- Addition of Alcohol to Olefinic Bonds by Paired Electrosynthesis with Raney-Nickel Cathode
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A one-pot addition reaction of an alcohol to an olefinic double bond was successfully performed by use of paired electrosynthesis with a Raney-nickel cathode.
- Yamada, Tsukasa,Osa, Tetsuo,Matsue, Tomokazu
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- Dimethyl sulfite a potential agent for methylation
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The synthesis of methylated ether compounds is an important challenge. A pathway for the synthesis of methyl ethers was investigated using dimethyl sulfite (DMSi). Methylation of 1-octanol was carried out in liquid phase upon different heterogeneous organic and inorganic catalysts at 130°C. Aluminium oxide gave the best result with high conversion and moderate selectivity for methyl 1-octyl ether. Reactions in gas phase at higher temperatures (200°C) were also performed. Methyl 1-octyl ether was obtained in a very high level of selectivity up to 98%. Primary and secondary ethers from unsymmetrical alkyl methyl sulfite were also performed by SO2 extrusion.
- Mouselmani, Rim,Da Silva, Eric,Lemaire, Marc
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p. 8905 - 8910
(2015/11/02)
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- Effective Au(III)-CuCl2-catalyzed addition of alcohols to alkenes
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Alkenes can be activated by Au(III) catalysts, and the effective addition of alcohols to alkenes can be carried out under mild conditions with Au(III), provided that catalytic amounts of CuCl2 are added, which significantly stabilize the cationic Au(III). The Royal Society of Chemistry.
- Zhang, Xin,Corma, Avelino
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p. 3080 - 3082
(2008/02/10)
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- The multiphoton photochemistry of 2-iodooctane in methanol
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The laser-induced photochemistry of 2-iodooctane in methanol at 266 nm occurs exclusively by homolytic reactions. This is in contrast to the lamp-induced photochemistry which is largely ionic.
- Gao, Fang,Compton, Robert N.,Pagni, Richard M.
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p. 1584 - 1585
(2007/10/03)
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- Photochemistry of racemic and resolved 2-iodooctane. Effect of solvent polarity and viscosity on the chemistry
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The photochemistry of racemic and resolved 2-iodooctane was examined in cyclopentane, methanol, and 2-methyl-2-propanol, media with differing polarities and viscosities. The photochemistry of racemic 2-iodooctane was also examined in the gas phase. The photochemistry of 2-deuterio- and 1,1,1-trideuterio-2-iodooctane in cyclopentane and methanol was also studied. The photoreactions in cyclopentane, 2-methyl-2-propanol, and the gas phase occurred exclusively through homolytic reactions, while in methanol, they occurred predominantly (> 53%) through heterolytic reactions. By comparing the disappearance of the optically active substrate with its loss of optical activity, F, the fraction of the initially formed radical pair (RP) or ion pair (IP) resulting in product was determined for the three solvents. Because F contains contributions of both escape of the partners in the RP or IP into the bulk of the solvent and reaction within the RP or IP to yield products other than the substrate, there was no correlation between F and solvent viscosity. The F values will be valuable in assessing the photochemistry of 2-iodooctane in the same media with circularly polarized light.
- Gao, Fang,Boyles, David,Sullivan, Rodney,Compton, Robert N.,Pagni, Richard M.
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p. 9361 - 9367
(2007/10/03)
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- Kinetics and Mechanisms of Nucleophilic Displacement with Heterocycles as Leaving Groups. 17. Solvolysis of 14-(Primary alkyl)-5,6,8,9-tetrahydro-7-phenyldibenzoacridiniums: Rates, Identification of Products, Activation Parameters, and a General Discussion of Mechanism
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Solvolysis rate are reported for the Me, Et, n-Pr, n-Pent, n-Oct, i-Bu, neo-Pent, PhCH2CH2, and MeOCH2CH2 title compounds in MeOH, EtPH, PentOH, CH3CO2H, and CF3CO2H.Rate variations with alkyl group structure are far less than the corresponding rate variations for the tosylate solvolysis, and afford no evidence for rate-enhancing participation by β-phenyl or β-methoxy groups in the acridinium solvolyses.The n-propyl, n-pentyl, and n-octyl title compounds solvolyze in CH3OD and CH3CO2D to give mixtures of normal and rearranged products, none of which contain deuterium and which are therefore not formed via olefin intermediates.Methanolysis of the isobutyl title compounds occurs via olefin, but the acetolysis also involves an important nonolefinic pathway yielding isobutyl and sec-butyl acetates.Methanolysis products from the neopentyl derivative are heavily deuterated, but acetolysis yields undeuterated neopentyl acetate as well as deuterated tert-pentyl acetate.Product proportions calculated using GC/MS were used to deduce the fractions of reactions by various mechanistic pathways.Individual rates are calculated for solvolysis to the various unrearranged and rearranged products.They indicate that normal substitution in MeOH occurs by a classical SN2 reaction, but that such substitution in AcOH involves ion-pair intermediates.It is concluded that such ion pairs under go Me and H migration after the rate-determining stage, in competition with substitution.Activation parameters provide further evidence for the mechanistic paths proposed which are discussed in relation to literature data available for the corresponding tosylate.
