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11.
Atri Mukhopadhyay Raj Kumar Moitra Debashis Mukherjee 《International journal of quantum chemistry》1975,9(3):545-554
We introduce here a new partitioning of the Hamiltonian in calculating pair-correlation energies using many-body perturbation theory, by which we are able to eliminate the off-diagonal particle–hole (p–h) ladders exactly to all orders in the perturbation expansion. In this formulation, the particle states turn out to be different for each distinct pair of hole states in the correlation energy calculation. We have also included the contributions of the diagonal particle–particle (p–p) and hole–hole ladders exactly to all orders. The effect of the off-diagonal p–p ladders has been estimated for each pair by computing the third-, foruth- and fifth-order energies. For highly symmetric systems the present partitioning yields in general symmetry-broken orbitals. Here one may use an average kind of partitioning for all the partners of the degenerate sets, which restores the symmetry and at the same time ensures cancellation of the p–h ladders exactly at the lowest order and approximately at the higher orders. Results are presented for a selection of 6π-electron conjugated systems. The correlation energy for each pair is in excellent agreement with that obtained from a partial CI calculation involving all double excitations from this pair. The advantages of implementing the present scheme in larger systems has been discussed. 相似文献
12.
Thermal behaviour of blends based on N,N'-bis(4-itaconimidophenyl) ether (IE) and 4,4'-bis(4-allyl-2-methoxyphenoxy) benzophenone
(R1) or 4,4'-bis(2-allylphenoxy) benzophenone (R2) are described in this paper. The reactive diluent content was varied from 5-50% (mass/mass) in these blends. A decrease
in the melting point and exothermic peak temperature was observed with increasing mass percent of reactive diluent. Thermal
stability of blends was affected at high mass percentage of reactive diluents.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
13.
Zusammenfassung Die durch Umsetzung von 5-Methyltryptamin, 5-Äthoxytryptamin und 5-Methylmercapto-tryptamin (I, R=CH3, OC2H5 bzw. SCH3) mit dem racemischen Aldehyd-Ester II entstandenenSchiffschen Basen wurden durch Natriumborhydrid-Reduktion in Methanol unter gleichzeitiger Cyclisierung und Desacetylierung in die entsprechenden 10-substituiertendl-Methyl-2,3-seco-3-oxodeserpidate (IV) übergeführt. Die bei der Einwirkung von 3,4,5-Trimethoxybenzoylchlorid in Pyridin erhaltenen Ester V wurden weiter mit Phosphoroxychlorid cyclisiert und die Produkte als Perchlorate (VI) mit Zink in sauerer Lösung zu den entsprechenden 10-substituiertendl-Deserpidinen (VII, R=CH3, OC2H5 bzw. SCH3) reduziert. Mit Hilfe der Chromatographie gelang es in zwei Fällen, aus den Rohprodukten auch die entsprechendendl-3-Isodeserpidine (VIII, R=CH3 bzw. OC2H5) zu isolieren. Zum Unterscheiden der Produkte der normalen Reihe (VII) und der 3-Iso-Reihe (VIII) wurden IR-Spektren und die Papierchromatographie angewendet.Mit 2 Abbildungen 相似文献
14.
Computations of the Diels-Alder (DA) reactions of azaphosphole representative namely, thiazolo[3,2-d][1,4,2]diazaphosphole with 1,3-butadiene and isoprene at the density functional theory level reveal concerted mechanisms via asynchronous transition states. The activation energies (B3LYP/6-311++G**// B3LYP/6-311G**), 16-19 kcal mol−1, are much smaller than the value (32.57 kcal mol−1) calculated for the DA reaction of the non-phosphorus analogue, imidazo[2,1-b]thiazole with 1,3-butadiene. An electron-withdrawing group at the 3-position of the dienophile enhances both stereo- and regioselectivities, which agree nicely with the experimental values. Inclusion of solvent effect (PCM model) reveals that the stereo- and regioselectivities are not affected appreciably. The relative stabilities of the transition structures corresponding to the endo/exo stereoisomers and meta (P/Me, 1:3)/para (P/Me, 1:4) regioisomers have been rationalized on the basis of the secondary molecular orbital interactions. 相似文献
15.
