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61.
62.
An etiobilirubin‐IIβ analog with the central C(10) CH2 group replaced by a diacetylene unit ( 1 ) was synthesized by base‐catalyzed condensation of bis‐[3‐methyl‐4‐ethyl‐5‐formylpyrrol‐2‐yl]‐diacetylene ( 3 ) with 3‐methyl‐4‐ethyl‐5‐p‐toluenesulfonyl‐2‐pyrrolinone ( 10 ). Diacetylenic rubin 1 is a dark red solid, giving orange solutions with uv‐visible absorption maxima near 460 nm. 相似文献
63.
Wang M Wang BM Shi L Tu YQ Fan CA Wang SH Hu XD Zhang SY 《Chemical communications (Cambridge, England)》2005,(44):5580-5582
A quinine/Selectfluor combination inducing rearrangement reaction of allylic alcohols was discovered, which involved a moderate yield with good enantioselective construction of alpha-quaternary carbon center and beta-fluoro aldehyde under base condition. 相似文献
64.
A rapid and efficient method for the preparation of a variety of substituted 2-quinolones has been developed through the reactions of o-aminoarylketones with ester compounds containing a reactive α-methylene moiety in the presence of a catalytic amount of cerium chloride heptahydrate under solvent-free conditions in high yields. The rate and yield of the reaction are considerably improved by employing microwave irradiation. 相似文献
65.
A series of KF/Al2O3 catalyzed Michael-addition reactions between malononitrile and α,β-unsaturated cycloketones in DMF solution were studied. At room temperature, 2-cyano-3-aryl-3-(1,2,3,4-tetrahydronaphthalen-1-one-2-yl) propionitrile derivatives were synthesized by the reaction between 2-arylmethylidene-1,2,3,4-tetra-hydronaphthalen-1-one and malononitrile. However, if the temperature was increased to 80℃, 2-amino-3-cyano-4-aryl-4H-benzo[h]chromene derivatives were obtained in high yields. When the α,β-unsaturated ketones were replaced by 2,6-biarylmethylidenecyclohexanone or 2,5-biarylmethylidenecyclopentanone, another series of 2-amino-3-cyano-4H-pyran derivatives was isolated successfully. The structures of the products were confirmed by X-ray diffraction analysis. 相似文献
66.
Novel bilirubin analogues with dipyrrinones conjoined to an acetylene rather than a methylene group were synthesized and examined spectroscopically. Despite the increased separation of the dipyrrinones forced by replacing a -CH(2)- by a -C(triple bond)C- unit, molecular dynamics calculations show that, like bilirubin, they may still engage in intramolecular hydrogen bonding to carboxylic acid groups when the propionic acid chains are slightly lengthened, e.g., butanoic acids. Unlike bilirubin, however, which is bent in the middle and has a ridge-tile shape, the acetylene orients the attached dipyrrinones along a linear path, and intramolecular hydrogen bonding preserves a twisted linear molecular shape. The extended planes of the dipyrrinones intersect along the -C(triple bond)C- axis at an angle of 136 degrees for the conformation stabilized by intramolecular hydrogen bonding in the bis-butyric acid rubin (1b). With shorter acid chains (propionic), only one CO(2)H can engage an opposing dipyrrinone in intramolecular hydrogen bonding, and in this energy-minimum conformation of the linear pigment 1a, the intersection of the extended planes of the dipyrrinones has an angle of 171 degrees. Spectroscopic evidence for such linearized and twisted structures was found in the pigments' NMR spectral data and their exciton UV-vis and induced circular dichroism spectra. 相似文献
67.
J. W. Hastings Shiao-Chun Tu James E. Becvar ‡ Robert P. Presswood 《Photochemistry and photobiology》1979,29(2):383-387
Abstract— The bioluminescent oxidation of reduced flavin mononucleotide by bacterial luciferase involves a long-lived flavoenzyme intermediate whose chromophore has been postulated to be the 4a-sub-stituted peroxy anion of reduced flavin. Reaction of long chain aldehyde with this intermediate results in light emission and formation of the corresponding acid. These experiments show that the typical aldehyde-dependent, luciferase-catalyzed bioluminescence can also be obtained starting with FMN and H2 O2 instead of FMNH2 and O2 . We postulate that the 4a-peroxy anion intermediate is formed directly by attack of H2 O2 on FMN. The latter may be bound to luciferase. An enzyme bound intermediate is formed which by kinetic analysis, flavin specificity for luminescence, aldehyde dependence, and bioluminescent emission spectrum appears to be identical with the species generated by reaction of FMNH, and O2 with luciferase. The quantum yield of the H2 O2 -- and FMN-initiated biolumlnescence is low but can be enhanced by certain metal ions, which also stimulate a chemiluminescent reaction of oxidized flavin with H2 O2 . The peak of this chemiluminescence. however, appears to be at a shorter wavelength than that (490 nm) of the bioluminescence. 相似文献
68.
