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361.
In an alternative strategy to the use of delta-lactam urethanes for the preparation of homologues of AMPA-type glutamate antagonists, we have used 5-exomethylene derivatives of pyroglutamate esters. The homochiral pyrazole amino acid derivatives 18 and 19 have been prepared in this way. Although this synthesis yields products with a glycine residue separated from a heterocyclic ring by two carbon atoms, the substitution of the heterocyclic ring is different from that in compounds prepared from delta-lactam urethanes. The branched chain compounds 32 and 33 have also been prepared in this way but the second chiral centre is epimerised during the synthesis. An interesting reaction, giving the pyridone 27 from the imino ether 24 and tert-butyl acetoacetate, is also reported.  相似文献   
362.
[Reaction: see text]. Several novel organoselenium and tellurium compounds were prepared and evaluated as mimetics of the selenoenzyme glutathione peroxidase, which protects cells from oxidative stress by reducing harmful peroxides with the thiol glutathione. The compounds were tested for catalytic activity in a model system wherein tert-butyl hydroperoxide or hydrogen peroxide were reduced with benzyl thiol and the rate of the reaction was measured by monitoring the formation of dibenzyl disulfide. Thus, aromatic derivatives 19, 22, 24, and 25 proved to be inferior catalysts compared to the parent cyclic seleninate ester 14 and spirodioxyselenurane 16. In the case of 19 and 22, this was the result of their rapid conversion to the relatively inert selenenyl sulfides 31 and 32, respectively. In general, hydrogen peroxide was reduced faster than tert-butyl hydroperoxide in the presence of the selenium-based catalysts. The cyclic tellurinate ester 27 and spirodioxytellurane 29 proved to be superior catalysts to their selenium analogues 14 and 16, respectively, resulting in the fastest reaction rates by far of all of the compounds we have investigated to date. Oxidation of 29 with hydrogen peroxide produced the unusual and unexpected peroxide 33, in which two hypervalent octahedral tellurium moieties are joined by ether and peroxide bridges. The structure of 33 was confirmed by X-ray crystallography. Although 33 displayed strong catalytic activity when tested independently in the model system, its relatively slow formation from the oxidation of 29 rules out its intermediacy in the catalytic cycle of 29.  相似文献   
363.
The dilithium salts of the phosphonate dianions [PhP(E)(N(t)Bu)(2)](2-) (E = O, S, Se) are generated by the lithiation of [PhP(E)(NH(t)Bu)(2)] with n-butyllithium. The formation of the corresponding telluride (E = Te) is achieved by oxidation of [Li(2)[PhP(N(t)Bu)(2)]] with tellurium. X-ray structural determinations revealed dimeric structures [Li(THF)(2)[PhP(E)(N(t)Bu)(2)]](2) in which the monomeric units are linked by Li-E bonds. In the case of E = Se or Te, but not for E = S, transannular Li-E interactions are also observed, resulting in a six-rung ladder. By contrast, for E = O, this synthetic approach yields the Li(2)O-templated tetramer [(THF)Li(2)[PhP(O)(N(t)Bu)(2)]](4).Li(2)O in THF or the tetramer [(Et(2)O)(0.5)Li(2)[PhP(O)(N(t)Bu)(2)]](4) in diethyl ether. The reaction of trimethylaluminum with PhP(E)(NH(t)Bu)(2) produces the complexes Me(2)Al[PhP(E)(N(t)Bu)(NH(t)Bu)] (E = S, Se), which were shown by X-ray crystallography to be N,E-chelated monomers.  相似文献   
364.
The synthesis of a novel five-membered inorganic ring, a stable N-heterocyclic carbene with a diboron backbone, is reported. A pentacarbonyltungsten complex containing the new carbene is also described. Spectroscopic evidence indicates that the sterically encumbered carbene is a better sigma-donor than classical N-heterocyclic analogues, demonstrating the significant influence of the inorganic backbone on the coordinating properties of the carbon ligand. Crystal structures have been determined for an iminium precursor, the free carbene, and the tungsten complex.  相似文献   
365.