- Katritzky, Alan R.,Dega-Szafran, Zofia,Lopez-Rodriguez, Maria L.,King, Roy W.
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p. 5577 - 5585
(2007/10/02)
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- Photochemistry of Alkyl Halides. 11. Competing Reaction via Carbene and Carbocationic Intermediates
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Isotopic analysis of the unsaturated products 6 and 15 resulting from irradiation of the labeled iodides 1-1,1-d2, 1-2,2-d2, and 13-1-d has revealed that they are formed substantially, but not exclusively, via α elimination.The unsaturated products thus arise via competing pathways involving carbene intermediates as well as the previously recognized radical and carbocationic intermediates.Irradiation of iodide 22 in methanol-d afforded ether 23 with partial incorporation of deuterium, but the accompanying ether 24 was formed with no detectable incorporation.Thus, ether 23 is formed via competing pathways involving the carbene 28 and the carbocation 25, whereas ether 24 is formed exclusively via the carbocationic pathway.A mechanism involving formation of the carbene intermediates via either α-hydrogen atom or α-proton transfer within the previously proposed intervening radical and ion pairs is suggested.One iodide studied, 17-2-d, exhibited no detectable α elimination.
- Kropp, Paul J.,Sawyer, Joy A.,Snyder, John J.
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p. 1583 - 1589
(2007/10/02)
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- Alkylations Using Methyltrialkoxyphosphonium Tetrafluoroborate Salts. Synthetic and Mechanistic Aspects of Methyl, Ethyl, 2-Propyl, and 2-Octyl Group Transfers
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Trialkyl phosphites, (RO)3P for R = methyl, ethyl, 2-propyl, and 2-octyl, were alkylated with Meerwein's salt (Me3O+BF4-) to yield the corresponding trialkoxymethylphosphonium tetrafluoroborate salts.These salts, which are all molten at room temperature, were reacted neat or in solvents with a series of nucleophiles.Thus, a variety of O, N, S, and halogen nucleophiles reacted by substitution at the R group C-O bond to give high yields after a trivial workup procedure.Rates of reaction were measured for substituted benzoic acids (4-XC6H4CO2H; X= CH3, t-Bu, CH3O, H, CF3, CN, NO2) with the neat salts under pseudo-first-order conditions or with the salt in CH3CN under second order conditions.The resulting Hammett plots indicate very little change in sensivity to the substituents when R = isopropyl compared with R = methyl and when the salt itself instead of CH3CN is solvent.
- Fry, Slaton E.,Pienta, Norbert J.
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p. 4877 - 4880
(2007/10/02)
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- Oxidative Displacement of Hypervalent Iodine from Alkyl Iodides
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Oxidative displacement of iodine from primary alkyl iodides and vic-substituted iodocyclohexanes with m-chloroperbenzoic acid in either dichloromethane or t-butyl alcohol-water gives primary alcohols and vic-substituted cyclohexanols, respectively.Retention of configuration at the displacement centre occurs for all of the trans-vic-substituted iodocyclohexanes except the iodoacetate and iodotrifluoroacetate where inversion of configuration occurs to give cis-hydroxy-esters.Oxidation of (S)-2-iodo-octane occurs with almost complete inversion to give (R)-octan-2-ol but also affords octan-1-ol, octan-3-ol, and octan-2-one.
- Cambie, Richard C.,Chambers, David,Lindsay, Barry G.,Rutledge, Peter S.,Woodgate, Paul D.
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p. 822 - 827
(2007/10/02)
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