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101.
Imines of (1S,9S)-t-butyl-9-amino-octahydro-6,10-dioxo-6H-pyridazino[1,2-a][1,2]diazepine-1-carboxylate undergo thermal (toluene, 110°C) or LiBr-DBU catalysed (MeCN, room temperature) regio- and stereo-specific cycloaddition to a range of chiral dipolarophiles giving enantiopure spiro-cycloadducts in excellent yield. The reactions proceed via intermediate NH azomethine ylides and litho azomethine ylides, respectively and results in the multiplication of chiral centres from 2 (one of which is lost in the process) to 5. 相似文献
102.
Shunsuke Hayashi Takashi Ishikawa Tatsuo Asai Colin Turnbull Kanzo Sakata Koji Ogawa 《Tetrahedron》2004,60(33):7005-7013
The hydrolysis of 2-phenylethyl β-d-glucopyranoside (3) was found to be partially inhibited by feeding with 2-phenyl-N-glucosyl-acetamidiumbromide (8), a β-glucosidase inhibitor, resulting in a decrease in the diurnal emission of 2-phenylethanol (2) from Rosa damascena Mill. flowers. Detection of [1,1,2,2′,3′,4′,5′,6′-2H8]-2 and [1,2,2′,3′,4′,5′,6′-2H7]-2 from R. ‘Hoh-Jun’ flowers fed with [1,1,2,2′,3′,4′,5′,6′-2H8]-3 suggested that β-glucosidase, alcohol dehydrogenase, and reductase might be involved in scent emission. Comprehensive GC-SIM analyses revealed that [1,2,2,2′,3′,4′,5′,6′-2H8]-2 and [1,2,2,2′,3′,4′,5′,6′-2H8]-3 must be biosynthesized from [1,2,2,2′,3′,4′,5′6′-2H8] l-phenylalanine ([2H8]-1) with a retention of the deuterium atom at α-position of [2H8]-1. 相似文献
103.
Douglas E. Moore Sarah Roberts-Thomson Dong Zhen Colin C. Duke 《Photochemistry and photobiology》1990,52(4):685-690
Irradiation with UVA light of the anti-inflammatory drug diclofenac [2-(2,6-dichloroanilino)phenylacetic acid] in aqueous buffer or methanol solution leads to sequential loss of both chlorine substituents and ring closure to carbazole-1-acetic acid as the major product. Minor products result from substitution by the solvent. The photosensitizing properties of diclofenac and its major photoproduct were tested with singlet oxygen substrates and in the free radical polymerization of acrylamide. Although the major carbazole product is a weakly phototoxic agent, able to generate singlet oxygen more efficiently than diclofenac, the free radical photodechlorination process is postulated as the probable initiation step of in vivo photosensitivity responses. 相似文献
104.
Ellen Herlihy Peter H. Gies Colin R. Roy Michael Jones 《Photochemistry and photobiology》1994,60(3):288-294
Abstract Quantifying individual exposure to ultraviolet radiation (UVR) is critical to understanding the etiology of a number of diseases including nonmelanotic and melanotic skin cancers. Measurements of personal exposure to solar UVR were made in Hobart, Tasmania in February (summer) 1991 for six different outdoor activities using UVR-sensitive polysulfone (PS) film attached at seven anatomical sites. Concurrent behavioral and environmental observations were also made. To date many studies have relied on subject recall to quantify past solar UVR exposures. To gain insight into the accuracy of subject recall the measured UVR exposures received by different subjects using the PS film were compared to those calculated from personal diaries and ambient solar UVB levels from a monitoring station. In general, when UVR exposure activities took place under close supervision, good correlations were obtained between the PS badges and the ambient measurements/diaries approach. Ultraviolet radiation exposures for the field study involving 94 subjects engaged in a number of outdoor activities are presented. 相似文献
105.
