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11.
Kunihito Miyake Yasuhiro Masaki Ikuya Miyamoto Shozo Yanagida Takeshi Ohno Akio Yoshimura Chyongjin Pac 《Photochemistry and photobiology》1993,58(5):631-636
We have investigated the photosensitized monomerization of the cis,syn -cyclobutane dimer of 1,3-di-methylthymine using riboflavin tetraacetate and a 5-deazaflavin derivative as photosensitizer. Although little monomerization of the dimer is induced by photoexcitation of the flavins in the absence of any additives, the flavins can function as an efficient photosensitizer in the presence of magnesium perchlorate. Mechanistic studies involving spectroscopic, quantum-yield and flash-photolysis measurements demonstrated that the photosensitized monomerization exclusively proceeds through electron transfer from the dimer to the triplet flavins complexed with Mg2+ . The effects of magnesium perchlorate are compared with those on the chloranil-photosensitized monomerization and also with the effects of HClO4 on the flavin-photosensitized reaction. 相似文献
12.
Optically active o-substituted diphenyl N-substituted sulphilimines are readily synthesised by the reaction of the corresponding sulphides and t-butyl hypochlorite in the presence of l-menthol and amide anions. (−)-N-p-Tolylsulphonylsulphilimines (1, 2) obtained were converted to the corresponding (−)-N-unsubstituted sulphilimines (8, 9) by treating them with concentrated sulphuric acid. When (−)-S-o-anisyl S-phenyl N-(unsubstituted) sulphilimine (8) was treated with acylating agents or acrylonitrile, the corresponding optically active (−)-N-substituted sulphilimines were prepared with complete retention at sulphur. The absolute configuration of (−)-S-o-anisyl S-phenyl N-p-tolylsulphonylsulphilimine (1) was determined by converting it to (+)-S-o-anisyl sulphoxide (17). CD curves of (−)-o-substituted diarylsulphilimines exhibited a negative Cotton effect at around 270–285 nm, which was assigned to (S)-configuration at sulphur by comparing with the analogous sulphoxides. The substituent on the imino group of the sulphilimine gave no appreciable effect on the CD behavior and the lack of substituent effect was considered to be due to the semi-polar character of the S(IV)-N bond. Unusual effect of o-methoxy group on the CD curves was discussed in connection with solvent effect. Mechanism of this asymmetric synthesis has been investigated, and it has become apparent that the diastereomeric menthoxysulphonium chloride was an excess of (RR)-configuration was formed initially and the amide anion attacks the S atom of the salt with net inversion. 相似文献
13.
Yan Ouyang Wei Zhang Yue Ma Na Xu Dai-Zheng Liao Kazuyoshi Yoshimura Shi-Ping Yan 《Structural chemistry》2007,18(6):891-898
Two new tetranuclear complexes of macrocyclic oxamide [Cd(CuL)3](NO3)2·2.5H2O 1, [Mn(CuL)3(OH)2](ClO4)2·Mn(H2O)6·4.5H2O 2 (L = 1,4,8,11-tatraazacyclotradecanne-2,3-dione) have been synthesized, structurally characterized and preliminary investigated
by magnetic studies. The structures of the title complexes consist of a tetranuclear units MCu3 (M = Cd, Mn), the packing diagram shows two-dimensional and three-dimensional system through intermolecular weak interactions.
The temperature-dependent magnetic susceptibilities of complex 2 were analyzed by an approximate treatment leading to J = −33 cm−1, gCu = 2.10, gMn = 1.95 indicating antiferromagnetic exchange between Cu(II) and Mn(II) ions. 相似文献
14.
Ion-exchanger colorimetry for chromium(VI) with 1,5-diphenylcarbohydrazide has been developed for the determination of chromium at mug/l. concentrations in natural water samples. About 90% of the chromium(VI) in a 1-litre sample solution is concentrated in 200-400 mesh Dowex 50W-X4 resin within half an hour. It is possible to obtain higher sensitivity by employing a larger amount of sample solution. Total chromium can be determined by oxidizing chromium(III) to chromium(VI) with ceric sulphate. 相似文献
15.