Krishna C. Joshi Vijai N. Pathak Raj Pal Singh 《Monatshefte für Chemie / Chemical Monthly》1980,111(6):1343-1350
Several new 2-(fluoroaryl)-3-dialkylaminomethylindoles, 3-acetyl-2-(fluoroaryl)-indoles, 2-(fluoroaryl)-3-indolylglyoxamides and corresponding tryptamines have been prepared as possible psychopharmacological agents. 2-(Fluoroaryl)-indoles have been synthesized by theFischer indole synthesis. 2-(Fluoroaryl)-indoles on treatment with oxalyl chloride and subsequent reaction with amines, gave 2-(fluoroaryl)-3-indolylglyoxamides. Some of these indolylglyoxamides were reducted with lithium aluminium hydride, to the corresponding tryptamines. 2-(Fluoroaryl)-indoles when subjected toMannich reaction afforded 3-dialkylaminomethyl-2-(fluoroaryl)-indoles. All these new compounds have been characterized by IR spectral studies.Possible Psychopharmacological Agents, Part XII, Part XI, J. Indian. Chem. Soc.57, 423 (1980). 相似文献
16.
A ring-closing metathesis approach was employed for the synthesis of a β-C-glycoside analog of the immunostimulant KRN7000. The protected C-glycosyl amino acid derivative 18 was converted to amino-olefin 20, and osmylation served to install the diol unit as a mixture of separable syn and anti isomers. Deprotection to the hydroxy-amine 21 was followed by N-acylation and debenzylation to deliver the target compound 5. 相似文献
17.
Reactions of titanium(IV) isopropoxide with acetamide, benzamide, and nicotinamide in different stoichiometric ratios in anhydrous benzene yielded imido derivatives of type (PriO)4-nTi(NHOCR)n where n = 1, 2, 3, and 4; R = CH3, C6H5, and C5H4N. All these complexes are insoluble in common organic solvents suggesting their polymeric nature. All these derivatives, with the exception of three which have characteristic melting points, did not sublime at 250°C in vacuo nor did they appear to decompose appreciably below 300°C. I.R. spectra of these derivatives are discussed. 相似文献
18.
Summary Novel bimetallic alkoxides of copper(II) of the type Cu[M(OPr-i)6]2 (M = Nb or Ta) have been synthesised by the interaction of CuCl2 (1 mol) with K[M(OPr-i)6] (2 mol). These bimetallic isopropoxides undergo facile alcohol interchange with primary alcohols such as MeOH, EtOH,n-PrOH andn-BuOH. However, witht-BuOH, the reaction cannot be driven to completion even under prolonged continuous azeotropic fractionation of the liberatedi-PrOH and the final product corresponded in analysis to Cu[Ta(OPr-i)2(OBu-t)4]2.I.r., electronic and electron spin resonance spectral and magnetic susceptibility measurements indicate a distorted octahedralD
4h geometry for copper(II) in these bimetallic alkoxides. 相似文献
19.
20.
Reaction of hexaamminecobalt(III) chloride with the silver salt of methanesulphonic acid in aqueous medium (1:3 molar ratio) forms hexaamminecobalt(III) methanesulphonate, [Co(NH3)6](CH3SO3)3, in high yield. This cobalt(III) complex has been characterized by spectroscopic techniques (UV/visible, IR and NMR) and its solubility product determined. The X-ray crystal structure shows that the [Co(NH3)6]3+ cations interact at the second sphere by sharing edges with the anions, via N–H O hydrogen bonds. The structure is related to that of [Co(NH3)6]Cl(CH3SO3)2, but is modified to accommodate additional anions in place of Cl−. 相似文献