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41.
A convenient synthetic approach is established to prepare a new class of 1-l-α-amino acid derivatives of phospholene oxides by amination of (±)-1-chloro-2-phospholene-1-oxides with several optically pure l-α-amino acid esters. All compounds obtained as a diastereomeric mixture in good to high yields. The two diastereomers were successfully separated by column chromatography and structurally identified by their spectral analyses. 相似文献
42.
Fumio Kiyono Hideo Tajima Keiichi Ogasawara Akihiro Yamasaki 《Fluid Phase Equilibria》2005,230(1-2):90-98
A method for determining quadruple points of a two-component system containing a simple hydrate phase is proposed. This method utilizes the quasi-static change of the system along three-phase equilibrium lines and was proved to be able to determine the quadruple points as accurately as the conventional method. By using this method, even though some preparation is necessary, a quadruple point can be determined in just a single experimental run. The behavior of the system near the quadruple points was also examined experimentally, for both the quasi-static and the irreversible change cases. At the quadruple points, the temperature and pressure of the system were kept constant for a while, as at the triple point of water. In both cases, the representative point of the state of the system passed through the quadruple point on a p–T diagram. 相似文献
43.
Masao Nohara Masaki Hasegawa Hatsuhiko Harashina Yoichi Iitaka 《Journal of polymer science. Part A, Polymer chemistry》1988,26(10):2695-2704
Photoreactive polyamides having m- or 1 -type cyclobutane moiety were prepared via a topochemical photodimerization of 4-(3-oxo-3-phenyl-1-propenyl)benzoic derivatives,4 followed by polycondensation of cyclobutane dicarboxylate derivatives with diamines. From the spectral studies of resulted polyamides compared with the corresponding reference diamides, it was concluded that both types of polyamides were depolymerized photochemically to give the same type of amide derivative having chalcone moiety with a small amount of undefined side reaction. The cyclobutane ring of the m-dimer from 4-(3-oxo-3-phenyl-1-propenyl)benzoic acid in crystal is severely twisted presumably because of the enhanced steric repulsions between two pairs of adjacent substituents. The higher quantum yield of the m-dimer for the photocleavege, compared with that of the 1 -dimer, has been interpreted in terms of such steric repulsions by the strained structure of the m-dimer. 相似文献
44.
Computer-aided structure elucidation methodology is discussed. Major processes involved in computer-aided structure elucidation systems are partial-structure elucidation, structure generation, and structure examination. For the three representative systems CONGEN, CASE, and CHEMICS, these processes are examined. There are four necessary conditions for automated chemical structure elucidation systems: reliability, width of application, ease of modification and portability. 相似文献
45.
An intensely sweet polyoxypregnane glycoside, telosmoside A15 (15), was isolated from an Asian Asclepiadaceae plant, Telosma procumbens, collected in Vietnam. This is the first time a sweet pregnane glycoside has been found, and its sweetness intensity is 1000 times greater than that of sucrose. From the same plant, 17 other new glycosides were isolated, having the same aglycone; they are named telosmosides A1-A14 (1-14) and A16-A18 (16-18). Some of these glycosides are also sweet, but others are tasteless or bitter. Chemical structures of the 18 glycosides were determined, and the structure-taste relationship was discussed. 相似文献
46.
Tetsuo Yamasaki Yuji Yoshihara Yoshinari Okamoto Tadashi Okawara Mitsuru Furukawa 《Journal of heterocyclic chemistry》1992,29(5):1313-1316
The reaction of 5-hydrazinopyridazin-3(2H)-ones 1 with α-keto diester 2 in acetic acid afforded the corresponding 4,6-dihydropyridazino[4,5-c]pyridazin-5(1H)-ones 3 and pyrrolo[2,3-d)pyridazin-4(5H)-ones 4 . Compounds 3 were also obtained from 4-bromo-5-hydrazinopyridazin-3(2H)-ones 8 and 2 under milder conditions. 5-Bromo-4-hydrazinopyridazin-3(2H)-one 9 , the regioisomer of 8b , also reacted readily with 2a to give 4,7-dihydropyridazino[4,5-c]pyridazin-8(1H)-one 10b , the regioisomer of 3b . 相似文献
47.
