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A carborane-containing stable simple enol — 1-2-isopropyl-o-carboran-I-yl)-1-phenyl2-mesityl-2-lrydroxyctlrylcne — has been synthesized. This enol does not isomerize to the starting ketone or keto-enol mixture even after prolonged heating in benzene in the presence of CF3COOH.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1561–1563, June, 1996. 相似文献
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K. A. Lyssenko D. V. Lyubetsky M. Yu. Antipin I. L. Odinets 《Russian Chemical Bulletin》2005,54(11):2484-2491
The nature of the intramolecular O—H...O bond was studied and its energy was estimated by X-ray diffraction analysis and quantum-chemical
calculations (B3LYP/6-311G**) of (diphenylphosphoryl)acylacetonitriles. The influence of the nature of the substituents at
the double bond in the H-bonded ring and the crystal packing effects on the hydrogen bond were investigated.
Dedicated to Corresponding Member of the Russian Academy of Sciences T. A. Mastryukova.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2406–2413, November, 2005. 相似文献
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Branchadell V Crévisy C Grée R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(22):5795-5803
The tandem isomerization-aldolization reaction between allyl alcohol and formaldehyde mediated by [Fe(CO)3] was studied with the density functional B3LYP method. Starting from the key [(enol)Fe(CO)3] complex, several reaction paths for the reaction with formaldehyde were explored. The results show that the most favorable reaction path involves first an enol/allyl alcohol ligand-exchange process followed by direct condensation of formaldehyde with the free enol. During this process, formation of the new C-C bond takes place simultaneously with a proton transfer between the enol and the aldehyde. Therefore, the role of [Fe(CO)3] is to catalyze the allyl alcohol to enol isomerization affording the free enol, which adds to the aldehyde in a carbonyl-ene type reaction. Similar results were obtained for the reaction between allyl alcohol and acetaldehyde. 相似文献
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Zvjezdana Lazarević Jasna Vorkapić-Furač Jasenka Mühl 《Monatshefte für Chemie / Chemical Monthly》1992,123(12):1175-1179
Summary Stable enolic isomers of 2-aroyl-4-aracyl-1,3-cyclopentanediones such as3 and4 were prepared by condensation of aryl methyl ketones and diethyl maleate using an excess of sodium ethoxide (Aryl=C6H5, 4-C6H4CH3, 4-C6H4Br and 4-C6H4Cl).
-Tricarbonyl Verbindungen. I. 2,4-Disubstituierte 1,3-Cyclopentandione
Zusammenfassung Stabile Enol-Isomere von 2-Aroyl-4-aracyl-1,3-cyclopentandionen wie3 und4 wurden durch Kondensation von Arylmethylketonen und Diethylmaleat mit einem Überschuß von Natriumethoxid dargestellt (Aryl=C6H5, 4-C6H4CH3, 4-C6H4Br und 4-C6H4Cl).相似文献
5.
Dr. Dominik Koszelewski Prof. Ryszard Ostaszewski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(43):10156-10164
A new protocol based on lipase-catalyzed tandem reaction toward α,β-enones/enoesters is presented. For the synthesis of the desired products the tandem process based on enzyme-catalyzed hydrolysis and Knoevenagel reaction starting from enol acetates and aldehyde is developed. The relevant impact of the reaction conditions including organic solvent, enzyme type, and temperature on the course of the reaction was revealed. It was shown that controllable release of the active methylene compound from the corresponding enol carboxylate ensured by enzymatic reaction diminishes significantly the formation of the unwanted co-products. Furthermore, this protocol was extended by including a second tandem chemoenzymatic transformation engaging various aldehyde precursors. After a careful optimization of the reaction conditions, the target products were obtained with yields up to 86 % and with excellent E/Z-selectivity. 相似文献
6.
Enhancement of Light Absorption Ability of Synthetic Chlorophyll Derivatives by Conjugation with a Difluoroboron Diketonate Group
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Dr. Yusuke Kinoshita Dr. Yuichi Kitagawa Prof. Dr. Hitoshi Tamiaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(29):9996-10001
The enhancement of the light absorption ability of synthetic chlorophyll derivatives is demonstrated. Chlorophyll derivatives directly conjugated with a difluoroboron 1,3‐diketonate group at the C3 position were synthesized from methyl pyropheophorbide‐d through Barbier acylmethylation of the C3‐formyl moiety, oxidation of the C3‐carbinol, and difluoroboron complexation of the diketonate. Electronic absorption spectra in a diluted solution showed that the synthetic conjugates gave an absorption band at λ=400–500 nm, with a Qy band shifted to a longer wavelength of λ≈700 nm. DFT calculations demonstrated that the absorption bands and redshifts were ascribable to the coupling of the LUMO of chlorin with that of the difluoroboron diketonate moiety. The introduction of a pyrenyl group at the C33‐position of the conjugate afforded an additional charge‐transfer band over λ=500 nm, producing a pigment that bridged the green gap in standard chlorophylls. 相似文献
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Inside Cover: Enhancement of Light Absorption Ability of Synthetic Chlorophyll Derivatives by Conjugation with a Difluoroboron Diketonate Group (Chem. Eur. J. 29/2016)
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