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11.
Adsorption of 2-propanol, (CH3)2CHOH, on a Si(111)-7x7 surface was studied by scanning tunneling microscopy. (CH3)2CHOH adsorbs equally on the faulted and unfaulted half unit cells by forming Si-OCH(CH3)2 and Si-H on an adatom and rest atom pair. Si-OCH(CH3)2 is consecutively increased in each half unit cell, and the adsorption is saturated when every half unit cell has three Si-OCH(CH3)2, which corresponds to 0.5 of the adatom coverage. The sticking probability for the dissociation of (CH3)2CHOH is independent of the adatom coverage from 0 to 0.4, but it depends on coverage at higher than 0.4. By counting the darkened adatoms, Si-OCH(CH3)2 on the center adatom (m) and that on the corner adatom (n), it was found the m/n ratio is ca. 4 for the first dissociation of (CH3)2CHOH in virgin half unit cell, but it becomes ca. 1.9 and 1.8 when two and three Si-OCH(CH3)2 are contained in a half unit cell. This result reveals that the dissociation probability of (CH3)2CHOH at the adatom-rest atom pair site is influenced by the nearest Si-OCH(CH3)2 in the half unit cell. 相似文献
12.
Ken-Ichi Ito Masamichi Nishimura Minoru Sashio Masahiro Tsunooka 《Journal of polymer science. Part A, Polymer chemistry》1994,32(11):2177-2185
It was found that amines were formed efficiently by the photolysis of O-acyloximes followed by hydrolysis in polystyrene films and the relationship between structures of O-acyloximes and yields of amines were investigated. O-phenylacetyl acetophenone oxime (PaApO), O-pivaloyl acetophenone oxime (PApO), and O-benzoyl acetophenone oxime (BApO) as monofunctional O-acyloximes and O,O′-succinyl diacetophenone oxime (SDApO) and O,O′-glutaryl diacetophenone oxime (GDApO) as bifunctional O-acyloximes were examined. The yields of amines for PaApO and SDApO under N2 were ca. 70%, which was the highest among O-acyloximes examined in this experiment. On the other hand, the yields for PApO, BApO, and GDApO were less than 15% and it was verified that the hydrogen abstraction by imino radicals via 6-membered cyclic intermediates resulted in the lowering of yields. Although the effect of oxygen under photolysis on the yields of amine for PaApO was negligible under 50% conversion of PaApO, the yield decreased with further increase in the conversion and was 50% at 90% conversion. © 1994 John Wiley & Sons, Inc. 相似文献
13.
Konoike T Matsumura K Yorifuji T Shinomoto S Ide Y Ohya T 《The Journal of organic chemistry》2002,67(22):7741-7749
A practical multikilogram-scale synthesis of enantiomerically pure S-1255 (1), a potent and orally active ET(A) receptor antagonist, is described. Utilizing readily available starting materials and reagents, the entire sequence of reactions starting from 2,5-dihydroxyacetophenone 8 proceeded under mild conditions to give 1 in an excellent chemical yield (8 steps, 41% overall yield) and in a high enantiopurity (98% ee). The crucial step of the synthesis is a dynamic resolution of key intermediate 16. (R)-Methoxy acid (R)-16 having 97-99% ee was obtained in 83-84% yield from racemic 16 as a crystalline (1S,2R)-(+)-norephedrine or (+)-cinchonine salt by the dynamic resolution comprising concurrent crystallization and in situ racemization. A mechanism of the dynamic resolution through a ring-opened zwitterionic intermediate is discussed. In the final synthetic step, an effective carbon-carbon bond formation between the C4 carbon and the p-anisyl group was accomplished by a conjugate addition-elimination reaction of Grignard reagent 3 to (R)-16 to give 1 having 98% ee. Owing to high efficiencies of functional group transformations, carbon-carbon bond formations, and the dynamic resolution, the synthesis required no chromatographic purification and was amenable to a multikilogram-scale preparation. Several kilograms of 1 for clinical trials were successfully prepared by this process. 相似文献
14.
