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1.
Popova L. M. Dmitrieva Yu. A. Vershilov S. V. 《Russian Journal of Applied Chemistry》2011,84(5):895-897
Maleopimar adducts of tall colophony esters with alcohols-telomers 1H,1H,5H-perfluoropentane-1-ol, 1H,1H,7H-perfluoroheptane-1-ol, and 1H,1H,9H-perfluorononane-1-ol were synthesized in conditions of Diels-Alder reaction. 相似文献
2.
A. V. Belovodskii E. E. Shults M. M. Shakirov I. Yu. Bagryanskaya Yu. V. Gatilov G. A. Tolstikov 《Russian Journal of Organic Chemistry》2010,46(11):1719-1734
By Heck reaction of isoalantolactone with aryl bromides or aryl iodides (3aR,4aS, 8aR,9aR,E)-3-arylmethylidene-8a-methyl-5-methylidenedecahydronaphtho[2,3-b]furan-2(3H)-ones and (4aS,8aR,9aS)-3-arylmethyl-8a-methyl-5-methylidene-4a,5,6,7,8,8a,9,9a-octahydronaphtho[2,3-b]furan-2(4H)-ones, products of the double bond shift, were synthesized. The yields of the arylation products depend on the nature of
the catalytic system and on the structure of the aryl halide. The structures of (3aR,4aS,8aR,9aR,E)-3-(3,4-dimethoxybenzylidene)-8amethyl-5-methylidenedecahydronaphtho[2,3-b]furan-2(3H)-one and (4aS,8aR,9aS)-3-(2-methylsulfanylbenzyl)-8amethyl-5-methylidene-4a,5,6,7,8,8a,9,9a-octahydronaphtho[2,3-b]furan-2(4H)-one were proved by XRD analysis. 相似文献
3.
The kinetic study of the gas-phase thermal elimination reactions of N-ethyl-3,5 dimethyl-pyrazole (I), N-ethyl-pyrazole (II), N-sec-butyl-pyrazole (III), and N-tert-butyl-pyrazole (IV) using a flow system is reported. After obtaining activation parameters for I we carried out competitive reactions with II, III and IV using I as internal standard to obtain their Ea. The values of Δ(ΔH) calculated for II, III and IV agree with the little differences in Ea experimentally found. 相似文献
4.
Bholanath Mandal Manas Banerjee Asok K. Mukherjee 《International journal of quantum chemistry》2005,101(2):119-126
A method for construction of the characteristic polynomial (CP) coefficients of the three classes of reciprocal graphs, viz., Ln + n(p), Cn + n(p), and K1,n?1 + n(p), has been developed that requires only the value of n. The working formulas have been expressed in matrix product form, computer programs for which can easily be developed. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
5.
Zhang Zhi-Ying 《中国化学》1986,4(1):7-19
On the basis of the experimental data reported in literature, the contributions of cation mass (m) and molar volume (V) to lattice heat capacity (C) were analyzed. The volumetric-mass formula, Cx=(l —f)·C1+f·C2+Cm·(mx — mx′), was presented for estimating the heat capacities of rare-earth compounds. In the formula C1 and C2 represent the lattice heat capacities of two reference substances respectively, f = Vx—V1/V2—V1 and Cm represents the lattice heat capacity variation with the variation 1 g of cation mass. The equation relating the Cm with temperatures was derived as follows: Cm = 0.084 e ?0.0074T ?0.27 e ?0.045T, and mx and mx′ (= (1 - f) m1+f m2) represent the practical and “assumed” cation masses of the substance in question respectively. 相似文献
6.
