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11.
Kazuhiro Kobayashi Hiroyasu Takeuchi Shinzo Seko Yoshikazu Kanno Sachiko Kujime Hiroshi Suginome 《Helvetica chimica acta》1993,76(8):2942-2950
The 2,3-dihydro-1H-benz[f]indole-4,9-diones 3a–d , h were formed in a one-step reaction in 13–82% yield by an unprecedented [3 + 2] regioselective photoaddition of 2-amino-1,4-naphthoquinone ( 1 ) with various electronrich alkenes 2 (Scheme 1, Table). The [3 + 2] photoadducts derived from 1 with vinyl ethers and vinyl acetate gave 1H-benz[f]indole-4,9-diones 4e , f , i , in 33–72% yield, by spontaneous loss of the corresponding alcohol or AcOH from the resulting adducts; 4i has a kinamycin skeleton. The [3 + 2] photoaddition also took place on irradiation of the differently substituted amino-1,4-benzoquinones 6 , 7 , and 12 and excess alkenes 2 in benzene, giving 1H-indole-4,7-dione derivatives 13 and 14 (Scheme 3), 15a and 16 (Scheme 4), and 18 (Scheme 4), respectively. The initial products in these photoadditions were proved to be hydroquinones, the air oxidation of which yielded the heterocyclic quinones; 2,3-dihydro-2-methoxy-2-methyl-5-phenyl-1H-indole-1,4,7-triyl triacetate ( 19 ) was isolated after treatment of the crude photoaddition mixture obtained from 2-amino-5-phenyl-1,4-benzoquinone ( 7 ) and 2-methoxyprop-1-ene ( 2f ) with Ac2O and pyridine under N2. A pathway leading to the annelated hydroquinones involving ionic intermediates arising from an electron transfer in these photoadditions is proposed (Scheme 5). 相似文献
12.
The development of solid strong base catalysts utilizable in green but acidic medium of scCO2 is reviewed. The strong base sites on mesoporous alumina and sulfated mesoporous alumina that had been generated by severe treatment at 773 K under vacuum (10?4 Torr) were not neutralized by the compressed Lewis acidic molecules of CO2, promoting a representative strong base-catalyzed reaction of the Tishchenko reaction as well as a typical base-catalyzed reaction of the Knoevenagel reaction in scCO2. Infrared spectroscopy of the adsorbed pyrrole, temperature-programmed desorption of CO2, and the poisoning by a very weak Brönsted acid of methanol have revealed that the average strengths of the base sites on mesoporous alumina and sulfated mesoporous alumina are weaker than that on conventional γ-alumina like JRC-ALO-4, but that they have a small number of strong base sites which function even in scCO2 medium. It was found that the addition of a slight amount of THF cosolvent into scCO2 remarkably accelerates the Tishchenko reaction over sulfated mesoporous alumina; the reaction rate in the scCO2–THF medium was 1.5-fold and 2-fold faster than those in ordinary organic solvents such as benzene and THF and that in pure scCO2, respectively. The unique structures of mesoporous alumina and sulfated mesoporous alumina have been fully characterized by N2 adsorption–desorption measurements and XRD analyses. 相似文献
13.
Smiles-type free radical rearrangements of arenesulfonates and arenesulfonamides are exploited for synthetic purposes. 4-Substituted benzenesulfonates cause Smiles-type rearrangement only when substituted by an electron withdrawing group. Therefore, ipso-attack by an alkyl radical on arenesulfonates takes place in an electrophilic manner. Arenesulfonamides rearrange only when the amide nitrogen is substituted by an alkoxycarbonyl group, due to the electron withdrawing nature of this group. Sulfonates and the N-ethoxycarbonylsulfonamide derivatives of naphthalene, quinoline, and thiophene cause more rearrangement and show synthetic utility. Aromatic amino acid analogues were synthesized by Smiles-type rearrangement with moderate yields. The radical Smiles-type rearrangement of sulfonate and sulfonamide derivatives can be a useful synthetic route when we understand the electronic character of these reactions. 相似文献
14.
Magnetic circular dichroism and NIR luminescence of nitroxide radical complexes, [Cr(III)(beta-diketonato)(2)(NIT2py or IM2py)]PF(6), demonstrate that the energy gaps between the singlet ((1)L(D)) and triplet ((3)L(D)) spin coupled levels in the lowest excited (2)E(g),(2)T(1g) states are much larger than those in the ground state. This is the first observation of magnetic interactions in the excited states of radical complexes, which could be elucidated in terms of the exchange mechanism. 相似文献
15.
