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41.
Based on the mechanism postulated for the formation of the cyclic carbonates 3 in the reactions of glycols 1 with oxalyl chloride in the presence of triethylamine, we present here three efficient syntheses of the cyclic oxalates 2 of various glycols 1 by controlling the formation of 3: replacement of the base by pyridine markedly diminishes yields of 3 in all reactions, realizing dramatic reversals of the product ratios in the reactions with the (R*,R*)-compounds 1g-i,q,r and pinacol (1k); although considerable amounts of the oxalate polymers are formed in the reactions with some (R*,S*)-glycols, this drawback can be removed by the use of 2,4,6-collidine instead of pyridine; 1,1'-oxalyldiimidazole is useful for the synthesis of two selected cyclic oxalates 2e,f. The cyclic oxalates 2 other than trisubstituted and tetrasubstituted ones were found to be very reactive: kinetic studies on the hydrolysis of 1,4-dioxane-2,3-dione (2a) as well as its mono- and some selected 5,6-disubstituted derivatives 2 have revealed that they undergo hydrolysis 260-1500 times more rapidly than diethyl oxalate (12) in acetate buffer-acetonitrile (pH 5.69) at 25 degrees C. Although the cyclic oxalate 21 from cis-1,2-cyclopentanediol (11) was 1.5 times more reactive than 2a, it has been shown with other substrates that increasing number of the alkyl substituents decreases the rate of hydrolysis. On the contrary, the phenyl group was found to have somewhat accelerative effect. 相似文献
42.
Hideo Hirai Kozo Sawada Matsuhiko Aratani Masashi Hashimoto 《Tetrahedron letters》1985,26(14):1739-1742
A stereoselective kinetic protonation of the azetidinone enolate was studied and an efficient synthesis of(cis) was achieved via aldol reaction of with acetone followed by the kinetic protonation with Ph3SnH as proton source. 相似文献
43.
Mugishima T Tsuda M Kasai Y Ishiyama H Fukushi E Kawabata J Watanabe M Akao K Kobayashi J 《The Journal of organic chemistry》2005,70(23):9430-9435
[Structure: see text]. Citrinadin A (2) is a pentacyclic indolinone alkaloid isolated from the cultured broth of a fungus, Penicillium citrinum, which was separated from a marine red alga. The absolute stereochemistry of the pentacyclic core in 2 and its new congener, citrinadin B (1), was elucidated by analysis of the ROESY spectrum for the chlorohydrin derivative (3) of 1 as well as comparison of the electronic circular dichroism (ECD) spectra for 1 and 2 with those of known spirooxiindole alkaloids. On the other hand, the absolute configuration at C-21 bearing an epoxide ring was assigned as S by comparison of the vibrational circular dichroism (VCD) spectra of 1 with those of model compounds 2S- and 2R-2,3-epoxy-3,3-dimethyl-1-phenylpropan-1-one (4a and 4b, respectively). 相似文献
44.
peri-Acenes have shown great potential for use as functional materials because of their open-shell singlet biradical character. However, only a limited number of peri-acene derivatives larger than peri-tetracene have been synthesized to date, presumably owing to the low stability of the target compounds in addition to the complicated synthesis scheme. Here, a very simple synthesis route for the tetrabenzo[a,f,j,o]perylene (TBP) structure enables the development of highly stable peri-tetracene analogues. Despite a high degree of singlet biradical character, the compounds with four substituents at the zigzag edge show a remarkable stability in solution under ambient conditions, which is better than that of acene derivatives with a closed-shell electronic configuration. The crystal structures of the TBP derivatives were obtained for the first time; these are valuable to understand the relationship between the structure and biradical character of peri-acenes. The application of peri-acenes in electronic devices should also be investigated. Therefore, the semiconducting properties of the TBP derivative were investigated by fabricating the field-effect transistors.Highly stable peri-tetracene analogues with a high degree of singlet biradical character were synthesized in a very simple route, and their crystal structures and semiconducting properties were investigated. 相似文献
45.
46.
K. Nagamine Y. Miyake P. Birrer K. Shimomura M. Iwasaki T. Kuga J. Marangos 《Hyperfine Interactions》1994,87(1):1083-1089
A concept, a construction and an account of commissioning experiments up to May 1993 are given for the recently completed ultra-slow positive muon facility at the pulsed muon facility of UT-MSL/KEK. The intense and ultra-slow
+ beam with an extremely small phase-space volume to be produced in this facility will open new muon sciences includingSR studies on material surfaces. 相似文献
47.
48.
P. Strasser K. Ishida S. Sakamoto M. Iwasaki E. Torikai K. Nagamine G. M. Marshall 《Hyperfine Interactions》1993,82(1-4):543-549
Slow – production via dd-CF using a two-layer arrangement is investigated. To determine its feasibility, experimental measurements are now in progress using the muonic X-ray detection method. The following experimental steps are being considered: (1) measurement of the number of – stopped inside a solid H2/D2 layer by detecting p K X-rays, (2) hot d emission detection by placing a secondary target at a distance of 10–30 mm from the layer and by detecting specific delayed X-rays, (3) measurement of the disappearance of d emission as the added D2 layer is increased, (4) dd-CF measurement by detecting fusion protons, and (5) slow – emission detection. Results of the initial test experiment are presented. 相似文献
49.
K. Nagamine Y. Miyake P. Birrer K. Shimomura M. Iwasaki K. Nishiyama P. Strasser T. Kuga J. Marangos 《Hyperfine Interactions》1993,80(1-4):1287-1295
A concept, a design, a construction and an account of commissioning experiments are given for the recently completed ultra-slow muon facility at the pulsed muon facility of UT-MSL/KEK. The intense (more than 103/s) slow + beam with an extremely narrow phase-space volume (0.2 eV×(3 cm)2) to be produced in this facility will open a new muon science including surface physics and chemistry and fundamental atomic physics.Post-doctoral fellow of Swiss National Science Foundation. 相似文献
50.