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31.
In spite of its industrial importance, the detailed reaction mechanism of cyclohexane autoxidation by O2 is still insufficiently known. Based on quantum chemical potential energy surfaces, rate coefficients of the primary and secondary chain propagation steps involving the cyclohexylperoxyl (CyOO) radical were evaluated using multiconformer transition-state theory. Including tunneling and hindered-internal-rotation effects, the rate coefficient for hydrogen-atom abstraction from cyclohexane (CyH) by CyOO was calculated to be k(T)= 1.46 x 10(-11) x exp(-17.8 kcal mol(-1)/ RT) cm3s(-1) (300-600K), close to the experimental data. A "Franck-Rabinowitch cage" reaction between the nascent cyclohexylhydroperoxide (CyOOH) and cyclohexyl radical, products from CyOO + CyH, is put forward as an initially important cyclohexanol (CyOH) formation channel. alphaH abstraction by CyOO. from cyclohexanone was calculated to be only about five times faster than that from CyH, too slow to explain all the observed side products. The a-hydrogen (alphaH) abstractions from CyOH and CyOOH by CyOO. are predicted to be about 10 and 40 times faster, respectively, than the CyOO. +CyH reaction. The very fast CyOO.+CyOOH reaction proceeds through the unstable Cy-alphaH .OOH radical that decomposes spontaneously into the ketone (Q=O) plus the OH radical; the "hot" .OH is found to produce the bulk of the alcohol via a second, "activated cage" reaction analogous to that above. It is thus shown how the very reactive CyOOH intermediate is the predominant source of ketone and alcohol, while it also leads to some side products. The alpha-hydroxycyclohexylperoxyl radical formed during the moderately fast oxidation of CyOH is shown to decompose fast into HO2 + cyclohexanone in a rapidly equilibrated reaction, which constitutes a smaller, second ketone source. These two fast cyclohexanone forming routes avoid the need for unfavorable molecular routes hitherto invoked as ketone sources. The theoretical predictions are supported and complemented by experimental findings. The newly proposed scheme is also largely applicable to the oxidation of other hydrocarbons, such as toluene, xylene, and ethylbenzene. 相似文献
32.
Thi Thanh-Tâm Nguyên Claude Delseth Jean-Pierre Kintzinger Pierre-Alain Carrupt Pierre Vogel 《Tetrahedron》1980,36(19):2793-2797
Natural-abundance 17O-NMR spectra of 7-oxanorbornane exo-3-oxatricyclo [3.2.1.02.4]octane and their unsaturated derivatives (endo cyclic and exocyclic double bonds) have been measured. Linear correlation laws were observed for of these ethers/corresponding hydrocarbons. The “cyclization shifts” for δo in ethers were not correlated by the “cyclization shifts” for δc of the corresponding hydrocarbons. 相似文献
33.
When metoprolol in methanol was analysed by capillary gas chromatography (GC), an additional peak was observed; mass spectrometry (MS) showed this additional peak to have a molecular weight 12 dalton higher than that of the parent compound. A similar phenomenon was observed with other beta-adrenergic blocking aryloxypropanolamines in methanol or dichloromethane. Capillary GC-MS using deuterated solvents as isotopic markers showed that a methylene group from the solvents was incorporated into the parent molecule. The structure of the observed products and the mechanism of their formation are proposed. 相似文献
34.
Propargyl ethers treated with dimsyl anion in DMSO at 80-100°C undergo terminal methylenation to afford corresponding (E) 1-alkoxy-1,3-butadienes. The reaction proceeds via an alkoxy-allene. 相似文献
35.
36.
A method of determination of adsorbed and absorbed hydrogen on palladium catalysts with carbon carriers is suggested and verified. The method allows Had and Hab to be determined with an accuracy of about 10% using catalysts containing at least 5% Pd.
- . . . 10% , , - , 5% Pd.相似文献
37.
Alexander I. Popov Alfred J. Smetana Jean-Pierre Kintzinger Thi Thanh-Tam Nguyêen 《Helvetica chimica acta》1980,63(3):668-673
Complexation between crown ethers 12C4, 15C5, 18C6 and cryptand 222, and alkali cations Li+, Na+, K+ in various solvents were studied by 17O-NMR. spectroscopy. Small diamagnetic shifts arising from the cation electric field are observed. They increase according to the sequence K+ < Na+ < Li+. 17O-linewidth are discussed and compared to the 13C relaxation times. Linewidth modification results mainly from modifications of the effective correlation time. In general, for crown ethers, considerable line broadening occurs when the cation fits well into the cavity but line narrowing occurs when the cation is much smaller than the cavity. 相似文献
38.
Synthesis and spectral characterization of some complexes of platinum(II) containing η-methyleugenol
Several complexes of the formula trans-[Pt(Meug)(Am)Cl2], Meug: methyleugenol (4-allyl-1,2-dimethoxybenzene), a η2-coordinated olefin, and Am: ammine, methylamine, diethylamine, o-toluidine, m-toluidine, p-toluidine, o-anisidine, m-anisidine and p-anisidine have been prepared. UV, IR, Raman, 1H NMR, 13C NMR and 2D NMR spectra of the complexes were recorded and analyzed. 相似文献
39.
AbstractA simple, efficient, and metal-free methodology for the preparation of 2-mercaptobenzothiazole and derivatives in excellent yields via microwave-assisted pathway is reported. Our condition provides a convenient protocol for the synthesis of a diverse collection of 2-mercaptobenzothiazoles and 6-(4-substituted-1H-1,2,3-triazol-1-yl)-2-mercaptobenzothiazoles with a very simple purification process. This report provides an alternative protocol for fast access to the wide range of compounds for sequence synthesis and biological studies. 相似文献
40.
A. Serier J. P. Pascault Thanh My Lam 《Journal of polymer science. Part A, Polymer chemistry》1991,29(8):1125-1131
The hydrolysis and reactions of alkoxy silane groups have been studied on a model compound (TA) prepared from 2 mol of phenyl glycidyl ether and 1 mol of aminopropyl triethoxy silane. At low (40°C) and high (140°C) temperatures, the monomer conversion and the evolution of the molecular mass are followed by size exclusion chromatography (SEC). During the same reaction time, the evolution of the functional groups, hydroxyl CH? OH, ethoxy ? O? C2H5, and siloxane Si? O? Si, is observed by FTIR spectroscopy. Without the presence of water, reactions between hydroxyl and ethoxy silane lead to gelation at the end of the reaction. A by-product, probably a cyclic tetramer is also formed. After the hydrolysis, the reaction of the model compound is quite different. The product of reaction is always soluble, even after a treatment at high temperatures, and the evolution of the molecular mass versus the reaction time seems to correspond to the condensation giving a dead cyclic tetramer. From this study it is evident that the curing cycle has a great influence on the properties of the interface of a composite based on a epoxy matrix. 相似文献