular weight carbodiimides and phosphane imide derivatives, as well as results on the fragmentation reactions of four-membered heterocyclic compounds containing oxygen, phosphorus, and nitrogen, and a better understanding of the diisocyanate polyaddition process are among the many by-products of this research. The “high- and low-temperature formation” of polycarbodiimides and the homogeneous and heterogeneous catalysis of this process are described, and the fundamental importance of four-membered ring fragmentation mechanisms resulting in the formation of phosphane imide derivatives is outlined. Interesting building blocks for the diisocyanate polyaddition and polycondensation processes can be synthesized by many derivatization reactions of oligomeric and high-molecular weight polycarbodiimides and polyuretonimines. The in situ production of polycarbodiimides via matrix reactions in flexible polyurethane foams leads to a cellular arrangement of the material due to the pronounced symmetrical growth processes. Combination-foams with increased carbonation tendencies are formed in this way. Attention is drawn to several industrial applications of α,ω-diisocyanatopolycarbodiimides, of high-molecular weight cross-linked polyuretonimines, and of polycarbodiimide foams. 相似文献
954.
均三氮苯类除草剂结构与活性的理论研究 总被引:1,自引:0,他引:1
利用Gaussian03程序包中的B3LYP方法,选择6-31G基组对均三氮苯类除草剂及类似衍生物2-(4-溴苄氨基)-4-甲基-6-三氟甲基-1,3,5-三氮苯进行了量子化学计算,从理论上讨论了它们的空间结构、电子结构特征与活性的关系.计算结果表明:三氮苯环与N(7)和N(8)原子形成了共轭结构,分子活性大小与LUMO轨道的得电子能力以及在LUMO轨道中占主要成分的原子有重要关系.N(7)和N(8)连接单个具有推电子能力的基团,有利于生物活性的提高.对于2-(4-溴苄氨基)-4-甲基-6-三氟甲基-1,3,5-三氮苯中,N(8)和C(9)是重要的活性部位,和传统的均三氮苯类除草剂分子相比,与D1蛋白上不同的氨基酸残基发生了键合作用. 相似文献
955.
J. Tolchard 《Journal of solid state chemistry》2007,180(10):2808-2815
The chemical and physical compatibility of SrCeO3 is investigated with respect to LaMO3 (M=Mn, Fe, Co) and La2−xSrxNiO4 (x=0, 0.8), via the reaction of fine-grained powder compacts and solid-state diffusion couples. Compositions were chosen so as to give predictive insight into possible candidate materials for all-oxide electrochemical devices. Results show the primary reaction in these systems to be the dissolution of SrO from SrCeO3 into the LaMO3/La2−xSrxNiO4, and corresponding formation of La-doped CeO2. Reaction kinetics are observed to be relatively fast, with element profiles suggesting the diffusion of Sr2+ in ceria to be surprisingly rapid. It is demonstrated that perovskite starting materials represent poor candidates for use with SrCeO3, reacting completely to form Ruddlesden-Popper/K2NiF4 type oxides. Reaction with La2NiO4 is less pronounced, and formation of secondary phases suppressed for the composition La1.2Sr0.8NiO4. It is thus concluded that Ruddlesden-Popper type oxides represent good candidate materials for use with a SrCeO3-based electrolytes when doped with appropriate levels of Sr. 相似文献
956.
R.-L. Yun Y.-M. Chang C.-H. Lin K.-H. Hu C.-M. Shu 《Journal of Thermal Analysis and Calorimetry》2006,85(1):107-113
In industrial processes, information
on the safety property of chemicals is essentially crucial for safe handling
during unit operations. Ensuring the safe use of combustible or flammable
substances in processes is unlikely without detailed investigations of their
flammability characteristics and related hazards. We studied 3-methyl pyridine
(3-picoline), e.g., flammability limits (LFL/UFL), maximum explosion pressure
(P
max), maximum
explosion pressure rise (dP/dt)max, minimum oxygen concentration
(MOC), vapor deflagration index (K
g),
and characterized the influence of inert steam (H2O)
on critical parameters for 3-picoline/water mixtures at 270°C, 1 atm,
various oxygen concentrations, and vapor mixing ratios (100/0, 30/70, 10/90
and 5/95 vol.%) with a 20-L-Apparatus in simulated conditions, respectively.
The results showed that the flammability characteristics
of 3-picoline(aq) all increased with the oxygen concentration.
