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71.
A flexible and stereodivergent synthesis of the cis- and trans-fused 2,5-disubstituted octahydroquinolinone ring systems bearing all four stereogenic centers for the synthesis of the decahydroquinoline type of dendrobatid alkaloids has been achieved. The strategy involves stereoselective and stereodivergent construction of 2,3,6-trisubstituted piperidine ring systems using the Michael type of conjugate addition reaction to the enaminoesters 1 and 3, the intramolecular aldol type of cyclization reaction of keto aldehydes 11 and 12, and ring-closing metathesis of 21 as key steps. 相似文献
72.
Hideo Nishii Toshinobu Higashimura 《Journal of polymer science. Part A, Polymer chemistry》1977,15(5):1179-1188
Ring-substituted methylstyrenes (p-, m-, and o-methylstyrenes) in conjunction with acetyl perchlorate (AcClO4) or trifluoromethanesulfonic acid as catalysts gave their linear unsaturated dimer in high yield in benzene at temperatures from 50 to 70°C. In particular, the yield of o-methylstyrene dimer was as high as 90% in the AcClO4 catalysis at 50°C. The dimer yield depended on solvent and catalyst. The terminal structures of the dimers and higher oligomers were analyzed by NMR spectroscopy. Oligomers with a cyclic terminal structure increased in the products at higher temperature. The dimer yield was improved by codimerizing p-methylstyrene with less reactive m-methylstyrene or styrene with AcClO4 catalyst. The dimers obtained partly consisted of linear unsaturated codimers. 相似文献
73.
Tetsuji Kametani Kazuo Kigasawa Mineharu Hüragi Nagatoshi Wagatsuma Setsu Saitoh Hideo Sugi 《Journal of heterocyclic chemistry》1973,10(3):313-315
Acid treatment of the alkylated products of (Va, Vb, and VIII) of piperidinols IVa and IVb, and tetrahydropyridine VII with β-bromoethylbenzene, afforded 1,2,3,4,5,6-hexahydro-8-hydroxy-2,6-methano-6,1 1-dimethyl-3-phenethyl-3-benzazocine (la) in good yield. Piperidinols Va and Vb were also obtained from the reaction of N-(3-methyl-3-pentenyl)-β-phenethylamine (IIb) with methyl 3-(4-methoxyphenyl)-2,3-epoxypropionate. 相似文献
74.
Hideo Kise Hiroshi Ogata 《Journal of polymer science. Part A, Polymer chemistry》1983,21(12):3443-3451
The reaction of poly(vinylidene fluoride) (PVDF) powder with aqueous sodium hydroxide solutions in the presence of quaternary ammonium or phosphonium halides as phase transfer catalysts afforded dehydrofluorinated polymers. The structure of the products was investigated by infrared spetroscopy, and a fluorine-substituted conjugated polyene structure was suggested which was found to be stable against air oxidation. Tetrabutylammonium bromide and tetrabutylphosphonium bromide were the most active among the catalysts used. The effects of the reaction conditions on the conversion are described. The treatment of PVDF films under phase transfer conditions increased the wettability of the surface and electric conductivity. The reaction of PVDF with potassium hydroxide in 2-propanol proceeded not only by elimination but also by substitution of hydroxide ions. 相似文献
75.
A stereoselectivity in an intramolecular cycloaddition of the olefinic -quinodimethanes 13 and 23 generated from the thermolysis of optically active 4β-[2-(4-methoxybenzocyclobutenyl)ethyl] -5α-methoxymethyl-3-phenyl-thio-methylenefuran-2-ones 12 and 22, respectively, is studied and a stereoselective synthesis of (+)--4,5-( 4-methoxybenzo) -1β,7aβ-(2α-methoxymethyl-5-oxofuro)hydrindane 1 is also described. 相似文献
76.
Polyanionic glycopolymers were synthesized aiming at establishing a simple process for assembling glycosyl arrays. The synthetic glycopolymers carry the key carbohydrate epitopes of α-d-galactobioside (Gb2), β-lactoside, and α-d-mannopyranoside, each of which serves as a ligand of bacterial toxins and adhesion proteins. The Gb2 epitope, prepared from penta-O-acetyl-d-galactopyranose, was coupled with poly(ethylene-alt-maleic anhydride) in a polymer reaction to afford a Gb2-embedded glycopolymer having also carboxylate (COO−) polyanions at the side chain. The polyanionic glycopolymer was then applied to a preparation of sugar-coated gold electrodes, which involves an alternating layer-by-layer adsorption based on electrostatic interactions. The presence of the Gb2-coat on the surface was evidenced by Fourier transform infrared reflection absorption spectroscopy. The Gb2-coated glyco-chip was stable in 10 mM HEPES buffer containing 150 mM NaCl aq. Other glycopolymers carrying the β-lactoside and α-d-mannopyranoside epitopes were applied to the same assembling process. The derived glycosyl arrays will be useful for detecting Shiga toxins, other pathogenic toxins and viruses when applied as glyco-chips for surface plasmon resonance or quartz crystal microbalance technique. 相似文献
77.