Arakawa Y Ohnishi M Yoshimura N Yoshifuji S 《Chemical & pharmaceutical bulletin》2003,51(8):1015-1020
Synthesis of (1R,2S,5S,6R,8S)-3-azabicyclo[3.3.0]octane-2,6,8-tricarboxylic acid (2) from trans-4-hydroxy-L-proline (5) was attempted. A Diels-Alder reaction of 3,4-dehydroproline derivative 9 and cyclopentadiene afforded a single stereoisomer 11. The Diels-Alder adduct was smoothly converted to the hydrochloride of 2 (24) via RuO(4) oxidation. Although some racemization of the material or product was observed during the synthetic processes, the amino acid 24 proved to be optically pure. 相似文献
16.
Allylation of carbonucleophiles with allylic carbamates under neutral conditions has been studied. The C-allylation of carbonucleophile is competitive with the N-allylation of amines, and the structure of amines is crucial for the selectivity. Bulky secondary amines gave the best results. Also a new method of protection-deprotection of amines as carbamates has been developed. Smooth deprotection is possible by the palladium-catalyzed reaction of allyl carbamates with formic acid. This method is particulary useful for primary amines, including optically active amino acids. 相似文献
17.
Jadranka Vuković Shiro Matsuoka Kazuhisa Yoshimura Vladimir Grdinić Renata Jurišić Grubešić 《Mikrochimica acta》2007,159(3-4):277-285
A simple, sensitive and rapid solid-phase spectrophotometric procedure was developed for the determination of traces of phenol
with 4-aminoantipyrine as a reagent (AAP-SPS), and the optimal experimental conditions were established. This method was performed by sorption and direct absorbance measurements
of the product phenol-AAP sorbed on the anion-exchanger Dowex 1-X4 (0.2 g) at 495 nm (absorption maximum) and 700 nm (non-absorption wavelength). The
sensitivity offered by the AAP-SPS procedure was higher by a factor of 40 compared with the respective conventional spectrophotometric method. Metrological
characteristics were established using a prevalidation strategy. The AAP-SPS procedure is characterized by a linear calibration function in the working range of 0.05–0.50 μmol, low standard deviation
of procedure (±0.012), low limit of determination (0.021 μmol), and favorable random (±0.85 to ±11.27%) and systematic deviations
(−4.55 to +11.50%). Moreover, the accuracy of the system investigated by the recovery test is acceptable (99–102%). Favorable
working and performance characteristics make the new SPS method ideal for phenol monitoring in pharmaceutical preparations
as well as other matrices. 相似文献
18.
A glucose electrode was composed of a dissolved oxygen electrode and an immobilized glucose oxidase membrane prepared by plasma polymerization of propargyl alcohol as a monomer. Fairly good precision of the electrode response to sample solutions was obtained by measurements using the steady-state method or the reaction rate method. Activity of the glucose oxidase immobilized within the membrane and mounted on the electrode lasted for 50 consecutive measurements over 5 days, and, if the membrane was stored in a buffer solution of pH 7.0 at a temperature of 0°C, the activity was preserved for more than 2 months. Such immobilization of the glucose oxidase with the plasma polymer effectively suppressed interference from Cu2+ions, which would seriously interrupt oxidation of the glucose in homogeneous solutions, in the sample solutions. 相似文献
19.
A trace method for iron, based on ion-exchanger colorimetry, has been developed. 1,10-Phenanthroline is used as the colour reagent for iron(II) and citrate as the masking reagent for iron(III). Total iron can be determined after reduction of iron(III) to iron(II) with hydroxylamine. It is possible to determine iron at mug/l.-levels in different oxidation states in natural waters. 相似文献
20.
Tomoyuki Yoshimura 《Tetrahedron letters》2004,45(50):9241-9244
Diastereoselective construction of the 19-epi-C18-C25 segment of (−)-lasonolide A was achieved using a 5-exo-trigonal mode of radical cyclization for the creation of the contiguous quaternary and tertiary stereogenic centers at C22 and C23 as the key reaction step. During the dehydration stage, it was found that an unusual inversion of configuration took place. 相似文献