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961.
Zhengjie Pi Joseph P. Kennedy James W. Summers 《Journal of polymer science. Part A, Polymer chemistry》2002,40(21):3644-3651
The tertiary chlorine (Clt) content of vinyl chloride/2‐chloropropene copolymers [P(VC‐co‐2CP)] was determined by NMR spectroscopy. Copolymers containing 6.8–47.0 Clt's per P(VC‐co‐2CP) chain were used to initiate the cationic grafting of α‐methylstyrene, norbornadiene, indene, and norbornene with Et2AlCl under various conditions. Grafting was demonstrated by selective solvent extraction, and the effect of the experimental conditions on the grafting efficiency was examined. Select rheological and thermal characteristics of P(VC‐co‐2CP) grafts, including the glass‐transition temperature, heat deflection temperature, and discoloration upon heating, were studied. P(VC‐co‐2CP) carrying 7–11 poly(α‐methylstyrene) or polynorbornadiene branches per chain raised the glass‐transition temperature to, or above, that of a blend control. P(VC‐co‐2CP)s fitted with polyindene or polynorbornene branches were less effective in raising the mechanical properties. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3644–3651, 2002 相似文献
962.
963.
X. Li Y. Zhao X. Jing F. Liu F. Hao 《International journal of quantum chemistry》2006,106(5):1086-1092
The equilibrium geometries, vibrational frequencies, and dissociation energies of rare gas iodine clusters Rg2I?(Rg = Ar, Kr, Xe) were calculated at the Hartree–Fock (HF), second‐order Møller–Plesset (MP2), the coupled cluster method with single and double excitation and a noniterative correction for triple excitations method [CCSD(T)] levels. The title species have bent C2v structure of about 60° angle. The electron correlation effects and relativistic effects on the geometry and stability were investigated at CCSD(T) level. Both effects stabilize title species. The calculated electron affinities are in good agreement with the experimental results available. The effect of high angular momentum functions (g and h) was studied. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 相似文献
964.
V. A. Nikanorov T. V. Storozhev S. G. Novikov S. V. Sergeev D. V. Zverev 《Russian Chemical Bulletin》1998,47(6):1224-1225
The possibility of redox troponization of a gem-polyhalomethylated semiquinoid system, π-coordinated to a metal atom, was
shown in relation to the reaction of (η5-cyclopentadienyl)(η4-4-menthyl-4-exo-trichloromethylcyclohexa-2,5-dien-1-one)rhodium with Pd(PPh3)4. The reaction occurs with retention of the metal coordination affording a sevenmembered organometallic derivative of the
nonbenzoid aromatic series, namely, (η5-cyclopentadienyl)(η4-4-chloro-5-menthylcyclohepta-2,4,6-trien-1-one)rhodium, whose structure was established by means of elemental analysis, NMR,
and mass-spectral data.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1255–1256, June, 1998. 相似文献
965.
Ivan Bernal D. C. Levendis Richard Fuchs G. M. Reisner Juanita M. Cassidy 《Structural chemistry》1997,8(4):275-285
The crystal structure of 4-cyclopropylacetanilide was investigated at room temperature (21C) and at –100C in order to determine the orientation of the phenyl ring with respect to the cyclopropane moiety and the effect of this substituent on the stereochemistry of the three-membered ring. The compound was chosen because it is one of the few species containing a simple phenyl ring as the sole cyclopropane ring substituent and whose crystals are suitable for X-ray diffraction at room temperature. The substance crystallizes in space groupP2l/c at either temperature (no phase transitions) with cell constants: (at 21C)a=9.725(2),b=10.934(3), andc=9.636(2) å,=106.13(1);V=984.21 å3 andd(calc;z=4)=1.182 g cm–3. The relevant parameters for the –100C structure area=9.557(4),b=10.980(2), andc=9.641(2) å,=106.34(3);V=970.76 å3 and d(calc;z=4)=1.199 g cm–3. Final values wereR(F)=0.042, Rw=0.035, using unit weights, and its nonhydrogen atoms were used to phase the low-temperature data, whose final discrepancy indices wereR(F)=0.051,R
w
=0.061. The phenyl substituent is almost exactly in the bisecting conformation with respect to the C-C-C angle at the point of attachment to cyclopropane and conjugative effects are clearly evident in the lengths of the cyclopropane ring [1.494(3), 1.498(3), and 1.474(4) å, the later being the distal bond]. If one omits the terminal methylene fragments at C10 and C11, the atoms comprising the acetanilide fragment and the substituted carbon of the cyclopropane ring lie in a nearly perfect plane. Molecular mechanics as well as semiempirical (AM1) calculations were carried out in order to determine the structure of the energy-minimized configurations in the two computational environments. The molecular conformations thus obtained are close to that experimentally observed from the X-ray diffraction experiment. In both theoretical models, the lowest energy conformation is that in which the plane of the phenyl ring bisects the cyclopropane C-C-C angle as was experimentally observed. Finally, the shape of the conformational barrier as a function of the orientation of the plane of the phenyl ring was computed, giving a maximum barrier to rotation of 2.2 kcal/mol. Similar calculations were carried out for two other aryl cyclopropanes, whose rings (naphthalene and anthracene) cannot adopt the bisecting position. Comparisons of experimental geometrical parameters as well as of the barriers to rotation are presented.on leave at the University of Houston, 1995–1996. 相似文献
966.
