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61.
Nucleophilic substitution reactions of alcohols with use of montmorillonite catalysts as solid Brønsted acids 总被引:1,自引:0,他引:1
Motokura K Nakagiri N Mizugaki T Ebitani K Kaneda K 《The Journal of organic chemistry》2007,72(16):6006-6015
We have developed an environmentally benign synthetic approach to nucleophilic substitution reactions of alcohols that minimizes or eliminates the formation of byproducts, resulting in a highly atom-efficient chemical process. Proton- and metal-exchanged montmorillonites (H- and Mn+-mont) were prepared easily by treating Na+-mont with an aqueous solution of hydrogen chloride or metal salt, respectively. The H-mont possessed outstanding catalytic activity for nucleophilic substitution reactions of a variety of alcohols with anilines, because the unique acidity of the H-mont catalyst effectively prevents the neutralization by the basic anilines. In addition, amides, indoles, 1,3-dicarbonyl compounds, and allylsilane act as nucleophiles for the H-mont-catalyzed substitutions of alcohols, which allowed efficient formation of various C-N and C-C bonds. The solid H-mont was reusable without any appreciable loss in its catalytic activity and selectivity. Especially, an Al3+-mont showed high catalytic activity for the alpha-benzylation of 1,3-dicarbonyl compounds with primary alcohols due to cooperative catalysis between a protonic acid site and a Lewis acidic Al3+ species in its interlayer spaces. 相似文献
62.
Mizuki Yamada Mio Matsumura Yuki Murata Masatoshi Kawahata Kohki Saito Naoki Kakusawa Kentaro Yamaguchi Shuji Yasuike 《Tetrahedron》2017,73(18):2614-2622
The Cu-catalyzed azide-alkyne cycloaddition by the reaction of various ethynylstibanes with benzylazide in the presence of CuBr (5 mol%) under aerobic conditions led to the formation of trisubstituted 5-organostibano-1H-1,2,3-triazoles. Further, the acyl-induced deantimonation of 5-stibanotriazoles with acyl chlorides in the presence of N,N-dimethyl-4-aminopyridine and triethylamine afforded the corresponding trisubstituted 5-acyltriazoles in moderate-to-good yields. 相似文献
63.
64.
Yasushi Kawata Kohki Takatoh Makoto Hasegawa Masanori Sakamoto 《Liquid crystals》1994,16(6):1027-1036
The alignment of nematic liquid crystals on micro-groove patterns was studied. It has been found that the order of the alignments is determined by the edge shape, spacing, and line pitch of the micro-groove patterns. On coarse patterns, with pitches greater than 2 μm, striped patterns of the liquid crystal alignment were observed using polarized light which manifested different orientations of the liquid crystals on the top, edge, and bottom of the grooves, respectively. On fine patterns, with pitches less than 2 μm, a uniform device-quality alignment has been realized, with which twisted nematic cells were constructed in combination with the rubbed alignment layer on the opposite substrate. Their viewing angle characteristics and tilt orientations of the director were also investigated. 相似文献
65.
Yoshikawa K Inoue Y Shimada M Akahane M Itoh S Seno A Hayashi S 《Magnetic resonance imaging》2004,22(7):937-942
The aim of this animal study was to evaluate the feasibility of contrast-enhanced magnetic resonance (MR) angiography with two hepatobiliary contrast agents, Gd-DTPA-DeA and Gd-EOB-DTPA. Coronal images of the rat abdomen were acquired using a three-dimensional spoiled gradient recalled sequence before and after the administration of Gd-DTPA-DeA, Gd-EOB-DTPA, or Gd-DTPA. Four sets of postcontrast images were collected every 90 s. Contrast ratios were calculated for the abdominal aorta on the source images, and the retention index was defined as the ratio of the contrast ratio on the last imaging to that on the first postcontrast imaging. Partial minimum intensity projection (MIP) images covering the abdominal aorta were generated from the first and second postcontrast imagings, and the image quality was visually evaluated. The contrast ratio on the first postcontrast imaging was the highest for Gd-DTPA-DeA, followed by Gd-EOB-DTPA and Gd-DTPA. Retention indices were higher with Gd-DTPA-DeA than with Gd-EOB-DTPA and Gd-DTPA, implying a prolonged contrast effect with Gd-DTPA-DeA. On the MIP image from the first postcontrast imaging, delineation of the abdominal aorta tended to be better with Gd-DTPA-DeA and Gd-EOB-DTPA than with Gd-DTPA, and the difference was evident at low injection doses. Image quality for the second postcontrast imaging was higher with Gd-DTPA-DeA than with the other two agents, suggesting a longer imaging window for Gd-DTPA-DeA. In conclusion, Gd-DTPA-DeA and Gd-EOB-DTPA showed stronger contrast enhancement for the rat abdominal aorta and provided MR angiograms of higher image quality when compared with Gd-DTPA at the same injection dose. These hepatobiliary agents may make it possible to perform contrast-enhanced MR angiography even at a low injection dose. 相似文献
66.