Sutasinee Kaewpuang-Ngam Koji Inazu Ken-Ichi Aika 《Research on Chemical Intermediates》2002,28(5):471-477
Catalytic wet air oxidation of ammonia over a co-precipitated transition metal-aluminium catalyst was investigated. Copper-aluminium (Cu-Al-O) catalyst exhibited the highest activity and N2 selectivity among those prepared from Co, Fe, Mn, and Ni. 50% of 1500 ppm of ammonia could be removed from wastewater of pH 12 at 503 K under 2.0 MPa of air by using 4.0 g of catalyst without formation of toxic nitrogen containing compounds. Cu and Al ions were not found in solution after the reaction. It has been found that the catalytic performance of Cu-Al-O catalyst was strongly dependent on the preparation methods. The co-precipitated Cu-Al-O catalysts showed high N2 selectivity. The presence of CuO is concluded to promote the reaction and CuAl2O4 in bulk phase is needed to stabilize the catalyst. 相似文献
15.
Motozaki T Sawamura K Suzuki A Yoshida K Ueki T Ohara A Munakata R Takao K Tadano K 《Organic letters》2005,7(11):2265-2267
[reaction: see text]. We have completed the total synthesis of natural (+)-tubelactomicin A (1), a 16-membered macrolide antibiotic. This Letter presents a highly efficient synthesis of the upper-half segment (C14-C24) and the completion of the total synthesis featuring a high-yielding Stille coupling for the connection of the upper-half and lower-half segments and Mukaiyama macrolactonization for the construction of the entire structure of 1. 相似文献
16.
Tetsuo Kusumoto Ken-Ichi Sato Kumiko Ogino Tamejiro Hiyama Sadao Takehara Masashi Osawa 《Liquid crystals》2013,40(3):727-732
Abstract New chiral dopants β-hydroxy ketones 1, 1,3-diols 2, 1,3-dioxanes 3 and 1,3-dioxan-2-ones 4 were designed and synthesized. Reaction of (R)-1,2-epoxyoctane with carbanions derived from 2-(4-substituted phenyl)-1,3-dithianes followed by hydrolysis of the resulting hydroxy dithianes afforded 1. Reduction of 1 gave the diols 2, which yielded 3 upon acetalization and 4 upon carbonation. The syn isomers of 2, 3, and 4 exhibited larger spontaneous polarizations, when applied as chiral dopants, than the anti isomers or hydroxy ketones 1. 相似文献
17.
18.
Yoshihiro Shigemasa Kuninori Oogaki Nasuo Ueda Ruka Hakashima Ken-Ichi Harada Naohito Takeda 《Journal of carbohydrate chemistry》2013,32(3):325-330
Abstract The formose reaction, by which a complex mixture of sugars and sugar alcohols (the so-called formose) are produced by the base-catalyzed condensation of formaldehyde, has received much attention in connection with the prebiotic synthesis of carbohydrates2 and the microbial utilization of formose.3–5 Formose, however, has not been useful yet, because of the complexity of this product mixture (Fig. 1a). Therefore, it seemed desirable to make the reaction more selective. 相似文献
19.
Ken-Ichi Kanno Yuichi Kobayashi Shin-Ichiro Nishimura Hiroyoshi Kuzuhara Kenichi Hatanaka 《Journal of carbohydrate chemistry》2013,32(4-5):481-490
Abstract 1,6-Anhydro-2-deoxy-3,4-di-O-benzyl-2-phthalimido-β-d- glucopyranose (5) was synthesized from 1,6-anhydro-β-d-mannopyranose (1) in five steps. Compound 5 was polymerized under cationic conditions and selectively yielded glucosamine oligomers (degree of polymerization 5-7). Copolymerization of 5 with 1,6-anhydro-2,3,4-tri-O-benzyl-β-d-glucopyranose indicated the low reactivity of 5 with the active cation derived from 5. Deprotection of 2-deoxy-3,4-di-O-benzyl-2-phthalimido-(1→6)-β-d-glucopyranan (7) and N-acetylation gave 2-acetamido-2-deoxy-(1→6)-β-d-glucopyranan (9). 相似文献
20.
Laser-diode pumped heavy-doped Yb:YAG ceramic lasers 总被引:1,自引:0,他引:1
Laser performance of heavy-doped Yb:YAG ceramics was investigated using a two-pass pumping miniature laser configuration. Slope efficiency of 52% and optical-to-optical efficiency of 48% have been achieved for 1-mm-thick YAG ceramic doped with 20 at.% ytterbium ions. Laser spectra of Yb:YAG ceramic and single-crystal lasers were addressed under different intracavity laser intensities. Heavy-doped Yb:YAG ceramic is more suitable for a thin disk laser than a single-crystal with the same Yb(3+)-ion lasants. 相似文献