Colin Eaborn Peter B. Hitchcock Paul D. Lickiss 《Journal of organometallic chemistry》1981,221(1):13-17
The structure of the crowded molecule (Me3Si)3C(SiMe2Ph) has been determined by single crystal X-ray diffraction. The steric strain manifest itself mainly in lengthening of the Me3SiC and Me2PhSiC bonds (average length 1.920(6) ) and closing up of the CSiC angles within the Me3Si and Me2PhSi groups (average 105.2(10)°), with correspondingly large C(1)SiC angles (113.5(13)°; C(1) is the central carbon atom). 相似文献
106.
As part of a programme to synthesize thione derivatives with pentacyclo[5.4.0.02,6.03,10.05,9]undecane moieties it was decided to sulfurize the monoacetal 6 of pentacyclo[5.4.0.02,6.03,10.05,9]undecane-8,11-dione 2. Unexpectedly the diol 9 was isolated as the product. 相似文献
107.
Ellipsometry, surface tensiometry, and contact-angle measurement have been used to study the transition between partial wetting and pseudo-partial wetting of surfactant solutions by alkanes. In the partial wetting regime, the air-water surface tension is the same with and without alkane. In the pseudo-partial wetting regime, the air-water surface tension is lowered by the presence of alkane, showing that oil is solubilised into the surfactant monolayer. A discontinuous change in the coefficient of ellipticity with increasing surfactant concentration provides unequivocal evidence for the first-order nature of the wetting transitions. Ellipsometry has been used to explore the generality of wetting transitions of alkanes (dodecane, hexadecane, and squalane) on surfactant solutions [dodecyltrimethylammonium bromide, tetredecyltrimethylammonium bromide, dibucaine hydrochloride, and Aerosol OT (AOT)]. Of the systems studied, only hexadecane on AOT solutions did not show a wetting transition. Excess alkane remains as a lens on the surface of the surfactant solutions at all concentrations, but the contact angle is a minimum at the wetting transition. A semiquantitative model for the variation of the contact angle with surfactant concentration is provided. 相似文献
108.
7,7'-Bis(((dimethylamino)carbonyl)oxy)-8,8'-biquinolyl (5) was prepared in 71% yield by regioselective directed ortho metalation (DoM) of N,N-dimethyl O-quinol-7-yl carbamate (2) with LDA followed by oxidation with anhydrous ferric chloride. DoM of 5 with excess LDA induced double anionic ortho-Fries rearrangement and gave 6,6'-bis((dimethylamino)carbonyl)-7,7'-dihydroxy-8,8'-biquinolyl (8). Treatment of N,N-diethyl O-(8-iodoquinol-7-yl) carbamate (16) with LDA in THF solvent at -78 degrees C, followed by addition of anhydrous ferric chloride, resulted in an efficient tandem halogen-dance dimerization process which afforded 7,7'-bis(((diethylamino)carbonyl)oxy)-6,6'-diiodo-8,8'-biquinolyl (17) directly in 54% yield. 相似文献
109.
Calculations on several free radicals derived from ascorbic acid, and α-hydroxytetronic acid are reported. The calculations have been carried out both with the INDO method and the ab initio UHF method. The calculated spin densities are only consistent with the assignment of the structure of the predominant radical derived from these molecules to the anion radical. 相似文献
110.
The preparation of the η4-4-2,3,5,6-tetramethyl-1,4-benzoquinonecomplex [CO(C5Me5)(C10H12O2)] (I) is reported. Complex I undergoesreversible protonation to yield the 2-6-η-4-hydroxy-1-oxo-2,3,5,6-tetramethylcyclohexadienyl complex [Co(C5Me5)(C10H13O2)BF4 (II) and diprotonation to yield the η6-6-1,4-dihydroxy-2,3,5,6-tetramethylbenzene complex [Co(C5Me5)(C10H14O2)] (BF4)2 (III). Methylation of complex I with MeI/AgPF6 gives the 2---6-η-4-methoxy-1-oxo-2,3,5,6-tetramethylcyclohexadienyl complex [Co(C5Me5)(C11H15O2])PF6 (IV). In trifluoroacetic acid solution complex IV is protonated to form the η6-1-hydroxy-4-methoxy-2,3,5,6-tetramethylbenzene cation [Co(C5Me5)-(C11H16O2)]2+ 相似文献