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Unsaturated Hydrocarbons (unsaturated + hydrocarbon)
Selected AbstractsChemInform Abstract: Nickel-Catalyzed Cycloadditions of Unsaturated Hydrocarbons, Aldehydes, and Ketones.CHEMINFORM, Issue 32 2008Thomas N. Tekavec Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Synthesis of ,-Amino Acid Derivatives by Nickel(0)-Mediated Sequential Addition of Carbon Dioxide and Dibenzoyldiazene onto Unsaturated Hydrocarbons.CHEMINFORM, Issue 32 2007Masahiro Murakami Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Nickel-Catalyzed Cycloaddition of Unsaturated Hydrocarbons and Carbonyl Compounds.CHEMINFORM, Issue 1 2006Thomas N. Tekevac No abstract is available for this article. [source] Fine Patterning of Hybrid Titania Films by Ultraviolet IrradiationJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 5 2003Hiyoro Segawa Photosensitive hybrid titania films have been prepared from titanium butoxide modified with ,-diketone and methacrylic acid. When this film is exposed to UV light, the ,-diketonato chelate from the alkoxide and ,-diketone is dissociated, and the unsaturated hydrocarbon of methacrylic acid is polymerized. These structural changes in the gel film have led to a difference between the solubility of irradiated and unirradiated parts in the film; therefore, a fine patternable hybrid titania film has been fabricated. [source] Rate coefficients and mechanisms of the reaction of cl-atoms with a series of unsaturated hydrocarbons under atmospheric conditionsINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 8 2003John J. Orlando Rate coefficients and/or mechanistic information are provided for the reaction of Cl-atoms with a number of unsaturated species, including isoprene, methacrolein (MACR), methyl vinyl ketone (MVK), 1,3-butadiene, trans -2-butene, and 1-butene. The following Cl-atom rate coefficients were obtained at 298 K near 1 atm total pressure: k(isoprene) = (4.3 ± 0.6) × 10,10cm3 molecule,1 s,1 (independent of pressure from 6.2 to 760 Torr); k(MVK) = (2.2 ± 0.3) × 10,10 cm3 molecule,1 s,1; k(MACR) = (2.4 ± 0.3) × 10,10 cm3 molecule,1 s,1; k(trans -2-butene) = (4.0 ± 0.5) × 10,10 cm3 molecule,1 s,1; k(1-butene) = (3.0 ± 0.4) × 10,10 cm3 molecule,1 s,1. Products observed in the Cl-atom-initiated oxidation of the unsaturated species at 298 K in 1 atm air are as follows (with % molar yields in parentheses): CH2O (9.5 ± 1.0%), HCOCl (5.1 ± 0.7%), and 1-chloro-3-methyl-3-buten-2-one (CMBO, not quantified) from isoprene; chloroacetaldehyde (75 ± 8%), CO2 (58 ± 5%), CH2O (47 ± 7%), CH3OH (8%), HCOCl (7 ± 1%), and peracetic acid (6%) from MVK; CO (52 ± 4%), chloroacetone (42 ± 5%), CO2 (23 ± 2%), CH2O (18 ± 2%), and HCOCl (5%) from MACR; CH2O (7 ± 1%), HCOCl (3%), acrolein (,3%), and 4-chlorocrotonaldehyde (CCA, not quantified) from 1,3-butadiene; CH3CHO (22 ± 3%), CO2 (13 ± 2%), 3-chloro-2-butanone (13 ± 4%), CH2O (7.6 ± 1.1%), and CH3OH (1.8 ± 0.6%) from trans -2-butene; and chloroacetaldehyde (20 ± 3%), CH2O (7 ± 1%), CO2 (4 ± 1%), and HCOCl (4 ± 1%) from 1-butene. Product yields from both trans -2-butene and 1-butene were found to be O2 -dependent. In the case of trans -2-butene, the observed O2 -dependence is the result of a competition between unimolecular decomposition of the CH3CH(Cl)CH(O,)CH3 radical and its reaction with O2, with kdecomp/kO2 = (1.6 ± 0.4) × 1019 molecule cm,3. The activation energy for decomposition is estimated at 11.5 ± 1.5 kcal mol,1. The variation of the product yields with O2 in the case of 1-butene results from similar competitive reaction pathways for the two ,-chlorobutoxy radicals involved in the oxidation, ClCH2CH(O,)CH2CH3 and ,OCH2CHClCH2CH3. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 334,353, 2003 [source] Energetic and topological analysis of the reaction of Mo and Mo2 with NH3, C2H2, and C2H4 moleculesJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 13 2004Maria Del Carmen Michelini Abstract The Density functional theory has been applied to characterize the structural features of Mo1,2NH3,C2H4, and C2H2 compounds. Coordination modes, geometrical structures, and binding energies have been calculated for several spin multiplets. It has been shown that in contrast to the conserved spin cases (Mo1,2NH3), the interaction between Mo (or Mo2) and C2H4 (or C2H2) are the low-spin (MoC2H4 and C2H2) and high-spin (Mo2C2H4 and C2H2) complexes. In the ground state of Mo1,2C2H4 and C2H2, the metal-center always reacts with the CC center. The spontaneous formation of the global minima is found to be possible due to the crossing between the potential energy surfaces (ground and excited states with respect to the metallic center). The bonding characterization has been performed using the topological analysis of the Electron Localization Function. It has been shown that the most stable electronic structure for a ,-acceptor ligand correlates with a maximum charge transfer from the metal center to the CC bond of the unsaturated hydrocarbons, resulting in the formation of two new basins located on the carbon atoms (away from hydrogen atoms) and the reduction of the number of attractors of the CC basin. The interaction between Mo1,2 and C2H4 (or C2H2) should be considered as a chemical reaction, which causes the multiplicity change. Contrarily, there is no charge transfer between Mo1,2 and NH3, and the partners are bound by an electrostatic interaction. © 2004 Wiley Periodicals, Inc. J Comput Chem 25: 1647,1655, 2004 [source] Theoretical