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41.
The mechanisms of nitrosation of acetone through sodium enolate [CH3CO1CH2]-Na+ (1) or naked enolate [CH3CO1CH2]- (2) with methyl nitrite CH3O3NO2 (3), and the reactivity of the syn-form of 3 (syn-3) during the C-N bond formation process were investigated using ab initio molecular orbital (MO) methods. Our results have demonstrated the predominant formation of E-1-hydroxyimino-2-oxo-propane CH3COCH=NOH (4E) when the complex [CH3CO1CH2NO2(O3CH3)]-Na+ was produced kinetically via a metal-chelated pericyclic transition state (TS(CHELATED)), in which the O3 atom of syn-3 was coordinated to the Na+ atom of 1. 相似文献
42.
peri-Acenes have shown great potential for use as functional materials because of their open-shell singlet biradical character. However, only a limited number of peri-acene derivatives larger than peri-tetracene have been synthesized to date, presumably owing to the low stability of the target compounds in addition to the complicated synthesis scheme. Here, a very simple synthesis route for the tetrabenzo[a,f,j,o]perylene (TBP) structure enables the development of highly stable peri-tetracene analogues. Despite a high degree of singlet biradical character, the compounds with four substituents at the zigzag edge show a remarkable stability in solution under ambient conditions, which is better than that of acene derivatives with a closed-shell electronic configuration. The crystal structures of the TBP derivatives were obtained for the first time; these are valuable to understand the relationship between the structure and biradical character of peri-acenes. The application of peri-acenes in electronic devices should also be investigated. Therefore, the semiconducting properties of the TBP derivative were investigated by fabricating the field-effect transistors.Highly stable peri-tetracene analogues with a high degree of singlet biradical character were synthesized in a very simple route, and their crystal structures and semiconducting properties were investigated. 相似文献
43.
T. Hondoh H. Anzai A. Goto S. Mae A. Higashi C. C. Langway Jr. 《Journal of inclusion phenomena and macrocyclic chemistry》1990,8(1-2):17-24
We have carried out X-ray diffraction studies on single crystals of natural air-hydrate in deep ice cores recovered at Dye-3 Greenland. Integrated intensities for 470 diffracting planes were measured by an automated four-circle diffractometer. The space group determined is cubicFd3m and the lattice constant is 17.21(3) Å. These results indicate that the crystallographic structure is the Stackelberg's structure II, in contrast to the previously anticipated structure. This finding agrees with the recent results on the synthetic air-hydrate by Davidsonet al. It was also found by difference Fourier synthesis for guest molecules that electron density in a 16-hedral cage has multiple maxima displaced from the center of the cage while that in the 12-hedron was approximately spherical.Dedicated to Dr D. W. Davidson in honor of his great contributions to the sciences of inclusion phenomena. 相似文献
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The total synthesis of a new platelet aggregation-inhibiting gamma-lactam PI-091 (1) gave a 1:1 diastereomeric mixture at the gamma-ketal carbon. The high-yielding aldol reaction of an appropriately protected 1,3,4-trihydroxy-4-methyldecan-2-one 42, prepared from D-glucose, with the kinetically generated enolate of 3-methyl-2-butanone provided 43. The resulting diastereomeric mixture of the aldol adduct 43 was converted to a 2,4-alkylated furan 45 via an intramolecular ketalization followed by dehydration. The addition of a singlet oxygen to the alpha-trimethylsilylated furan 48derived from 45 under photochemical conditions efficiently provided an alpha,gamma-dialkylated gamma-hydroxy gamma-lactone 47. The transformation of methyl ketal 52 prepared from 47 into gamma-hydroxy gamma-lactam 53 was achieved by exposure to liquid ammonia in MeOH. The total synthesis of 1 was achieved from 52 through the Dess-Martin periodinane oxidation of the secondary hydroxy group in the side chain. The present total synthesis revealed that the stereogenic carbon center in the side chain in natural 1 is S. 相似文献
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Akchurin N Langland J Onel Y Bonner BE Corcoran MD Cranshaw J Nessi-Tedaldi F Nessi M Nguyen C Roberts JB Skeens J White JL Bravar A Giacomich R Penzo A Schiavon P Zanetti A Bystricky J Lehar F de Lesquen A van Rossum L Cossairt JD Read AL Derevschikov AA Matulenko YA Meschanin AP Nurushev SB Patalakha DI Rykov VL Solovyanov VL Vasiliev AN Grosnick DP Hill DA Laghai M Lopiano D Ohashi Y Shima T Spinka H Stanek RW Underwood DG Yokosawa A Funahashi H Goto Y Imai K Itow Y Makino S Masaike A 《Physical review D: Particles and fields》1993,48(7):3026-3036