However, as the composition of inert steam increased, the flammability parameters
and the degree of fire and explosion hazards were significantly reduced, instead.
This study elucidated the flammability properties of 3-picoline mixed with
inert steam. The conclusions could be applied to proactively prevent the relevant
processes from incurring fire and explosion accidents. 相似文献
957.
N. G. Komissarova N. G. Belenkova L. V. Spirikhin O. V. Shitikova M. S. Yunusov 《Chemistry of Natural Compounds》2002,38(1):58-61
Oxidation of betulin by pyridinium dichromate, pyridinium chlorochromate, and K2Cr2O7 -H2SO4 in the presence of tetrabutylammonium bromide was studied. Products of regioselective C-3, C-28-, and exhaustive oxidation, 28-hydroxylup-20(29)-3-one, 3-hydroxy- and 3-oxolup-20(29)-en-28-al were obtained. 相似文献
958.
Hiratake J 《Chemical record (New York, N.Y.)》2005,5(4):209-228
Carefully designed molecules that are intimately related to the reaction mechanism of enzymes are often highly selective and potent inhibitors that serve as extremely useful chemical probes for understanding the reaction mechanism and structure of enzymes. This article describes the design, synthesis, and applications of specific inhibitors of two mechanistically distinct groups of enzymes, ATP-dependent amide ligases and Ser- and Thr-hydrolases. Our strategy is based on the premise that stable analogues of the transition state (transition-state analogues) are highly potent inhibitors that serve as good mechanistic probes, and that a key structure of a good inhibitor of one enzyme is also utilized for the inhibitors of other enzymes that share the same chemistry in their catalyzed reactions, irrespective of the degree of structural similarity and evolutionary link between the enzymes. According to these principles, we designed and synthesized a series of phosphinate- and sulfoximine-based transition-state analogue inhibitors of glutathione synthetase, gamma-glutamylcysteine synthetase and asparagine synthetase. For the second group of enzymes, we synthesized a gamma-monofluorophosphono glutamate analogue for mechanism-based affinity labeling of gamma-glutamyltranspeptidase and fluorescent phosphonic acid esters for the active-site titration of lipase. These inhibitors were used successfully as ligands for detailed kinetic analyses, X-ray crystallography, and mass analysis of the enzymes to identify the key amino acid residues responsible for catalysis and substrate recognition in the transition state. 相似文献
959.
V. V. Nikitenko A. I. Martynenko S. A. Ostrovsky V. V. Rusak V. V. Kryuchkov D. A. Topchiev 《Russian Chemical Bulletin》1993,42(2):378-380
3-Methyl-l-vinylpyrazole (M3VP) and 5-methyl-1-vinylpyrazole (M5VP) were isolated as individual substances by vacuum rectification of their mixture (M3VP: M5VP 60 40). For each of them the kinetics of free-radical polymerization in MeOH were measured at low conversions. In both cases the rate of polymerization is proportional to 0.5 order with respect to the initiator (AIBN) concentration. On the other hand, a first order of reaction with respect to monomer concentration is observed only when the latter is relatively low (3M). At higher initial concentrations of monomers the order of reaction becomes less than unity. The overall rate of polymerization for M5VP was higher than for M3VP, whereas the initiation rate remained constant in the whole range of monomer concentrations and did not depend on the exact structure of the monomer. The difference in the rates of polymerization observed for M3VP and M5VP is probably connected with the difference in the key parameterk
p/k
t
1/2
for each of the two isomers. It is concluded that the correct kinetic information about homo- and co-polymerization of M3VP and M5VP cannot be obtained without their adequate separation.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 413–415, February, 1993. 相似文献
960.
Andreas Manz Elisabeth Verpoorte Carlo S. Effenhauser Norbert Burggraf Daniel E. Raymond D. Jed Harrison H. Michael Widmer 《Journal of separation science》1993,16(7):433-436
Miniaturization of separation columns implies equally reduced vol- umes of injectors, detectors, and the connecting channels. Planar chip technology provides a powerful means for the fabrication of micron-sized structures such as channels. This is demonstrated by two examples. An optical absorbance detector chip exhibits the expected behavior of a 1 mm optical path length cell despite its volume of 1 nL. A capillary electrophoresis device allows integrated injections of 100 pL samples, efficiencies of 70,000 to 160,000 theoretical plates in 10 to 20 seconds, and external laser-induced fluorescence detection at any capillary length of choice between 5 and 50 mm. 相似文献