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991.
Raman phonon spectroscopy has been used to study photodimerization reaction inp-chloro cinnamic acid (pCCA) crystal. The β-form of the crystal yields the 4,4′-dichloro-β-truxinic acid dimer. Six distinct low frequency phonon
bands are observed in thepCCA monomer crystal. On reaction progress, these bands show a monotonic shift to lower frequencies and broaden out. Finally,
in the dimer crystal the phonon spectrum shows two weak broad bands. These results suggest that the reaction is homogeneous
in the initial stages and, as the product concentration increases, the lattice becomes highly disordered. The reactant and
the product were characterised by infrared and Raman spectroscopy. The disappearance of aliphatic C=C bond stretching vibration
and appearance of cyclobutane ring deformation and cyclobutane ring-breathing vibrations on reaction confirm photodimerization
by cyclobutane ring formation. The large Stoke's shift between the absorption and emission band suggest strong exciton-phonon
coupling in the monomer lattice. This reaction seems to be phonon-mediated. 相似文献
992.
Y. E. Kuznetsov N. L. Sukhov F. V. Pichugin B. G. Ershov 《Russian Chemical Bulletin》1996,45(12):2816-2819
Reactions ofmyo-inositiol hexa-O-nitrate with ammonia and primary amines yield tetrahydroxy-1,4-benzoquinone derivatives,viz., its tetraammonium salt and its diimines, respectively. Reactions with secondary and tertiary amines give salts of rhodizonic acid, which are converted into salts of croconic acid under certain conditions. The reactions with secondary amines involve intermediate formation of radical species, which were dectected by ESR spectroscopy. A scheme for the chemical transformations ofmyo-inositol hexa-O-nitrate under the action of amines was proposed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2962–2967, December, 1996. 相似文献
993.
The title compound, [Zn(AIP)(4,4-bipy)0.5(H2O)]n·0.75nH2O 1, was synthesized via the hydrothermal reaction of Zn(OAc)2 with 5-aminoisophthalic acid (H2AIP) and characterized by elemental analysis and infrared spectra. The complex crystallizes in monoclinic system, space group P21/c with a = 12.672(1), b = 7.6557(4), c = 16.181(1) (A),β = 109.187(2)o, V = 1482.6(2) (A)3, Z = 1, C52H52N8O23Zn4, Mr = 1418.58, Dc = 1.589 g/cm3, F(000) = 724 and μ(MoKα) = 1.685mm-1. The final R = 0.0702 and wR = 0.1524 for 1847 observed reflections with Ⅰ > 2σ(I), and R = 0.0873 and wR = 0.1664 for all data. X-ray diffraction studies reveal that the title compound has an interesting 2D microporous architecture with guest water molecules inside the channel. 相似文献
994.
V.V. Govande 《Tetrahedron letters》2004,45(35):6563-6566
The highly stereoselective synthesis of 1,3-disubstituted-4-trichloromethyl azetidin-2-ones by the [2+2] cycloaddition of ketenes with imines derived from chloral is described. 相似文献
995.
Céline Jousse-KarinthiFatima Zouhiri Jacqueline MahuteauDidier Desmaële 《Tetrahedron》2003,59(12):2093-2099
The palladium-catalyzed condensation of a variety of active methylene compounds with methyl 6-acetoxymethyl-hepta-2,6-dienoate was investigated. The six-membered adducts resulting from a η3 palladium complex alkylation-Michael addition sequence were obtained with moderate to good yields. In some cases, further evolution of the primary adduct was observed. The process has been expanded to access nitrogen heterocycles by using sodium p-toluenesulfonamide as the nucleophilic partner. 相似文献
996.
Hang GONG Nian Fa YANG? Wei Jun TANG Qing Hua FAN Li Wen YANG The College of Chemistry Xiangtan University Xiangtan Laboratory of Chemical Biology Center for Molecular Science Institute of Chemistry Chinese Academy of Sciences Beijing 《中国化学快报》2005,16(8)
Among the reactions in which C-C bonds are formed, the Baylis-Hillman coupling of aldehydes with α, β-unsaturated carbonylic compounds is currently attracting much interest due to the atom economy, the mild conditions and the generation of functional groups1,2. Furthermore, compared to the Heck, Suzuki and other palladium catalyzed C-C bond forming reaction3, the Baylis-Hillman reaction can be promoted by using organic bases in the complete absence of any metal4. However, almost all the … 相似文献
997.
N. Heldt K. Heldt H. Anderson W. Gaube 《Journal of Thermal Analysis and Calorimetry》1993,40(3):1213-1221
Telomerization of isoprene is characterized by intense thermal effects. The reaction system di-μ-chlorobis(η3-allyl)-dipalladium(II): tri-n-butylphosphine: sodium methylate: isoprene=1∶2∶3∶200 in a solvent-mixture of methanol∶benzene=1∶3 is used as a model. It is concluded that reaction of the catalyst combined with reduction of Pd(II) is followed by the telomerization reaction. There is a marked influence of Pd and phosphine concentration in the catalyst as well as concentration of isoprene. Results are available to optimize technical applications. 相似文献
998.
William H. Donovan 《Structural chemistry》1995,6(4-5):243-254
Ab initio and semiempirical molecular orbital calculations have been applied to study the concerted and stepwise isotopic scrambling mechanisms of 2-chloroethyl methyl sulfide in the gas phase and in aqueous solution. The calculations reveal the structural details of the reactants, transition structures, and intermediates involved in this reaction and provide relative energy estimates. The concerted mechanism is found to be competitive with the stepwise mechanism in the gas phase, but the stepwise mechanism is favored in aqueous solution as no true transition structure for the concerted mechanism could be found using the solvation models. A combined approach of evaluating solvation energies with the generalized-Bom-plus-surface-tensions SM
x
solvation models of Cramer and Truhlar at ab initio optimized geometries is found to deliver the best agreement with experimentally determined reaction barriers. Together with the recent experimental results of McManus and co-workers, the present study provides insights into the controlling factors involved in the elementary reaction steps of sulfur mustards and a solid foundation for investigations into more complex reactions of related compounds. 相似文献
999.
The γ(HO2) was elevated with increase of Cu(II) concentrations in aqueous (NH4)2SO4 aerosol. The threshold of Cu(II) concentration was 10-3 mol/L for the dramatic increase of γ(HO2) to 0.1, suggesting sensitive γ(HO2) value to concentration of transition metal ions in aerosol. 相似文献
1000.
《Tetrahedron letters》2003,44(26):4831-4834
A convenient and efficient synthesis of 3,5-di(silylethynyl)phenylacetylene and p-[3,5-di(silylethynyl)phenylethynyl]phenylacetylene has been carried out. These compounds serve to prepare nanometer-sized conjugated 1,4- and 1,3,5-phenylethynyl oligomers, by means of cross-coupling with a convenient haloaryl derivative, catalysed by palladium(II), in excellent yields. The phenylethynyl homologues show fluorescence emission, the wavelength of which is displaced by approximately 20 nm by each phenylethynyl unit increasing the conjugate chain. 相似文献