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41.
Jesús M. Ruiz Gonzalez Marcos Loroo Tania Crdova Gabriel Chuchani 《Journal of Molecular Structure》2005,732(1-3):55-61
Møller-Plesset MP2/6-31G method was used to examine the gas-phase elimination of 2-substituted alkyl ethyl N,N-dimethylcarbamates. The results of these calculations support a concerted non-synchronous six-membered cyclic transition state mechanism for carbamates containing a Cβ–H bond at the alkyl side of the ester. These substrates produce the N,N-dimethylcarbamic acid and the corresponding olefin. The unstable intermediate, N,N-dimethylcarbamic acid, rapidly decomposes through a four-membered cyclic transition state to dimethylamine and CO2 gas. Correlation of the logarithm of theoretical rate coefficients against original Taft's σ* values gave an approximate straight line (ρ*=−1.39, r=0.9558 at 360 °C). In addition to this fact, when log krel is plotted against the theoretical log krel for 2-substituted ethyl N,N-dimethylcarbamates a reasonable straight line (r=0.9919 at 360 °C) is obtained, suggesting similar mechanism. 相似文献
42.
Valerie Autissier 《Journal of organometallic chemistry》2005,690(7):1763-1771
The complexes [Ni(η2-CH2C6H4R-4)(triphos)]BPh4 {R = H, Me or MeO; triphos = PhP(CH2CH2PPh2)2} have been prepared and characterised by spectroscopy and X-ray crystallography. In all cases the coordination geometry of the nickel is best described as square-planar with an η2-benzyl ligand occupying one of the positions. The orientation of the η2-benzyl ligand is dictated by the steric restrictions imposed by the phenyl groups on the triphos ligand, so that the phenyl group on the unique secondary phosphorus and the aromatic group of the benzyl ligand (which are trans to one another) are oriented in the same direction. [Ni(η2-CH2C6H4R-4)(triphos)]+ react with an excess of anhydrous HCl in MeCN to form [NiCl(triphos)]+ (characterised as the [BPh4]− salt by X-ray crystallography) and the corresponding substituted toluene. The kinetics of the reaction of all [Ni(η2-CH2C6H4R-4)(triphos)]+ and HCl in the presence of Cl− have been determined using stopped-flow spectrophotometry. All reactions exhibit a first-order dependence on the concentration of complex and a first-order dependence on the ratio [HCl]/[Cl−]. Varying the 4-R-substituent on the benzyl ligand shows that electron-withdrawing substituents facilitate the rate of the reaction. It is proposed that the mechanism involves initial rapid protonation at the nickel to form [NiH(η2-CH2C6H4R-4)(triphos)]2+, followed by intramolecular proton migration from nickel to carbon to yield the products. 相似文献
43.
Pedro J.?Silva Pedro A.?Fernandes Maria J.?RamosEmail author 《Theoretical chemistry accounts》2003,110(5):345-351
Prostaglandin H synthase catalyzes the oxygenation of arachidonic acid into the cyclic endoperoxide, prostaglandin G2 (PGG2), and the subsequent reduction of PGG2 to the corresponding alcohol, prostaglandin H2 (PGH2), the precursor of all prostaglandins and thromboxanes. Both radical abstraction by a neighboring tyrosyl radical and combined radical/carbocationic models have been proposed to explain the cyclooxygenase part of this reaction. We have used density functional theory calculations to study the mechanism of the formation of the cyclooxygenated product PGG2. We found an activation free energy for the initial hydrogen abstraction by the tyrosine radical of 15.6 kcal/mol, and of 14.5 kcal/mol for peroxo bridge formation, in remarkable agreement with the experimental value of 15.0 kcal/mol. Subsequent steps of the radical-based mechanism were found to happen with smaller barriers. A combined radical/carbocation mechanism proceeding through a sigmatropic hydrogen shift was ruled out, owing to its much larger activation free energy of 36.5 kcal/mol. Supplementary material is available in the online version of this article at http://dx.doi.org/10.1007/s00214-003-0476-9. Electronic Supplementary MaterialSupplementary material is available in the online version of this article at
Electronic Supplementary Material: Supplementary material is available in the online version of this article at 相似文献
44.
A highly efficient strategy for Cu(OTf)2 mediated SN2-type nucleophilic ring opening followed by [4+2] cycloaddition reactions of enantiopure 2-phenyl-N-tosylazetidines with various aldehydes and ketones afforded a variety of substituted 1,3-oxazinanes and 1,3-amino alcohols in excellent yields, excellent de and good to excellent ee. The proposed SN2-type mechanism of the cycloaddition reaction is supported by experimental evidence. 相似文献
45.
The mechanism for the 1,3-dipolar cycloaddition between the hindered thiocarbonyl ylide 1 and tetracyanoethylene 2 has been studied at the B3LYP/6-31G∗ level. Formation of the [3+2] cycloadduct 4 takes place through a stepwise mechanism that is initiated by the nucleophilic attack of the thiocarbonyl ylide 1 to the ethylene derivative 2 to give a zwitterionic intermediate IN. The subsequent cyclization of IN yields a seven-membered cyclic ketene imine 6, which equilibrates with the thermodynamically more stable [3+2] cycloadduct 4. The computed free energies are in agreement with the experimental outcomes. 相似文献
46.