approach to the mechanism of reactions between halogen atoms and unsaturated hydrocarbons: The Cl + propene reactionJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 16 2003Pedro Braña Abstract The potential energy surface for the Cl + propene reaction was analyzed at the MP2 level using Pople's 6-31G(d,p) and 6-311+G(d,p), and Dunning's cc-pVDZ and aug-cc-pVDZ basis sets. Two different channels for the addition reaction leading to chloroalkyl radicals and five alternative channels for the abstraction reaction leading to C3H + HCl were explored. The corresponding energy profiles were computed at the QCISD(T)/aug-cc-pVDZ//MP2/aug-cc-pVDZ level of theory. Theoretical results suggest that the previously established mechanism consisting of (1) direct abstraction and (2) addition,elimination steps is instead made up of (1) addition through an intermediate and (2) two-step abstraction processes. No direct abstraction mechanism exists on the potential energy surface. The kinetic equations derived for the new mechanism are consistent with the pressure dependence experimentally observed for this reaction. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 2044,2062, 2003 [source] Cubic-plus-association equation of state for water-containing mixtures: Is "cross association" necessary?AICHE JOURNAL, Issue 7 2009Zhidong Li Abstract We have recently proposed an accurate version of the cubic-plus-association (CPA) equation of state (EOS) for water-containing mixtures which combines the Peng-Robinson equation (PR) for the physical interactions and the thermodynamic perturbation theory for the hydrogen bonding of water molecules. Despite the significant improvement, the water composition in the nonaqueous phase is systematically underestimated for some systems where the nonwater species are methane and ethane at very high pressures, unsaturated hydrocarbons, CO2, and H2S. We attribute the deficiency to the neglect of the "cross association" between water and those nonwater molecules. In this work, the accuracy is drastically improved by treating methane, ethane, unsaturated hydrocarbons, CO2 and H2S as "pseudo-associating" components and describing the cross association with water in the framework of the perturbation theory. It is shown that the cross association is more significant for the nonaqueous phase. In addition to binary mixtures, reliable predictions are achieved for H2O/C1/CO2/H2S quaternary mixture in two and three phases. © 2009 American Institute of Chemical Engineers AIChE J, 2009 [source] Isotope analysis of hydrocarbons: trapping, recovering and archiving hydrocarbons and halocarbons separated from ambient airRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 4 2005M. Pupek It is argued that isotope analysis of atmospheric non-methane hydrocarbons (NMHCs) and, in particular, the analysis of the deuterium/hydrogen (D/H) ratio is valuable because the dominant self-cleansing property of the troposphere is based on the OH radical which removes, e.g., CH4 and other alkanes by H-atom abstraction, which induces large kinetic isotope effects. The major obstacle in applying D/H isotope analysis to atmospheric NMHCs is not only the low abundance of D itself but, in particular, the low concentrations of NMHCs in the parts per trillion range. We show how a selection of NMHCs can be quantitatively separated from 300,L air samples together with CO2 as carrier gas matrix, by using high efficiency cryogenic traps. After diluting the extracted NMHC mixtures with hydrocarbon free air, and determining the mixing ratios, good agreement with original whole air sample analysis exists for alkanes and several halocarbons. For unsaturated hydrocarbons and some other halocarbons the extraction and recovery yield under the given conditions fell considerably, as a function of boiling point. Furthermore, the mixture of NMHCs in the CO2 matrix is proven to remain unchanged over several years when conveniently stored in glass ampoules. The ,extracts' or ,concentrates' of condensables extracted from larger air samples will enable the D/H isotope analysis of ultra trace gases in the atmosphere. Copyright © 2005 John Wiley & Sons, Ltd. [source] Myrcene as a Natural Base Chemical in Sustainable Chemistry: A Critical ReviewCHEMSUSCHEM CHEMISTRY AND SUSTAINABILITY, ENERGY & MATERIALS, Issue 12 2009Arno Behr Prof. Abstract Currently, a shift towards chemical products derived from renewable, biological feedstocks is observed more and more. However, substantial differences with traditional feedstocks, such as their "hyperfunctionalization," ethical problems caused by competition with foods, and problems with a constant qualitative/quantitative availability of the natural products, occasionally complicate the large-scale market entry of renewable resources. In this context the vast family of terpenes is often not taken into consideration, although the terpenes have been known for hundreds of years as components of essential oils obtained from leaves, flowers, and fruits of many plants. The simple acyclic monoterpenes, particularly the industrially available myrcene, provide a classical chemistry similar to unsaturated hydrocarbons already known from oil and gas. Hence, this Review is aimed at reviving myrcene as a renewable compound suitable for sustainable chemistry in the area of fine chemicals. The versatility of the unsaturated C10 -hydrocarbon myrcene, leading to products with several different areas of application, is pointed out. [source] | ||||||||||