Fukushima S Miyata K Nishiyama N Kanayama N Yamasaki Y Kataoka K 《Journal of the American Chemical Society》2005,127(9):2810-2811
An A-B-C type triblock copolymer, tandemly aligning two types of polycations with different pKa values in a single polymer strand, was developed for the construction of novel polyplex micelles, satisfying a high DNA condensing ability as well as a proton buffering activity directed to elevating gene transfection. The micelle might feature the distinctive three-layered structure, where an inner polyplex layer of condensed pDNA with poly(l-lysine) (pKa approximately 9.4) as the C segment is successively wrapped with an intermediate layer of poly[(3-morpholinopropyl)aspartamide] (B segment) with a comparatively low pKa of approximately 6.2, to provide a buffering effect, and an outer PEG layer (A segment) as a biocompatible palisade. 相似文献
48.
Wang CR Kai T Tomiyama T Yoshida T Kobayashi Y Nishibori E Takata M Sakata M Shinohara H 《Angewandte Chemie (International ed. in English)》2001,40(2):265
The cover picture shows a section of the electron charge density of the first metal carbide endohedral metallofullerene (Sc(2)C(2))@C(84) obtained from a synchrotron X-ray powder diffraction study by the maximum entropy method (MEM). The several density maxima, which correspond to scandium and carbon atoms, are clearly seen inside the C(84) carbon cage. The MEM charge density distribution also reveals that the C(84) cage has D(2d) symmetry (no. 23) and that the C(2) axis is parallel to the <100> face-centered cubic (fcc) direction of the unit cell. As a consequence of the site symmetry being 4mm, the C(2) axis of (Sc(2)C(2))@C(84) is oriented to six equivalent <100> directions and shows a merohedral disorder. The resultant Sc small middle dot small middle dot small middle dotSc distances and C-C bond lengths of the Sc(2)C(2) cluster are 0.429(2) and 0.142(6) nm, respectively. The observed C-C bond length is between that of a typical single and a double bond, and is very close to that of the C-C bond (0.143 nm) combining two pentagons in a C(60) molecule. More about this fascinating structure can be found in the contribution by Shinohara and co-workers on p. 397 ff. 相似文献
49.
Koji Nakabayashi Masaki Kawano Prof. Dr. Tatsuhisa Kato Prof. Dr. Ko Furukawa Dr. Shin‐ichi Ohkoshi Prof. Dr. Toshiya Hozumi Dr. Makoto Fujita Prof. Dr. 《化学:亚洲杂志》2007,2(1):164-170
We show a new approach to manipulating the through‐space spin–spin interaction by utilizing the confined cavity of a self‐assembled M6L4 coordination cage. The coordination cage readily encapsulates stable organic radicals in solution, which brings the spin centers of the radicals closer to each other. In sharp contrast to the fact that the radical in solution in the absence of the cage is in a doublet state, in the presence of the cage through‐space spin–spin interaction is induced through cage‐encapsulation effects in solution as well as in the solid state, resulting in the triplet state of the complex. These results were confirmed by ESR spectroscopy and X‐ray crystallography. The quantity of triplet species generated by encapsulation in the cage increases with increasing affinity of the radicals to the cage. We estimated the affinity between several types of guests and the cage in solution by cyclic voltammetry. We also demonstrate that the through‐space interaction of organic radicals within the self‐assembled coordination cage can be controlled by external stimuli such as heat or pH. 相似文献
50.
(Ss)-3-(p-Tolylsufinyl)-2-furaldimine was synthesized, and condensation of the chiral furaldimine with lithium ester enolates has been examined. The product distribution of the reaction is dependent upon reaction conditions and on the kind of the substituent placed on the esters. Disubstituted ester enolate resulted in the exclusive formation of (4R)-beta-lactam, while unsubstituted, tert-butyl ester enolate preferentially gave (3R)-beta-amino ester. With the monosubstituted ester enolates, the condensation afforded (4R)-beta-lactams and/or (3R)-beta-amino esters as major products. This method has been applied to an efficient route to chiral furyl beta-lactams. 相似文献