Takiue T Hirose D Murakami D Sakamoto H Matsubara H Aratono M 《The journal of physical chemistry. B》2005,109(34):16429-16434
The interfacial tension gamma of the hexane solution of 1H,1H-perfluorononanol (FDFC(9)OH) and its omega-hydrogenated analogue, 1H,1H,9H-perfluorononanol (HDFC(9)OH), against water was measured as a function of pressure and concentration at 298.15 K in order to clarify the effect of omega-dipole on the orientation of fluorononanol molecules from the viewpoint of volume. The adsorbed films of both alcohols exhibit two kinds of phase transitions among three different states: the gaseous, expanded, and condensed states. The partial molar volume changes of adsorption - in the expanded and condensed states were evaluated and compared between the two systems. The - values of both alcohols are negative, and thus the alcohol molecules have smaller volume in the adsorbed film than in the bulk solution. Furthermore, the value was obtained through the evaluation of by the density measurement of the bulk hexane solution. It was found that the value of HDFC(9)OH is smaller than that of FDFC(9)OH in the condensed state. On the basis of three matters concerning the molecular structure of alcohols, the occupied area at the interface, and the orientation of FDFC(9)OH in the adsorbed film deduced from the earlier results of X-ray reflectivity measurement, the mean tilt angle of HDFC(9)OH from the interface normal in the condensed film was estimated to be 15 degrees . The thermodynamic estimation demonstrated here is highly valuable one to provide structure information on an adsorbed film. 相似文献
16.
Kazuyuki Kubo Hiroshi Nakazawa Hiroyasu Inagaki Tomoyuki Miyake Tsutomu Mizuta Katsuhiko Miyoshi 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8-9):2159-2160
Treatment of [Cp*(CO) 2 M{P(NHPh)(OMe) 2 }]PF 6 (M = Fe and Ru) with NaNH 2 gives metallaiminophosphoranes, Cp*(CO) 2 M{P(NPh)(OMe) 2 }. The x-ray structures and reactivity of the complexes are reported. 相似文献
17.
Makoto Kiso Hideki Katagiri Hiroyasu Furui Akira Hasegawa 《Journal of carbohydrate chemistry》2013,32(5):627-644
Abstract Suitably protected 1-deoxynojirimycin (l, 5-dideoxy-l, 5-imino-D-glucitol; DNJ) and its 2-acetamido derivative, i.e., 2, 3, 6-tri-O-benzyl-.N-benzyloxycarbonyl-l, 5-dideoxy-1, 5-imino-D-glucitol (6) and 2-acetamido-3, 6-di-O-benzyl-N-benzyloxycarbonyl-1, 2, 5-trideoxy-l, 5-imino-D-glucitol (14) were each coupled with methyl 2, 3, 4, 6-tetra-O-acetyl-1-thio-β-D-galactopyranoside (15) in the presence of dimethyl(methylthio)-sulfonium triflate (DMTST) as a promoter, to give 16 and 18, which were converted to the novel disaccharides (20, 21) related to lactose and lactosamine. Coupling of 14with methyl 3, 4, 6-tri-O-acetyl-2-deoxy-2-phthalimido-l-thio-β-D-glucopyranoside (22) gave achitobiose analog (25). O-(β-D-Galactopyranosyl)-(l→3)-DNJ derivatives (38, 39) and O-(β-D-glucopyranosyl)-(l→3)-DNJ (45) were also synthesized. Conformational analysis of a variety of DNJ derivatives, based on the 1H NMR data, is also discussed. 相似文献
18.
Kentaro Yonesato Hiroyasu Ito Daisuke Yokogawa Kazuya Yamaguchi Kosuke Suzuki 《Angewandte Chemie (International ed. in English)》2020,59(38):16361-16365
Small Agn nanoclusters (n<10) have been emerging as promising materials as sensing, biolabeling, and catalysis because of their unique electronic states and optical properties. However, studying synthesis, structure determination, and exploration of their properties remain major challenges as a result of the low stability of small Ag nanoclusters. Herein, we synthesized an atomically precise face‐centered‐cubic‐type small {Ag7}5+ nanocluster supported by a novel triangular hollow polyoxometalate (POM) framework [Si3W27O96]18?. The cluster showed unique {Ag7}5+‐to‐POM charge transfer bands in both visible and UV light regions. Furthermore, this small {Ag7}5+ nanocluster exhibited an unprecedented ultrastability in solution, despite having exposed Ag sites that can be accessed by small molecules, such as O2, water, and solvents. 相似文献
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