In the solid state, OP[N(H)Me](3) (1a) and OP[N(H)(t)Bu](3) (1b) have hydrogen-bonded structures that exhibit three-dimensional and one-dimensional arrays, respectively. The lithiation of 1b with 1 equiv of (n)BuLi generates the trimeric monolithiated complex (THF)[LiOP(N(t)Bu)[N(H)(t)Bu](2)](3) (4), whereas reaction with an excess of (n)BuLi produces the dimeric dilithium complex [(THF)(2)Li(2)OP(N(t)Bu)(2)[N(H)(t)Bu]](2) (5). Complex 4 contains a Li(2)O(2) ring in an open-ladder structure, whereas 5 embraces a central Li(2)O(2) ring in a closed-ladder arrangement. Investigations of the lithiation of tris(alkyl or arylamido)thiophosphates, SP[N(H)R](3) (2a, R = (i)Pr; 2b, R = (t)Bu; 2c, R = p-tol) with (n)BuLi reveal interesting imido substituent effects. For the alkyl derivatives, only mono- or dilithiation is observed. In the case of R = (t)Bu, lithiation is accompanied by P-S bond cleavage to give the dilithiated cyclodiphosph(V/V)azane [(THF)(2)Li(2)[((t)BuN)(2)P(micro-N(t)Bu)(2)P(N(t)Bu)(2)]] (9). Trilithiation occurs for the triaryl derivatives EP[N(H)Ar](3) (E = S, Ar = p-tolyl; E = Se, Ar = Ph), as demonstrated by the preparation of [(THF)(4)Li(3)[SP(Np-tol)(3)]](2) (10) and [(THF)(4)Li(3)[SeP(NPh)(3)]](2) (11), which are accompanied by the formation of small amounts of 10.[LiOH(THF)](2) and 11.Li(2)Se(2)(THF)(2), respectively.  相似文献   
366.
367.
368.
A very short (three steps) asymmetric synthesis of enantiomerically pure 1,4-disubstituted tetrahydro-1H-3-benzazepines 14 has been elaborated upon, starting from the trans- and cis-configured 11a-substituted 3-phenyl-2,3,11,11a-tetrahydro[1,3]oxazolo[2,3-b]-[3]-benzazepin-5(6H)-ones 6 and 7. The stereoisomerically pure lactams 6 and 7 were benzylated to give 6-benzyl-substituted products 8 and 9. NOE experiments showed a trans-configuration of the benzyl residue and the residue in the 11a-position indicated that the stereochemistry of the benzylation reaction was controlled by the stereocenter at the 11a-position. Reduction of the benzylated tricyclic benzolactams 8 and 9 with AlCl3/LiAlH4 (1/3) yielded the 1,3,4-trisubstituted 3-benzazepines 12 and 13, which were formed stereoselectively with the retention of configuration. Finally, removal of the N-(2-hydroxy-1-phenylethyl) residue by hydrogenolytic cleavage resulted in the formation of enantiomerically pure 1,4-disubstituted 3-benzazepines 14. The σ1, σ2, and NMDA receptor affinities of the enantiomerically pure 3-benzazepines 14 and ent-14 were investigated in competitive receptor binding studies. The butyl derivative ent-14c showed a high affinity towards σ1 and σ2 receptors, with Ki-values of 26 nM and 41 nM, respectively.  相似文献   
369.
The assumption that a fluid adheres to a solid boundary (‘no-slip’ boundary condition) is one of the central tenets of the Navier-Stokes theory. However, there are situations wherein this assumption does not hold. In this communication we examine the effects of slip at the wall when an Oldroyd 6-constant fluid is considered in a channel. The slip assumed depends on the shear stress at the wall. The three non-linear problems are solved using homotopy analysis method (HAM). The results for the velocity profiles are presented and discussed. Received: January 13, 2004; revised: September 7, 2004  相似文献   
370.
W. Masood 《Physics letters. A》2009,373(16):1455-1459
Linear and nonlinear propagation characteristics of quantum drift ion acoustic waves are investigated in an inhomogeneous two-dimensional plasma employing the quantum hydrodynamic (QHD) model. In this regard, the dispersion relation of the drift ion acoustic waves is derived and limiting cases are discussed. In order to study the drift ion acoustic solitons, nonlinear quantum Kadomstev-Petviashvilli (KP) equation in an inhomogeneous quantum plasma is derived using the drift approximation. The solution of quantum KP equation using the tangent hyperbolic (tanh) method is also presented. The variation of the soliton with the quantum Bohm potential, the ratio of drift to soliton velocity in the co-moving frame, , and the increasing magnetic field are also investigated. It is found that the increasing number density decreases the amplitude of the soliton. It is also shown that the fast drift soliton (i.e., v*>u) decreases whereas the slow drift soliton (i.e., v*<u) increases the amplitude of the soliton. Finally, it is shown that the increasing magnetic field increases the amplitude of the quantum drift ion acoustic soliton. The stability of the quantum KP equation is also investigated. The relevance of the present investigation in dense astrophysical environments is also pointed out.  相似文献   
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