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71.
本文综述了中环萜类化合物的各种合成方法,它们根据成环方式可以分为四类:1.双环或三环化合物的桥键断裂,2.无环化合物的环合,3.常规环化合物的环扩大,4.大环化合物的环缩小。 相似文献
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V. B. Vol'eva I. S. Belostotskaya O. V. Shishkin Yu. T. Struchkov V. V. Ershov 《Russian Chemical Bulletin》1995,44(8):1489-1491
Anhydrodimers have been synthesized by reactions of salicylaldehyde and 3,5-di-tert-butylsalicylaldehyde with SOCl2 or PCl5. A mechanism of condensation has been proposed, and the molecular structure of dibenzo-2,6,9-trioxabicyclo[3.3.1]nona-3,7-diene has been determined by X-ray structural analysis.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1549–1551, August, 1995.The work was supported by the Russian Foundation for Basic Research (Project No. 94-03-08653). 相似文献
74.
Monot Frédéric Benoit Yves Ballerini Daniel Vandecasteele Jean-Paul 《Applied biochemistry and biotechnology》1990,(1):375-386
Utilization of lipases for synthesis of esters of hydrophilic polyols has been investigated. The choice of a suitable solvent
is crucial in this type of reaction. An interesting case is fatty acid esters from neopentylpolyols, such as trimethylolpropane,
which are of great interest as high temperature lubricants. Enzymatic synthesis of trimethylolpropane tricaprylate was studied
as an alternative to chemical manufacturing. Triester production occurred only if the water produced by esterification was
continuously removed from the medium. In these condition, kinetics of appearance and transformation of mono-, di- and triesters
were determined in order to define optimal conditions. 相似文献
75.
The addition of the macrocyclic polyether 18-Crown-6 (18C6) increases the selectivity of oxidation of ethylbenzene to -phenylethylhydroperoxide (PEH) in the presence of Ni(acac)2. The initial oxidation rate, selectivity and degree of conversion of ethylbenzene to PEH are greater than those catalyzed by Ni(acac)2 only. The efficiency of the macrocyclic ligand as an activator of Ni(acac)2 exceeds that of monodentate donor ligands. The high selectivity of the process is due to both the primary Ni(acac)2 · 18C6 complexes and the products of their transformation in the course of oxidation. The mechanism of ethylbenzene oxidation catalyzed by Ni(acac)2 · 18C6 complexes is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1406–1411, August, 1994. 相似文献
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Bassan A Blomberg MR Siegbahn PE Que L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(2):692-705
The reactivity of [HO-(tpa)Fe(V)=O] (TPA=tris(2-pyridylmethyl)amine), derived from O-O bond heterolysis of its [H(2)O-(tpa)Fe(III)-OOH] precursor, was explored by means of hybrid density functional theory. The mechanism for alkane hydroxylation by the high-valent iron-oxo species invoked as an intermediate in Fe(tpa)/H(2)O(2) catalysis was investigated. Hydroxylation of methane and propane by HO-Fe(V)=O was studied by following the rebound mechanism associated with the heme center of cytochrome P450, and it is demonstrated that this species is capable of stereospecific alkane hydroxylation. The mechanism proposed for alkane hydroxylation by HO-Fe(V)=O accounts for the experimentally observed incorporation of solvent water into the products. An investigation of the possible hydroxylation of acetonitrile (i.e., the solvent used in the experiments) shows that the activation energy for hydrogen-atom abstraction by HO-Fe(V)=O is rather high and, in fact, rather similar to that of methane, despite the similarity of the H-CH(2)CN bond strength to that of the secondary C-H bond in propane. This result indicates that the kinetics of hydrogen-atom abstraction are strongly affected by the cyano group and rationalizes the lack of experimental evidence for solvent hydroxylation in competition with that of substrates such as cyclohexane. 相似文献
80.
In the presence of [Ru(terpyridine)(2,6‐pyridinedicarboxylate)], aliphatic and benzylic alcohols are oxidized to the corresponding aldehydes or ketones with high selectivity by using hydrogen peroxide as the oxidant. There is no need for the addition of co‐catalysts or organic solvents. By applying an optimized reaction protocol, high catalyst productivity (turnover number>10 000) and activity (turnover frequency up to 14 800 h?1) has been achieved. 相似文献