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51.
52.
The macroradical decay in poly(methyl methacrylate) samples with different thermal histories was investigated in the temperature interval 20–100 °C using ESR spectroscopy and the second order kinetic model. The rate constants exhibit two different regimes with the transitions atT
tr=68±1°C which are independent of thermal treatment. ForT<T
tr andT>T
tr the rate constants as well as the corresponding activation parameters are sensitive to history because of different physical microstructures. The compensation law, i.e., the linear relation between lnk
o, eff andE
eff, was analyzed in terms of the so-called compensation quantitiesk
c andT
c and a proximity betweenT
c=T
tr andT
o=53±3 °C — Vogel temperature for -segmental dynamics was found. A comparison of kinetic and dynamic data suggests that the decay of terminal macroradicals in the low-temperature region is controlled by secondary relaxations and that the -mobility contributes to a more rapid decay at higher temperatures belowT
g. 相似文献
53.
Molar excess mixing enthalpies h
E
, Gibbs free energies g
E
and hence entropies s
E
have been obtained using calorimetry and the vapor sorption method at 25°C for hexane isomers+2,2,4,4,6,8,8-heptamethylnonane, a highly branched C
16
. The h
E
and g
E
are negative while Ts
E
are positive, but small. The values are explained by the Prigogine-Flory theory through negative free volume contributions to h
E
and Ts
E
, counterbalanced in the case of Ts
E
by the positive combinatiorial Ts
E
for mixing molecules of different size. No contribution is seen from the interaction between methyl and methylene groups. The excess quantities are also obtained for hexane and heptane isomers mixed with n-hexadecane. Values of h
E
and Ts
E
are now strongly positive, while those of g
E
are only slightly less negative. The interpretation requires two recently advanced contributions in addition to those of the Prigogine-Flory theory: 1) a decrease of order when correlations of orientations between n-C
16
molecules in the pure liquid are replaced in the solution by weaker correlations whose strengths depend on the shapes of the lower alkane isomers. For lower alkane isomers of the same shape, but highly sterically hindered, h
E
and Ts
E
are small, manifesting, 2) a negative contribution, ascribed to a rotational ordering of n-C
16
segments on the sterically-hindered molecule. Enthalpy-entropy compensation is observed for these new contributions, arising from their rapid fall-off with increase of temperature. 相似文献
54.
55.
Alcaide B Almendros P Alonso JM Aly MF 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(14):3415-3426
Imines derived from 4-oxoazetidine-2-carbaldehydes have been found to be versatile Diels-Alder reagents in that they exhibit two reactivity patterns. 2-Azetidinone-tethered imines undergo diastereoselective reaction with Danishefsky's diene in the presence of different Lewis acids. The effect of the amount of catalyst on the conversion rate as well as on the product ratio has been studied. Under standard reaction conditions, indium(III) chloride and zinc(II) iodide provided the best yields, and indium(III) triflate the highest diastereoselectivity in the Lewis acid promoted aza-Diels-Alder cycloaddition. Treatment of the aforementioned imines with cyclopentadiene, 2,3-dimethyl-1,3-butadiene or 3,4-dihydro-2 H-pyran led to cycloadducts arising from inverse electron-demand condensation involving the beta-lactam-tethered aryl imine as the heterodiene component. In addition, the first methodology for preparing indolizidines from beta-lactams has been developed. This process involves amide bond cleavage of the beta-lactam ring in the aza-Diels-Alder cycloadducts with concomitant cyclization. Full chirality transfer occurs when the reaction is performed with an enantiomerically pure substrate. 相似文献
56.
57.
The asymmetric dihydroxylation of α,β-unsaturated sulfones under Sharpless conditions affords enantioenriched α-hydroxyaldehydes in a complex mixture of dimeric species. These mixtures undergo olefination generating the corresponding α,β-unsaturated esters or furan-2(5H)-ones with high levels of enantiomeric excess. The application of this method for the rapid stereoselective synthesis of the furanone natural products; quercus lactone and maritolide, are described. 相似文献
58.
A general route for the synthesis of highly substituted aryl cyclopentanes has been developed involving Diels-Alder reaction of asymmetric dienes prepared from (+)-camphoric acid followed by aromatization of the resulting cyclohexene derivatives. Employing this protocol enantiospecific synthesis of (+)-herbertene and (+)-cuparene has been accomplished. 相似文献
59.
Halland N Alstrup Lie M Kjaersgaard A Marigo M Schiøtt B Jørgensen KA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(23):7083-7090
The mechanism for the 2,5-diphenylpyrrolidine-catalyzed enantioselective alpha-chlorination of aldehydes with electrophilic halogenation reagents has been investigated by using experimental and computational methods. These studies have led us to propose a mechanism for the reaction that proceeds through an initial N-chlorination of the chiral catalyst-substrate complex, followed by a 1,3-sigmatropic shift of the chlorine atom to the enamine carbon atom. The suggested reaction course is different from previously proposed mechanisms for organocatalytic enamine reactions, in which the carbon-electrophile bond is formed directly. Furthermore, the rate-determining step in the overall reaction was determined and the presence of nonlinear effects was probed. 相似文献
60.
本文在两次标准加入法[1]的基础上,提出了三组份同时测定的三次标准加入法,并应用于钼、钨和钛的流动注射同时测定。测定条件:[水杨基荧光酮(SAF)]=1.25 ×10-4mol/L,[溴化+六烷基三甲基铵(CTMAB)」=2.5×10-3mol/L,pH1.35,25℃,采样、进样时间分别为10s和18s,进样频率128次/h。为消除组份间协同作用引起的吸光度加合性的偏离,定义了三组份协同系数。将其引入三组份同时测定方法,补偿了吸光度对线性的偏离。补偿后钼、钨和钛的测定范围分别为0.05~0.35,0.25~1.00,0.025~0.30mg/L。测定了钢样及模拟样品中钼、钨和钛含量,结果较好。 相似文献