Nianwei Yin 《European Polymer Journal》2005,41(6):1357-1372
A general kinetic model of particle formation in an ultrasonically initiated emulsion polymerization system is presented. This model takes into account homogeneous, micelle entry, and monomer droplet nucleation mechanism. The effects of the ultrasound in producing free radical, degrading free radical and influencing the fashion of the nucleation are also considered. Moreover, chain transfer to monomer and termination in the aqueous phase, capture of oligomer radicals by particles, and coagulation of particles are also considered. An analytical solution is obtained for the initial particle stage consideration. This model predicts that, if the desorption of radical from particles can be neglected, the concentration of the total radical in the aqueous phase is directly proportional to the cavitation concentration. Model predictions are in good agreement with experimental data obtained from the literature. 相似文献
47.
The kinetics of oxidation of allyl alcohol byN-bromosuccinimide (NBS) has been studied at 35 °C in aqueous medium. The reaction shows first order dependence on bothNBS and allyl alcohol. In fairly high acid concentration, there is no change in the rate of the reaction but at low acid concentration, the rate is considerably enhanced. There is no primary salt effect. At varying mercuric acetate concentrations, the rate constant remains the same. But in the absence of mercuric acetate, the rate is enhanced. The kinetic parameters,E
a,Arrhenius factorA, H, G and S have been calculated. A rate law in agreement with experimental results has been derived. A mechanism is proposed.
Kinetik und Mechanismus der Oxidation von Allylalkohol mixN-Bromsuccinimid
Zusammenfassung Die Kinetik der Oxidation von Allylalkohol mitN-Bromsuccinimid (NBS) wurde bei 35 °C in wäßrigem Medium untersucht. Die Reaktion zeigt erste Ordnung gegenüberNBS und Allylalkohol. Bei relativ hoher Säurekonzentration zeigt sich keine Änderung der Reaktionsgeschwindigkeit, bei niedriger Säurekonzentration wird die Reaktionsgeschwindigkeit beträchtlich erhöht. Es wurde kein primärer Salzeffekt festgestellt. Bei varriierender Quecksilberacetatkonzentration bleibt die Reaktionsgeschwindigkeit gleich, bei Abwesenheit von Quecksilberacetat wird jedoch die Geschwindigkeitskonstante erhöht. Die kinetischen Parameter,E a, derArrheniusfaktorA, H , G und S wurden bestimmt. Ein Geschwindigkeitsgesetz in Übereinstimmung mit den experimentellen Befunden wurde abgeleitet und ein Mechanismus vorgeschlagen.相似文献
48.
Sabry A. El-Korashy 《Monatshefte für Chemie / Chemical Monthly》2002,133(3):333-343
Summary. Solid crystalline calcium silicate hydrate (I) synthesized from equimolar amounts of Ca and Si under hydrothermal conditions
at 120°C shows cation exchange properties towards divalent metal cations such as Ni, Cu, Cd, or Hg. It also exhibits caesium
selectivity in the presence of Na+. The exchange capacity and selectivity of the solid can be increased by 10 and 28%, respectively, upon substitution of 0.01 mol
of the Ca2+ in its structure by Na+. The ability of metal cation uptake by the solid was found to obey the order Ni2+ > Hg2+ > Cu2+ > Cd2+. The different affinities of calcium silicate hydrate (I) towards these ions can be used for their separation from solutions
and also in nuclear waste treatment. The mechanism of the exchange reaction is discussed.
Received June 11, 2001. Accepted September 10, 2001 相似文献
49.
Anil K. Awasthi Santosh K. Upadhyay 《Monatshefte für Chemie / Chemical Monthly》1985,116(6-7):729-736
The kinetics of ruthenium(III) catalyzed oxidation of formaldehyde and acetaldehyde by alkaline hexacyanoferrate(III) has been studied spectrophotometrically. The rate of oxidation of formaldehyde is directly proportional to [Fe(CN)
3–
6
] while that of acetaldehyde is proportional tok[Fe(CN)
3–
6
]/{k +k[Fe(CN)
3–
6
]}, wherek, k andk are rate constants. The order of reaction in acetylaldehyde is unity while that in formaldehyde falls from 1 to 0. The rate of reaction is proportional to [Ru(III)]
T
in each case. A suitable mechanism is proposed and discussed.
Die Kinetik der Ru(III)-katalysierten Oxidation von Formaldehyd und Acetaldehyd mittels alkalischem Hexacyanoferrat(III)
Zusammenfassung Die Untersuchung der Kinetik erfolgte spektrophotometrisch. Die Geschwindigkeitskonstante der Oxidation von Formaldehyd ist direkt proportional zu [Fe(CN) 3– 6 ], währenddessen die entsprechende Konstante für Acetaldehyd proportional zuk[Fe(CN) 3– 6 ]/{k +k[Fe(CN) 3– 6 ]} ist, wobeik,k undk Geschwindigkeitskonstanten sind. Die Reaktionsordnung für Acetaldehyd ist eine erste, die für Formaldehyd fällt von erster bis zu nullter Ordnung. Die Geschwindigkeitskonstante ist in jedem Fall proportional zu [Ru(III)] T . Es wird ein passender Mechanismus vorgeschlagen.相似文献
50.
Trifluoromethylation of alkyl radicals is emerging as a powerful tool for C(sp3)–CF3 bond formations. Based on the hypothesis of CF3 group transfer from Cu(II)–CF3 to alkyl radicals, a number of trifluoromethylation reactions have been developed, including trifluoromethylation of alkyl halides, decarboxylative trifluoromethylation of aliphatic carboxylic acids, C(sp3)–H trifluoromethylation, amino‐ and carbo‐trifluoromethylation of alkenes, etc. Challenges in this intriguing field are also discussed. 相似文献