Xing‐Yun Chai Zheng‐Ren Xu Hong‐Yan Ren Hai‐Ming Shi Ya‐Nan Lu Fei‐Fei Li Peng‐Fei Tu 《Helvetica chimica acta》2007,90(11):2176-2185
Eight new benzoylated gentisyl alcohol (=2‐(hydroxymethyl)benzene‐1,4‐diol) glucosides, itosides A–H ( 1 – 8 ), together with the new pyrocatechol (=benzene‐1,2‐diol) glycoside itoside I ( 9 ) were isolated from the bark and twigs of Itoa orientalis (Flacourtiaceae). In itosides B–D ( 2 – 4 ), the gentisyl alcohol moiety was esterified by 1‐hydroxy‐6‐oxocyclohex‐2‐ene‐1‐carboxylic acid, while itosides E–H ( 5 – 8 ) contained instead an additional 2‐hydroxybenzoic acid moiety. The compounds were accompanied by the known derivatives 4‐hydroxytremulacin ( 10 ), poliothyrsoside ( 11 ), poliothyrsin ( 12 ), homaloside D ( 13 ), tremulacin, and pyrocatechol β‐D ‐glucopyranoside. The structures of the new compounds were elucidated by spectral and chemical methods. 相似文献
69.
Roca M Martí S Andrés J Moliner V Tuñón I Bertrán J Williams IH 《Journal of the American Chemical Society》2003,125(25):7726-7737
A comparative theoretical study of a bimolecular reaction in aqueous solution and catalyzed by the enzyme catechol O-methyltransferase (COMT) has been carried out by a combination of two hybrid QM/MM techniques: statistical simulation methods and internal energy minimizations. In contrast to previous studies by other workers, we have located and characterized transition structures for the reaction in the enzyme active site, in water and in a vacuum, and our potential of mean force calculations are based upon reaction coordinates obtained from features of the potential energy surfaces in the condensed media, not from the gas phase. The AM1/CHARMM calculated free energy of activation for the reaction of S-adenosyl methionine (SAM) with catecholate catalyzed by COMT is 15 kcal mol(-1) lower the AM1/TIP3P free-energy barrier for the reaction of the trimethylsulfonium cation with the catecholate anion in water at 300 K, in agreement with previous estimates. The thermodynamically preferred form of the reactants in the uncatalyzed model reaction in water is a solvent-separated ion pair (SSIP). Conversion of the SSIP into a contact ion pair, with a structure resembling that of the Michaelis complex (MC) for the reaction in the COMT active site, is unfavorable by 7 kcal mol(-1), largely due to reorganization of the solvent. We have considered alternative ways to estimate the so-called "cratic" free energy for bringing the reactant species together in the correct orientation for reaction but conclude that direct evaluation of the free energy of association by means of molecular dynamics simulation with a simple standard-state correction is probably the best approach. The latter correction allows for the fact that the size of the unit cell employed with the periodic boundary simulations does not correspond to the standard state concentration of 1 M. Consideration of MC-like species allows a helpful decomposition of the catalytic effect into preorganization and reorganization phases. In the preorganization phase, the substrates are brought together into the MC-like species, either in water or in the enzyme active site. In the reorganization phase, the roles of the enzymic and aqueous environments may be compared directly because reorganization of the substrate is about the same in both cases. Analysis of the electric field along the reaction coordinate demonstrates that in water the TS is destabilized with respect to the MC-like species because the polarity of the solute diminishes and consequently the reaction field is also decreased. In the enzyme, the electric field is mainly a permanent field and consequently there is only a small reorganization of the environment. Therefore, destabilization of the TS is lower than in solution, and the activation barrier is smaller. 相似文献
70.
Ya-Ping Tu Guan-Yu Yang Yu-Hua Liu Shao-Nong Chen Yao-Zu Chen 《Journal of mass spectrometry : JMS》1991,26(7):645-648
The reaction mass spectrometry of cyclic glycols and monosaccharides with methylene chloride as reagent was studied. In the presence of ammonia, it was found that methylene chloride reacted stereoselectively with the quasi-molecular ions of cyclic glycols and monosaccharides to form characteristic ions, by comparison of the relative abundances of which the stereoisomers of cyclopentane-l,2-diols and cyclohexane-l,2-diols and some monosaccharides could be definitely distinguished. 相似文献