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11.
The complexation of tetramethylresorc[4]arene with primary and secondary amines in acetonitrile was investigated spectrophotometrically. The stoichiometry of the complexes formed was shown to depend on the amine concentration. Based on the proposed complexation models, the formation constants of the complexes as well as their thermodynamical parameters were determined and discussed. Depending on the amine concentration, two types of solid complexes of tetramethylresorc[4]arene with amines were obtained. The composition of these complexes was confirmed by 1H NMR. 相似文献
12.
Adam W Alsters PL Neumann R Saha-Möller CR Seebach D Beck AK Zhang R 《The Journal of organic chemistry》2003,68(21):8222-8231
The epoxidation of allylic alcohols is shown to be efficiently and selectively catalyzed by the oxidatively resistant sandwich-type polyoxometalates, POMs, namely [WZnM(2)(ZnW(9)O(34))(2)](q)(-) [M = OV(IV), Mn(II), Ru(III), Fe(III), Pd(II), Pt(II), Zn(II); q = 10-12], with organic hydroperoxides as oxygen source. Conspicuous is the fact that the nature of the transition metal M in the central ring of polyoxometalate affects significantly the reactivity, chemoselectivity, regioselectivity, and stereoselectivity of the allylic alcohol epoxidation. For the first time, it is demonstrated that the oxovanadium(IV)-substituted POM, namely [ZnW(VO)(2)(ZnW(9)O(34))(2)](12-), is a highly chemoselective, regioselective, and also stereoselective catalyst for the clean epoxidation of allylic alcohols. A high enantioselectivity (er values up to 95:5) has been achieved with [ZnW(VO)(2)(ZnW(9)O(34))(2)](12)(-) and the sterically demanding TADOOL-derived hydroperoxide TADOOH as regenerative chiral oxygen source. Thus, a POM-catalyzed asymmetric epoxidation of excellent catalytic efficiency (up to 42 000 TON) has been made available for the development of sustainable oxidation processes. The high reactivity and selectivity of this unprecedented oxygen-transfer process are mechanistically rationalized in terms of a peroxy-type vanadium(V) template. 相似文献
13.
PHOTOCHEMISTRY and PHOTOBIOLOGY WITHOUT LIGHT 总被引:3,自引:0,他引:3
Abstract— This review covers the literature since 1980 on chemically and enzymatically generated electronically excited species. The emphasis lies on triplet states of carbonyl products that are derived from dioxetanes and dioxetanones as precursors or from suitable enzymatic oxygenations. Singlet oxygen, an important excited state species in biological processes, is not explicitly treated. The utilization of triplet excited carbonyl products to promote photochemical and photobiological transformations by energy transfer are of primordial interest and not the photomechanistic behavior, photophysical properties and inherent photochemical reactions of such excited state species. Thus, the coverage concentrates on photodamage of DNA and RNA, the photochemistry of flavins, vitamin D, tryptophan, arachidonic acid, chlorophyll, lipid peroxidation, urocanase activation, excitation of chlorophlasts, and the aerobic oxidation of Schiff bases derived from amino acids and proteins. The potential perspectives of employing authentic dioxetanes and enzymatically generated dioxetane intermediates as effective photon equivalents in photochemotherapy, phototoxicity, photoaffinity labeling and photogenotoxicity are pointed out, in the hope of stimulating more intensive activity in this emerging and novel bioorganic and photobiological field. 相似文献
14.
Tetraphenylporphyrin-sensitized photooxygenation of 2-methyl-5-trimethylsilylfuran () affords quantitatively trimethylsilyl 2-oxo-4-pentenoate (), presumably via intramolecular Baeyer-Villiger rearrangement of the intermediary dioxirane (). 相似文献
15.
Comparison of different strains of the yeastYarrowia lipolytica for citric acid production from glucose hydrol 总被引:3,自引:0,他引:3
Maria Wojtatowicz Waldemar Rymowicz Helena Kautola 《Applied biochemistry and biotechnology》1991,31(2):165-174
Four commercial strains and two mutants of the yeast species Yarrowia lipolytica were screened using batch fermentation. Strain Y. lipolytica A-101-1.14 (induced with UV irradiation) was found to be the most suitable for citric acid production from glucose hydrol (39.9% glucose and 2.1% other sugars), a byproduct of glucose production from potato starch. The specific rate of total citric and isocitric acid production was 0.138 g/g.h, the yield on consumed glucose 0.93 g/g, and the productivity achieved was as high as 1.25 g/L.h. All of the tested yeast strains were able to utilize only the glucose from the glucose hydrol medium. Thus, some residual higher oligosaccharides remained in the process effluent. 相似文献
16.
Waldemar Adam 《Angewandte Chemie (International ed. in English)》1974,13(10):619-627
The photodecarboxylation of malonyl peroxides into α-lactones[1] and the thermal conversion of the 1,4-endo-peroxide 4,5-epoxy-3,6-epidioxy-1-cyclohexene into the novel benzene trioxide[2] are two recent examples of the potential of cyclic peroxides in the synthesis of unusual organic molecules. The former transformation entails a fragmentation, the latter a rearrangement process. Most reported examples fall into one of these two gross reaction types. Of the numerous examples that have been reported in the literature during the last two decades, only those shall be focused on that lead to unusual compounds or constitute efficient syntheses of known compounds, in order to stress the convenience of cyclic peroxides in the synthesis of organic compounds. 相似文献
17.
A micro determination for free uronic acids based on Tollens' reaction is proposed. Sources of error in earlier methods are avoided by the use of phosphoric acid, a reagent solution in glacial acetic acid, and extraction of the dye with toluene. Free glucuronic acid can be determined in presence of glucuronosides of the phenol-ether type up to molar ratios of ca. 1 : 5. Reliable results can also be obtained in the presence of other carbohydrates. 相似文献
18.
Kazimierz?DarowickiEmail author Waldemar?Felisiak Artur?Zieliński 《Journal of mathematical chemistry》2005,38(4):701-711
Oscillations of species concentration are phenomena accompanying several types of electrochemical and purely chemical processes.
Importance of analyzing of such processes results from both scientific and practical reasons. In the paper the authors deal
with investigation of time dependent spectra of various stages of Belousov-Zhabotinsky type chemical oscillations. As the
analytical tool the discrete wavelet transform is proposed. 相似文献
19.
Photo-extrusion of nitrogen from the azoalkane 1 in the presence of molecular oxygen gave besides the hydrocarbons 3 and 5, the endoperoxide 10 and hydroperoxide 11, the former via trapping of the 1,4-diradical 4 by triplet oxygen, the latter by ene-reaction-6f hydrocarbon 5 with singlet oxygen. 相似文献
20.
The 6-hydroperoxy-1,4-cyclooctadiene (), which is formed in the photosensitized oxygenation of 1,5-cyclooctadiene (), affords on further singlet oxygenation 5,8-dihydroperoxy-1,3-cyclooctadiene (), which via triphenylphosphine reduction leads to -5,8-dihydroxy-1,3-cyclooctadiene () and subsequent pyridinium chlorochromate oxidation to 1,3-cyclooctadien-5,8-dione (). 相似文献