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241.
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Nakayama J Aoki S Takayama J Sakamoto A Sugihara Y Ishii A 《Journal of the American Chemical Society》2004,126(29):9085-9093
5,6-Di-tert-butyl-2,3,7-trithiabicyclo[2.2.1]hept-5-ene 7-endo-oxide (4) was prepared by addition of S(2)Cl(2) to 3,4-di-tert-butylthiophene 1-oxide (3) in high yield. The oxidation of 4 with dimethyldioxirane gave a 7:1 isomeric mixture of 5,6-di-tert-butyl-2,3,7-trithiabicyclo[2.2.1]hept-5-ene 2-endo-7-endo-dioxide (5a) and 2-exo-7-endo-dioxide (5b) quantitatively. The thermally labile 5 was shown to undergo a retro-Diels-Alder reaction that produces S(2)O and 3 in a reversible way. The resulting S(2)O was trapped by Diels-Alder reactions with dienes to give 3,6-dihydro-1,2-dithiin 1-oxides in good yields. In the absence of the dienes, S(2)O disproportionates to SO(2) and S(3), and the resulting S(3) underwent a 1,3-dipolar cycloaddition with 3 on its syn-pi-face with respect to the S[double bond]O bond to give a trithiolane derivative, whereas in the presence of excess norbornene, it produced the 1,3-dipolar cycloadduct with norbornene in good yield. Thus, the retro-Diels-Alder reaction of 5 functions as an S(2)O and S(3) source. DFT calculations at the B3LYP/6-311+G(3df,2p) level were carried out in order to explain why S(2)O disproportionates to SO(2) and S(3) and why S(2)O acts as a dienophile and not a 1,3-dipole, whereas O(3) and S(3) serve as 1,3-dipoles. 相似文献
244.
Yoshiaki Toba 《Fluid Dynamics Research》1988,2(4):263-279
The statistical properties of growing wind waves are known to obey certain self-similarity laws. One of these is expressed as the
-power law relation between the significant wave-height and the significant wave period in nondimensional forms. Recent experiments on turbulence above and below laboratory wind waves indicate that both the air and the water layers have a structure which is similar to that of the turbulent boundary layer over a rough solid wall. The continuity of the momentum flux through the air and water boundary layers combined with the
-power law of wind waves means that all the characteristic velocities related to the air-water boundary process are proportional to one another. Our laboratory experimental data on the several characteristic variables concerned support this picture. The state of local equilibrium as expressed by the
-power law is thought to be brought about by the “breaking adjustment of the wind wave” which is required by the overall continuity of the velocity and the momentum flux across a thin surface layer. The above proportionality of the characteristic velocities provides a physical basis for the observed friction velocity scaling of the ocean mixed layer. 相似文献
245.
Dr. Yuya Ashida Akihito Egi Dr. Kazuya Arashiba Prof. Dr. Hiromasa Tanaka Taichi Mitsumoto Dr. Shogo Kuriyama Prof. Dr. Kazunari Yoshizawa Prof. Dr. Yoshiaki Nishibayashi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(25):e202200557
A series of chromium-halide, -nitride, and -dinitrogen complexes bearing carbene- and phosphine-based PCP-type pincer ligands has been newly prepared, and some of them are found to work as effective catalysts to reduce dinitrogen under atmospheric pressure, whereby up to 11.60 equiv. of ammonia and 2.52 equiv. of hydrazine (16.6 equiv. of fixed N atom) are produced based on the chromium atom. To the best of our knowledge, this is the first successful example of chromium-catalyzed conversion of dinitrogen to ammonia and hydrazine under mild reaction conditions. 相似文献
246.
Yoshiaki Wakita Tomoyuki Yasunaga Masaharu Kojima 《Journal of organometallic chemistry》1985,288(3):261-268
Secondary and/or tertiary alcohols and unsymmetrical ketones have been obtained in moderate to good yields by the palladium-catalyzed (5 mol%) carbonylative coupling of aryl iodides with alkylaluminum compounds under very mild conditions (20–50°C, 1 atm of carbon monoxide). The type of the reaction product depended on the aluminum reagent employed. While the selective formation of secondary alcohols was observed in the reaction with i-Bu3Al, the use of Et3Al led to a mixture of a ketone and two alcoholic products. With Et2AlCl predominantly unsymmetrical ketones were produced. In all cases, formation of directly cross-coupled products was not observed. DME and benzene can be used as solvents, but THF is unsuitable. Nickel catalysts were found to be ineffective for this reaction. 相似文献
247.
The α-alkyl β-oxoesters undergo type II photoreactions. The process of back hydrogen transfer in the 1,4-biradical intermediate to revert to the starting ester is suppressed because of the intramolecular hydrogen bonding between the hydroxyl and carboalkoxyl groups in the biradical intermediate. The hydrogen bonding determines the stereochemistry of 1,4-biradical cyclization. The cyclobutanols having the hydroxyl group cis to the carboalkoxyl group are formed exclusively from the α-alkyl β-oxoesters . The enol form of the type II elimination product, the benzoylacetate , acts as an effective internal filter for the photoreaction of the α-alkyl β-oxoester . 相似文献
248.
Takeuchi H Nagira S Tanimura S Yamamoto H Kawashima Y 《Chemical & pharmaceutical bulletin》2005,53(5):487-491
We attempted to make the rapidly dissolving tablet (Tab) containing solid dispersion particles (SD) with indomethacin (IMC) and porous silica (Sylysia350) as carrier prepared by using spray-drying technique. Rapidly dissolving tablet was formulated with mannitol as a diluent and low substituted hydroxypropylcellulose (L-HPC) or partly pre-gelatinized starch (PCS) as a disintegrant. The percent dissolved from Tab (SD) was higher than that of tablet containing physical mixture (PM) at 20 min. Nearly 100% of drug in Tab (SD) was dissolved within 60 min, while the drug dissolution of Tab (PM) was not completed at the same time period. In addition, the tensile strength of Tab (SD) was much higher than that of Tab (PM). Adding L-HPC in Tab (SD) (Tab (SD-L-HPC)), the percent dissolved from Tab (SD-L-HPC) at 5 min became much higher than that from Tab (SD). The dissolution profile of IMC from Tab (SD-L-HPC) was almost the same irrespective of the compression pressure, while the tensile strength of tablet increased with increasing the compression pressure. In comparing the compaction property of these tablets by observing the ratio of residual die wall pressure (RDP) to maximum die wall pressure (MDP) (RDP/MDP), it was found that addition of L-HPC in the tablet formulation improved compactibility. In case that PCS was formulated as disintegrant, Tab (SD-PCS), similar improvement in the dissolution profile and tensile strength was observed, though the dissolution rate of IMC from Tab (SD-PCS) was slightly lower than that from Tab (SD-L-HPC) irrespective of the compression pressure. 相似文献
249.
Shimada Y Akane H Taniguchi N Matsuhisa A Kawano N Tanaka A 《Chemical & pharmaceutical bulletin》2005,53(5):589-590
Stereoselective synthesis of methyl (Z)-(4,4-difluoro-2,3,4,5-tetrahydro-1H-1-benzazepin-5-ylidene)acetate (1a) is described. Z-selectivity of the Horner-Wadsworth-Emmons (HWE) reaction was obtained based on an investigation of the reaction conditions for introduction of a methylidene group onto the 5-position of benzazepine. 相似文献
250.