Shunji Nomura Nobiru Nakamura Hiromichi Kawai 《Journal of Polymer Science.Polymer Physics》1971,9(3):407-420
The orientation distribution function for noncrystalline structural units in polymer systems cannot be determined completely from any experimental source; only the second and/or fourth moments of the distribution function, i.e., the second and/or fourth orders of the generalized orientation factors Flmj, can be evaluated. It is there-fore necessary to estimate the distribution function from F2mj and F4mj. In this paper, a graphical representation of the state of orientation is first discussed in terms of plots of F40j against F20j for several types of distribution functions for uniaxial orientation. These are three types of extreme concentration of the distribution at particular polar angles θ0 given by θ0 = 0, 0<θ0<π/2, and θ0 = π/2; five types of rather realistic distributions having single maxima at θj = 0, θ0, π/2 and double maxima at θj = 0, π/2, and a single minimum at θj = θ0; and four types of more realistic distributions including Kratky's floating rod model in an affine matrix. Second, estimation of the distribution function for uniaxial orientation from F40j and F20j is discussed quantitatively in terms of the mean-square error by three approximation methods: (a) expansion of the distribution function in finite series of spherical harmonics through the fourth order, (b) approximation of the distribution function as a composite of two components, random orientation and a particular orientation distribution given by Na (cos2θj)a, Na being a constant, and (c) approximation of the distribution function by Na (cos2θj)a alone. It is concluded that when the orientation distribution is sharp, estimation by the second method of approximation gives a smaller error than the first. 相似文献
7.
A. A. Miller 《Journal of Polymer Science.Polymer Physics》1968,6(6):1161-1175
The melt viscosity, the glass transition, and the effect of pressure on these are analyzed for polystyrene on the basis of the Tammann-Hesse viscosity equation: log η = log A + B/(T ? T0). Evidence that the glass transition is an isoviscosity state (log ηg ? 13) for lower molecular weight fractions (M < Mc) is reviewed. For a polystyrene fraction of intermediate molecular weight (M ? 19,000; tg = 89°C.), it is shown that B is independent of the p–v–T state of the polymer liquid and that dT0/dP = dTg/dP. This is consistent with the postulate that B is determined by the internal barriers to rotation in the isolated polymer chain. Relationships are derived for flow “activation energies” at constant pressure and at constant volume, and for the “activation volume.” Values for polystyrene along the zero-pressure isobar and along the constant viscosity, glasstransition line are reported. For the latter, ΔVg* is constant and corresponds to about 10 styrene units. The “free volume” viscosity equation: log η = log A + b/2.3?, is reexamined. For polystyrene and polyisobutylene, ?g/b = 0.03, but ?g and b themselves differ appreciably in these polymers. The parameter b is the product of an equilibrium term Δα and the kinetic term B, and none of these is a “universal” constant for different polymers. The physical significance of the free volume parameter ?, particularly with regard to the “excess” liquid volume, remains undefined. Two new relationships for dTg/dP, one an exact derivation and the other an empirical correlation, are presented. 相似文献
8.
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10.
The fracture energy G of an adhesive bond appears to be a product of two terms: G = GO [1 + f(R, T)], where GO is the intrinsic (chemical) strength of the interface and f(R, T), usually much larger than unity, reflects energy dissipated within the adherends at a crack speed R and temperature T. Values of GO have been determined for interlinked sheets of an SBR elastomer by measuring the peel strength at low rates and high temperatures, and in the swollen state, to minimize internal losses. Both the density ΔN and molecular length L of interlinking molecules were varied. GO was found to increase in proportion to (ΔN)L3/2, in accord with the molecular theory of Lake and Thomas. As the peel rate was raised and the test temperature lowered, G was considerably increased by internal dissipative processes, becoming as much as 1000 × GO near the glass transition. The loss function f(R, T) was found to depend somewhat upon the strand length L, being about twice as large at intermediate peel rates when L was increased by 40%. It also depended on the density ΔN of interlinking molecules, being about twice as large at high peel rates when the density of interlinks was reduced by a factor of six. Thus, the loss function f(R, T) is greater when the interlinking molecules are few and long, and it is lower when they are many and short. However, it is mainly governed by two parameters: peel rate R and temperature difference (T − Tg), in accord with a viscoelastic loss mechanism. © 1996 John Wiley & Sons, Inc. 相似文献
11.
R. Kublashvili 《Chemistry of Natural Compounds》2003,39(6):586-588
N-o-, -m-, and -p-carboxyphenyl-D-glucosylamines and N-o-, -m-, and -p-hydroxyphenyl-D-glucosylamines were synthesized by reaction of D-glucose with o-, m-, and p-aminobenzoic acids and o-, m-, and p-aminophenols. It was demonstrated that both - and -anomers were formed by N-glycosylation of o-, m-, and p-aminobenzoic acids; only -anomers, by N-glycosylation of o-, m-, and p-aminophenols. 相似文献
12.
