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91.
Tobisu M Kitajima A Yoshioka S Hyodo I Oshita M Chatani N 《Journal of the American Chemical Society》2007,129(37):11431-11437
The Br?nsted acid catalyzed formal insertion of an isocyanide into a C-O bond of an acetal is described. A diverse array of acyclic and cyclic acetals can be applied to the catalytic insertion to form alpha-alkoxy imidates. Functional groups, such as nitro, cyano, halogen, ester, and alkoxy groups, are tolerant to the reaction conditions employed. The course of the reaction is highly dependent on the structure of the isocyanide. The use of an electron-deficient aryl isocyanide, such as 2c and 2d, is required to selectively obtain the monoinsertion product. When aryl isocyanides containing alkyl substituents, such as 2a and 2b, are employed, two molecules of the isocyanide are incorporated, and the double-insertion product is obtained. The reaction of tert-octyl isocyanide also induces a double incorporation, but the subsequent acid-mediated fragmentation leads to the 2-alkoxy imidoyl cyanide. The monoinsertion products, alpha-alkoxy imidates, can readily be hydrolyzed to alpha-alkoxy esters, realizing the formal carbonylation of an acetal. 相似文献
92.
Yoshikawa M Morikawa T Asao Y Fujiwara E Nakamura S Matsuda H 《Chemical & pharmaceutical bulletin》2007,55(4):606-612
The methanolic extract from the flowers buds of Camellia japonica L. (Theaceae) were found to exhibit potent inhibitory activities on ethanol- or indomethacin-induced gastric mucosal lesions in rats. Through bioassay-guided separation, 28-noroleanane-type triterpene oligoglycosides, camelliosides A, B, and C, and an oleanane-type triterpene oligoglycoside, camellioside D, were isolated from the methanolic extract together with five known compounds. The absolute stereostructures of camelliosides were determined on the basis of chemical and physicochemical evidence, which included the structure revision of the nortriterpene aglycons (camellenodiol and camelledionol). The principal oligoglycosides, camelliosides A and B, showed platelet aggregation activity in addition to the gastroprotective effects on ethanol- or indomethacin-induced gastric mucosal lesions in rats. 相似文献
93.
Masayuki Muroi Konomi Haibara Mitsuko Asai Kazuhide Kamiya Toyokazu Kishi 《Tetrahedron》1981,37(6):1123-1130
Macbecin I 1, C30H42N2O8, and macbecin II 2, C30H44N2O8, were shown to be 2,6-disubstituted benzoquinone and hydroquinone derivatives by an oxidation-reduction relationship, UV. 1H and 13C NMR spectra. Alkaline methanolysis of 1 gave a 2-aminobenzoquinone derivative 5, suggesting an ansa-structure for 1, and acid hydrolysis of 1 gave decarbamoyl products 9,10 and 11, indicative of the location of carbamoyloxy group in allylic position. Spin decoupling studies on 1,3 and 5clarified the partial structures [A], [B], [C] and [D]. From their mutual disposition two structures 1a and 1b, were proposed out of which 1a has been selected for the structure of 1 on the basis of the structure of oxidative degradation product 12. X-Ray analysis of the bromoacetyl derivative of 1 confirmed the above proposed structure and determined the absolute stereochemistry of 1 and 2. 相似文献
94.
Reaction of 3-acetyl-4,6-dimethyl-2-(1H)pyridone ( 9a ) with phosphoryl chloride gives 2-chloro-3-ethynyl-4,6-dimethylpyridine ( 10a ). 3-Acetyl-4-hydroxy-6-methyl-2(1H)pyridone (14a) and 3-acetyl-2,6-dimethyl-4-(1H)-pyridone (21) undergoes similar reaction to give the corresponding ethynyl (16 and 23) and chlorovinyl (15 and 22) pyridines, respectively. The chlorination of 3-acetylpyridine and pyrimidine derivatives is further described. 相似文献
95.
Kikuo Miyokawa Masayuki Itoh Takummi Etoh Setsuko Kinoshita Isao Masuda 《Thermochimica Acta》1985,96(1):227-234
Kinetic and thermodynamic aspects of the axial base dissociation of solid Co(salen) (X-py) complexes, X = H (1), 3-Me (2), 4-Me (3), 3,4-Me2 (4), 3,5-Me2 (5), 3-NH2 (6), 3-Cl (7), 3-CN (8), 4-CN (9), have been investigated by means of TG-DSC and isothermal weight-loss measurements. These adducts endothermically dissociate the axial base giving rise to the oxygen-active Co(salen) complex. The axial base dissociation reactions fit the contracting disc equation and the kinetic compensation effect is observed for all the adducts excepting Adducts 4–6. For the remaining adducts the kinetic and thermodynamic stabilities of the Co-(X-py) bond are found to increase linearly with increasing Hammett's substitution constants of X except for Adducts 3 and 9. These results are discussed in terms of the σ and π interactions between cobalt(II) and substituted pyridine. Factors dominating the kinetic bond stability are briefly discussed. 相似文献
96.