Three macroreticular polystyrene-based resins with amino- or imino-thiazole and thiazoline groups as the functional groups have been prepared. The resins are highly stable in acid and alkaline solutions and have high selectivity for mercury(II). In the presence of hydrochloric acid, sorption of mercury attains equilibrium fairly rapidly, the time for 50% uptake of mercury being 3-6 min. There are practically no interferences. In a column operation, mercury is quantitatively recovered by elution with 0.1M hydrochloric acid containing 5% thiourea. The thiazoline resin column can be used to concentrate mercury from sea-water. 相似文献
78.
Suzuki N Aihara N Takahara H Watanabe T Iwasaki M Saburi M Hashizume D Chihara T 《Journal of the American Chemical Society》2004,126(1):60-61
Five-membered metallacyclic alkynes that have no substituents adjacent to the triple bond have been synthesized, isolated, and structurally characterized. Zirconocene dichlorides, Cp'2ZrCl2 (Cp' = C5H5, C5H4-t-Bu), reacted with 1,4-dichlorobut-2-yne in the presence of magnesium to give 1-zirconacyclopent-3-yne compounds (5 (a) Cp' = C5H5, (b) Cp' = C5H4-t-Bu) that have a -CH2CCCH2- moiety in good yields. They are stable enough to be isolated in a pure form, despite the absence of substituents. 5a reacted with an equimolar amount of Cp2Zr(but-1-ene)(PMe3) to produce a bimetallic complex in which the zirconacyclopentyne coordinates to the other zirconocene moiety as an alkyne. 相似文献
79.
A novel synthesis of 5-cyano[n](2,4)pyridinophane-6-ones 12a-d (n= 9, 8, 7, and 6) consists of allowing cyanoacetatoamide to react with cycloalk-2-enones. Their static and dynamic properties as well as structural characteristics are studied on the basis of their spectroscopic properties, cyclic voltammetry, and theoretical calculations. The (1)H and (13)C NMR spectra at various temperatures have clarified the dynamic behavior of the methylene chains for [7](2,4)- and [6](2,4)pyridinophane-6-one derivatives 12c and 12d. The energy barrier (Delta G(++)) of the bridge flipping of 12c is estimated to be 12.0 kcal mol(-1)(T(c)= 0 degree C). On the other hand, compound 12d undergoes pseudorotation (conformational change of the methylene chain) at room temperature, and does not undergo bridge flipping even at 150 degree C in DMSO-d(6). The energy barrier (Delta G(++)) of the pseudorotation of the methylene chain 12d of is found to be 10.5 kcal mol(-1)(T(c)=-25 degree C), and thus, two stable conformers of the hexamethylene bridge of 12d are determined as predicted by theoretical calculations. Deformation of the pyridone ring of 12d is also determined by X-ray crystallographic analysis. Furthermore, chemical transformations of 12a-c leading to 5-carbamoyl[n](2,4)pyridinophanes 15a-c are also accomplished successfully in moderate to good yields. 相似文献
80.
Yamashita M Yamamoto Y Akiba KY Hashizume D Iwasaki F Takagi N Nagase S 《Journal of the American Chemical Society》2005,127(12):4354-4371
Pentacoordinate and tetracoordinate carbon and boron compounds (27, 38, 50-52, 56-61) bearing an anthracene skeleton with two oxygen or nitrogen atoms at the 1,8-positions were synthesized by the use of four newly synthesized tridentate ligand precursors. Several carbon and boron compounds were characterized by X-ray crystallographic analysis, showing that compounds 27, 56-59 bearing an oxygen-donating anthracene skeleton had a trigonal bipyramidal (TBP) pentacoordinate structure with relatively long apical distances (ca. 2.38-2.46 A). Despite the relatively long apical distances, DFT calculation of carbon species 27 and boron species 56 and experimental accurate X-ray electron density distribution analysis of 56 supported the existence of the apical hypervalent bond even though the nature of the hypervalent interaction between the central carbon (or boron) and the donating oxygen atom was relatively weak and ionic. On the other hand, X-ray analysis of compounds 50-52 bearing a nitrogen-donating anthracene skeleton showed unsymmetrical tetracoordinate carbon or boron atom with coordination by only one of the two nitrogen-donating groups. It is interesting to note that, with an oxygen-donating skeleton, the compound 61 having two chlorine atoms on the central boron atom showed a tetracoordinate structure, although the corresponding compound 60 with two fluorine atoms showed a pentacoordinate structure. The B-O distances (av 2.29 A) in 60 were relatively short in comparison with those (av 2.44 A) in 59 having two methoxy groups on the central boron atom, indicating that the B-O interaction became stronger due to the electron-withdrawing nature of the fluorine atoms. 相似文献