Louis Watts Clark 《国际化学动力学杂志》1975,7(6):807-816
Rate constants and activation parameters are reported for the decarboxylation of n-butylmalonic acid in four normal alkanols (hexanol? 1, octanol? 1, decanol? 1, and dodecanol? 1) and in five amines (aniline, N-methylaniline, N-ethylaniline, N-n-propylaniline, and N-n-butylaniline). Both ΔH? and ΔS? of the reaction in both homologous series decrease regularly with increasing length of the hydrocarbon chain of solvent. If we compare data for the reaction in alkanol–amine pairs containing the same total number of carbon atoms in the molecule, we find that the ΔH? values are identical, but that the value of ΔS? is 0.8 eu/mole higher for the reaction in the amines as compared with the alcohol. The rate constant, at all temperatures, is 1.5 times as large in the amine as it is in the corresponding alcohol. Empirical equations are deduced relating the parameters ΔH? ΔS? ΔG? and k of the reaction to the parameters n and T, where n is the total number of carbon atoms in the solvent molecule and T is the absolute temperature. The results reported herein are compared with previously reported data for malonic acid. 相似文献
13.
Sarapulova G. I. Rozinova L. G. Rozinov V. G. Kolbina V. E. 《Russian Journal of Organic Chemistry》2002,38(9):1266-1270
Reactions of new enehydrazides, N',N'-dimethyl-N-vinylpropenohydrazide and N',N'-dimethyl-N-vinylbenzohydrazide with chloroform, phenol, and hydrogen chloride in carbon tetrachloride were studied by IR spectroscopy. In the first two cases, molecular complexes are formed between the hydrazide and proton donor. The reaction of N',N'-dimethyl-N-vinylpropenohydrazide with HCl results in formation of dihydropyrazole derivative which exists as a tautomeric mixture of the major lactam and minor lactim forms. N',N'-dimethyl-N-vinylbenzohydrazide reacts with hydrogen chloride to give protonated form in which proton is localized on the amino nitrogen atom. The structure of the initial compounds and the products was analyzed in terms of AM1 quantum-chemical calculations. 相似文献
14.
V. I. Baranov L. A. Gribov V. E. Dridger M. Kh. Iskhakov I. V. Mikhailov 《High Energy Chemistry》2009,43(5):362-369
The possibility of construction of a semiempirical method for simulation of photochemical processes and calculation of quantum
yields of reactions has been studied. The practicability of the approach was demonstrated for the o-xylene → m-xylene, m-xylene → p-xylene, m-xylene → o-xylene, and o-diethylbenzene → m-diethylbenzene photoisomerization reactions as an example. The calculated quantum yields of the reactions are in qualitative
agreement with experimental data. 相似文献
15.
The spread s(G) of a graph G is defined as s(G) = max
i,j
|λ
i
− λ
j
|, where the maximum is taken over all pairs of eigenvalues of G. Let U(n,k) denote the set of all unicyclic graphs on n vertices with a maximum matching of cardinality k, and U
*(n,k) the set of triangle-free graphs in U(n,k). In this paper, we determine the graphs with the largest and second largest spectral radius in U
*(n,k), and the graph with the largest spread in U(n,k).
相似文献
16.
Roland Achini 《Helvetica chimica acta》1981,64(7):2203-2218
The construction of new or novelly functionalized annulated and bridged tricylic compounds by two consecutive C,C-bond formations (a and b in la , Scheme 1) is described. In a first step, chloroalkyl-substituted aminonitriles yielded pyrrolidines 8 , 15a , 15b , 23 , 25 and piperidine 18 by carbanionic ring closure (Schemes 5, 6, 7 and 8). Subsequent Friedel-Crafts cyclization transformed the β-aminonitriles 8 , 15a , 15b , and 18 either directly or via their carboxylic acid derivatives to the indeno [1, 2-c]pyrrole, 2, 5-methano-3-benzazocine, benz [f]isoindoline and 1, 4-ethano-2-benzazapine skeletons 11 , 16a , 16b and 21 , respectively (Schemes 5, 6 and 7). By classical ring expansion reactions the pyrrolo [3, 4-c]isoquinoline and benzopyrano-[3, 4-c]pyrrole skeletons 28 resp. 31 were obtained from 11 (Scheme 9). 相似文献
17.