Steric structures of dysprosium(III) aminobenzoate complexes with the 11 and 12 molar ratio in aqueous solutions were determined on the basis of pH-metric and paramagnetic birefringence data. An increase in conjugation observed for the series of the acids,viz., benzoic,meta-, ortho-, andpara-aminobenzoic acids, results in the increased stability of the complexes with the 11 and 12 composition. In the case ofpara-aminobenzoic acid, the polyhedra [DyL(H2O)6]2+ and [DyL2(H2O)4]+ are cubes with the ligands coordinated to one and two edges, respectively. In the case ofmeta-aminobenzoic acid, the polyhedra [DyL(H2O)6]2+ and [DyL2(H2O)4]+ are a dodecahedron with the ligand coordinated to one edge and a square anti-prism with the ligands coordinated to two edges, respectively. In the case ofortho-aminobenzoic acid, both the 11 and 12 complexes have structures that are intermediate between the structures ofmeta- andpara-aminobenzoic acids.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1767–1770, October, 1994. 相似文献
967.
2,4-Dihydroxyphenylthioamide derivatives modified on the N-aryl ring have substantial fungicidal activity. To determine their quantitative structure–activity relationships their lipophilicity was determined by use of the chromatographic methods column liquid chromatography and thin-layer chromatography. Methanol–water systems were used as mobile phases and the linear dependences of retention (RM and log k) on volume fraction of organic modifier, φ, were determined. This enabled precise determination of lipophilicity (RMw and log kw) by extrapolation. Correlations were found between quantities characterizing the lipophilicity of the compounds. Deviations enabled discovery of compound structural features which increase or reduce lipophilicity. When these data were correlated with biological activity against the phytopathogenic fungi Alternaria alternata and Botrytis cinerea parabolic dependences were obtained. 相似文献
968.
A structure and kinetic stability study on some complexes with the general formula MN5, where M are the alkali-metal atoms, Li, Na, K, and Rb, has been carried by using hybrid density functional methods. Complex B (C2v) with two points of attachment to the N5 ring is the most energetically favored for all metals considered here. Pyramidal structures A (C5v) are kinetically unstable and they rapidly rearrange to the most stable planar structures B. At the QCISD(T)/6-311 + G*//B3LYP/6-311 + G* + ZPE (B3LYP/6-311 + G*) level, the decomposition barrier heights of LiN5-B, NaN5–B, KN5-B, and RbN5-B are predicted to be 19.9, 22.0, 22.5, and 23.0 kcal/mol, respectively. In addition, the rate constants of the decomposition reaction MN5-B MN3 + N2 (M + Li, Na, K, and Rb) are also predicted using conventional transition state theory and canonical variational transition state theory, respectively. 相似文献
969.
E. Asmus und W. Klank 《Fresenius' Journal of Analytical Chemistry》1973,265(4):267-268
Zusammenfassung 2-Chinolylfluoron bildet mit Zirkonium einen 14-Komplex, dessen Extinktionskoeffizient bei 539 nm
max=165000 ist. Das Bestimmungsverfahren für ZrOCl2 in Speisesalz wird auf dieser Farbreaktion aufgebaut.
Photometric determination of ZrOCl2 in table salt
2-Quinolylfluorone forms a 14-complex with zirconium. Owing to its high extinction coefficient max=165000 at =539 nm the complex can be used for the determination of ZrOCl2 in table salt.相似文献
970.
The thermal characterization (DSC and TG) of benzylcellulose derivatives prepared from the benzylation of bleached Pinus Kraft
pulp is described in this paper. The objective of this study was to examine the changes in glass transition temperature (T
g) and the thermal stability of the benzylated product as a function of the benzylation extent (degree of substitution). The
DSC analysis showed that the benzylcelluloses can display glass transition temperature at two different regions and that thermal
stability is slightly higher than that of the parent cellulose.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献