97.
Virginie Gueu Hongpeng You Tomokatsu Hayakawa Masayuki Nogami 《Journal of Sol-Gel Science and Technology》2007,41(3):231-236
Fluorescence and spectral hole burning properties of Eu3+ ions were studied in nanocrystals-precipitated SnO2-SiO2 glasses. The glasses were prepared to contain various amount of Eu2O3 using the sol-gel method, in which SnO2 nanocrystals were precipitated by heating in air. In the glasses containing Eu2O3 less than 1%, the Eu3+ ions were preferentially doped in the SnO2 nanocrystals and their fluorescence intensities were enhanced by the energy transfer due to the recombination of electrons
and holes excited in SnO2 crystals. The SnO2 nanocrystals-precipitated glasses exhibited the persistent spectral holes with the depth of ∼25% of the total fluorescence
intensities of the Eu3+ ions. With the increasing Eu2O3 concentration, the amount of SnO2 nanocrystals decreased and the Sn4+ ions formed the random glass structure together with the silica network. This structure change induced the fluorescence intensities
and the hole depth to decrease. 相似文献
98.
Morikawa T Sun B Matsuda H Wu LJ Harima S Yoshikawa M 《Chemical & pharmaceutical bulletin》2004,52(10):1194-1199
A new beta-carboline-type alkaloidal glycoside, glucodichotomine B, four new neolignan glycosides, dichotomosides A, B, C, and D, and a new phenylpropanoid glycoside, dichotomoside E, were isolated from a Chinese natural medicine, the roots of Stellaria dichotoma L. var. lanceolata. The structures of the new glycosides were determined on the basis of chemical and physicochemical evidence. Among them, dichotomoside D inhibited the release of beta-hexosaminidase (IC(50)=64 microM) as well as tumor necrosis factor-alpha and interleukin-4 (IC(50)=16, 34 microM) in RBL-2H3 cells. These findings suggest that dichotomoside D is more effective against the late-phase reactions in type I allergy than in the immediate phase. 相似文献
99.
Masayuki Inoue 《Tetrahedron letters》2004,45(10):2053-2056
We report a new reaction for the direct construction of O,S-acetals, key intermediates in the assembly of fused polycyclic ethers. α-Fluorosulfides and secondary alcohols were coupled by the action of Yb(OTf)3 to generate O,S-acetals in high yield. The neutral and selective nature of the reaction should be useful for synthesizing natural and artificial polyethers with multisensitive functionalities. 相似文献
100.
Ando K Tsuji E Ando Y Kunitomo J Kobayashi R Yokomizo T Shimizu T Yamashita M Ohta S Nabe T Kohno S Ohishi Y 《Organic & biomolecular chemistry》2005,3(11):2129-2139
Variable benzo[b]furan derivatives having (E)- and (Z)-2-alkylcarbamoyl-1-methylvinyl groups at the 2-, 4- and 5-positions and a carboxylpropoxy or (1-phenyl)ethoxy group at the 7-position were prepared to find novel and selective leukotriene B4(LTB4) receptor antagonists. (E)-2-(2-diethylcarbamoyl-1-methylvinyl)-7-(1-phenylethoxy)benzo[b]furan (4v) showed selective inhibition to the human BLT2 receptor (hBLT2). On the other hand, (E)-2-acetyl-4-(2-diethylcarbamoyl-1-methylvinyl)-7-(1-phenylethoxy)benzo[b]furan (7v) inhibited both human BLT(1) receptor (hBLT1) and hBLT2. The (E)-2-(2-diethylcarbamoyl-1-methylvinyl) group lay on approximately the same plane as the benzo[b]furan ring, whereas the (E)-4-(2-diethylcarbamoyl-1-methylvinyl) group had the torsion angle (45.7 degree) from the benzo[b]furan ring plane. However, the (Z)-(2-alkylcarbamoyl-1-methylvinyl)benzo[b]furans were inactive. The inhibitory activity depended on the conformation of the 2-diethylcarbamoyl-1-methylvinyl group. 相似文献