Two cyclic peptides, PF1171F (1) and PF1171G (2), were isolated from okara fermented with the unidentified ascomycete OK-128, and their structures were determined by NMR, MS, and Marfey amino acid analysis. Both peptides showed paralytic activity against silkworms. 相似文献
67.
Uchiyama S Kimura K Gota C Okabe K Kawamoto K Inada N Yoshihara T Tobita S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(31):9552-9563
An environment-sensitive fluorophore can change its maximum emission wavelength (λ(em)), fluorescence quantum yield (Φ(f)), and fluorescence lifetime in response to the surrounding environment. We have developed two new intramolecular charge-transfer-type environment-sensitive fluorophores, DBThD-IA and DBSeD-IA, in which the oxygen atom of a well-established 2,1,3-benzoxadiazole environment-sensitive fluorophore, DBD-IA, has been replaced by a sulfur and selenium atom, respectively. DBThD-IA is highly fluorescent in n-hexane (Φ(f) =0.81, λ(em) =537?nm) with excitation at 449?nm, but is almost nonfluorescent in water (Φ(f) =0.037, λ(em) =616?nm), similarly to DBD-IA (Φ(f) =0.91, λ(em) =520?nm in n-hexane; Φ(f) =0.027, λ(em) =616?nm in water). A similar variation in fluorescence properties was also observed for DBSeD-IA (Φ(f) =0.24, λ(em) =591?nm in n-hexane; Φ(f) =0.0046, λ(em) =672?nm in water). An intensive study of the solvent effects on the fluorescence properties of these fluorophores revealed that both the polarity of the environment and hydrogen bonding with solvent molecules accelerate the nonradiative relaxation of the excited fluorophores. Time-resolved optoacoustic and phosphorescence measurements clarified that both intersystem crossing and internal conversion are involved in the nonradiative relaxation processes of DBThD-IA and DBSeD-IA. In addition, DBThD-IA exhibits a 10-fold higher photostability in aqueous solution than the original fluorophore DBD-IA, which allowed us to create a new robust molecular nanogel thermometer for intracellular thermometry. 相似文献
68.
Fujimoto H Okamoto Y Sone E Maeda S Akiyama K Ishibashi M 《Chemical & pharmaceutical bulletin》2005,53(8):923-929
In a screening study on immunomodulatory fungal constituents, eleven new 2-pyrones tentatively named TT-1 (1), and TT-2-11 (2-11) have been isolated from a Fungi Imperfecti, Trichurus terrophilus, and designated rasfonin (1), and trichurusin B-K (2-11), respectively. Compounds 1-4 exhibited considerably high immunosuppressive activities, and compounds 8-11 have shown moderate ones. The structure-activity relationships of these constituents have also been discussed. 相似文献
69.
Mori K Mitani Y Hara T Mizugaki T Ebitani K Kaneda K 《Chemical communications (Cambridge, England)》2005,(26):3331-3333
A zinc-based hydroxyapatite catalyst in conjunction with a Lewis base proved to be efficient for the coupling of CO2 and epoxide in the absence of additional organic solvents under an atmospheric CO2 pressure; the work-up procedure is straightforward and the catalyst could be reused without loss of catalytic activity and selectivity. 相似文献
70.
Noriaki Fujita Kohsuke Mori Kohki Ebitani Kiyotomi Kaneda 《Tetrahedron letters》2006,47(29):5083-5087
Treatment of a hydrotalcite with an aqueous solution of rhodium trichloride results in a Rh-grafted hydrotalcite (Rh/HT) with monomeric Rh species on the surface, which successfully promoted 1,4-addition of organoboron reagents to α,β-unsaturated carbonyl compounds. Furthermore, this catalyst was reusable and was found to be applicable to a one-pot synthesis of 3,3-diarylnitrile. 相似文献