Kenji Yanagihara H. Yasuda 《Journal of polymer science. Part A, Polymer chemistry》1982,20(7):1833-1846
The double probe method was applied to plasma of tetrafluoroethylene (TFE) and ethylene and the electron temperature (Te) and density of positive ions (np) were measured at various discharge wattages. The probe current-probe voltage diagrams for TFE were different from those for ethylene. The shape of its diagram indicates that a considerable number of negative ions exist in TFE plasma. The levels of np for TFE were also nearly six times greater than those for ethylene at the same discharge current. The dependence of TFE polymer deposition and the chemical structure of the polymer, based on ESCA data on discharge current, was related to Te and np measured by the probe method. The values of Te and np may not be directly related to the polymer formation in a plasma; the method provides a direct measure of plasma energy density where plasma polymerization takes place, whereas it cannot be accurately estimated by the input energy of a discharge. It was found that plasma energy density based on (npTe) for TFE plasma and that for ethylene differ significantly at the same level of input parameter (W/FM), where W is the discharge wattage, F is the volume flow rate, and M is the molecular weight of the monomer. 相似文献
18.
The polymerization of N-vinylcarbazole (NVC) initiated by PhMgBr in benzene was studied at 32°C. Rp is second order with respect to PhMgBr concentration but increases with NVC concentration (up to 0.06 M) and falls thereafter. Rp and P n are depressed by the addition of thiophene and water. Modifiers such as benzaldehyde, butanone, and ethylene glycol practically inhibit the polymerization. Carbon tetrachloride and carbon dioxide, when passed through the NVC solution first, enhance the Rp and P n increases with increasing PhMgBr and NVC concentrations, respectively. Rp increases with temperature, but P n shows a maxium at a certain temperature. A cationic mechanism has been proposed where the polymerization is initiated by RMg+ cations produced from the ionization of PhMgBr by the Ashby and Smith mechanism. 相似文献
19.
Marion Schmitz Stefan Leininger Uwe Bergstrßer Manfred Regitz 《Heteroatom Chemistry》1998,9(4):453-460
Hydrostannylation reactions of the phosphaalkenes 9,11, and 21 with the triorganotin hydrides 1 proceed by different routes. Whereas the trior-ganotin hydrides 1a,b undergo regioselective 1,2-addition to the P/C double bond of the P-aminophosphaalkene 9 to furnish the 2-stannylphosphanes 17a,b, the 1,2-addition products to the P-halophosphaalkenes 11 and 21 can only be postulated as the reactive intermediates 20 and 23, respectively. The reactions of 11 with 1a,b proceed with cleavage of the triorganotin halide via the diphosphene 15 to furnish the cyclophosphanes 18 and 19. On the other hand, the hydrostannylation reactions of the phosphaalkene 21 are not selective, and the 1,3-diphosphetane 22 is isolated as one of the reaction products. © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9:453–460, 1998 相似文献
20.
S. S. Labana 《Journal of polymer science. Part A, Polymer chemistry》1968,6(12):3283-3293
The kinetics of high-intensity electron beam-induced polymerization of di(2′-methacryloxyethyl)-4-m-phenylenediurethane during the network formation has been studied up to complete gelation and up to 56% conversion of unsaturation. From experimentally determined gel fractions, rate of disappearance of unsaturation, kinetic chain length, and intensity dependence, it is proposed that the polymerization takes place in a swollen network where the growing chains undergo unimolecular termination, and where gel-gel reaction is prohibited. The rate expression derived is: In [α(1 ? g)0.545] = In α0 ? 2.51 kikpt/kt where α is the total unsaturation and g is the gel fraction. The value of kp/kt is found to be 2.1 and that of GR, the free radical yield per 100 eV absorbed, to be 16; these high values are ascribed to the high viscosity of the polymerizing system. 相似文献