1192-18-3Relevant articles and documents
EVIDENCE FOR A SINGLE ELECTRON TRANSFER MECHANISM IN REACTIONS OF LITHIUM DIORGANOCUPRATES WITH ORGANIC HALIDES
Ashby, E. C.,DePriest, R. N.,Tuncay, A.,Srivastava, Sushil
, p. 5251 - 5254 (1982)
It has been demonstrated by means of spectroscopic studies involving cyclizable alkyl halides that lithium dimethylcuprate can react with organic halides by a single electron transfer pathway.
CONCERNING THE REDUCTION OF ALKYL HALIDES BY LiAlH4. EVIDENCE THAT AlH3 PRODUCED IN SITU IS THE ONE ELECTRON TRANSFER AGENT.
Ashby, E. C.,DePriest, R. N.,Pham, T. N.
, p. 2825 - 2828 (1983)
The reduction of 10 and 20 alkyl iodides by LiAlH4 has been shown to involve a radical intermediate formed by the reaction of the alkyl iodide with the AlH3 and LiI produced in situ in conjunction with LiAlH4 rather than by LiAlH4 alone, as evidenced by cyclized products in the reduction of 6-iodo-1-heptene, by the trapping of the radical and by stereochemical studies of the 2-halooctanes.
Cyclization of (1-Methyl-5-hexenyl)sodium in Ethers
Garst, John F.,Hines, John B.
, p. 6443 - 6445 (1984)
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Evidence for Inversion of Configuration in Reactions Involving Radical Processes
Ashby, E. C.,DePriest, Robert
, p. 6144 - 6146 (1982)
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A novel reduction of polycarboxylic acids into their corresponding alkanes using n-butylsilane or diethylsilane as the reducing agent
Nimmagadda, Rama D.,McRae, Christopher
, p. 3505 - 3508 (2006)
A convenient one-pot reaction has been developed for the reduction of polycarboxylic acids on aliphatic and aromatic systems to their corresponding alkanes. The reduction utilises either diethylsilane or n-butylsilane as the reducing agent in the presence of the Lewis acid catalyst tris(pentafluorophenyl)borane.
Rate Constants and Arrhenius Parameters for the Reactions of Some Carbon-Centered Radicals with Tris(trimethylsilyl)silane
Chatgilialoglu, C.,Dickhaut, J.,Giese, B.
, p. 6399 - 6403 (1991)
Rate constants for the reactions of some carbon-centered radicals with (Me3Si)3SiH have been measured over a range of temperatures by using competing unimolecular radical reactions as timing devices.For example, the rate constants (at 298 K) are 3.7, 1.4, and 2.6 x 1E5 M-1 s-1 from primary, secondary, and tertiary alkyl radicals, respectively.Comparison of the radical trapping abilities of tri-n-butylstannane and tris(trimethylsilyl)silane is discussed.The use of 1,1-dimethyl-5-hexenyl cyclization as a radical clock has been recalibrated by using new data and data from the literature.
Insights into the Major Reaction Pathways of Vapor-Phase Hydrodeoxygenation of m-Cresol on a Pt/HBeta Catalyst
Sun, Qianqian,Chen, Guanyi,Wang, Hua,Liu, Xiao,Han, Jinyu,Ge, Qingfeng,Zhu, Xinli
, p. 551 - 561 (2016/02/20)
Conversion of m-cresol was studied on a Pt/HBeta catalyst at 225-350°C and ambient hydrogen pressure. At 250°C, the reaction proceeds through two major reaction pathways: (1) direct deoxygenation to toluene (DDO path); (2) hydrogenation of m-cresol to methylcyclohexanone and methylcyclohexanol on Pt, followed by fast dehydration on Br?nsted acid sites (BAS) to methylcyclohexene, which is either hydrogenated to methylcyclohexane on Pt or ring-contracted to dimethylcyclopentanes and ethylcyclopentane on BAS (HYD path). The initial hydrogenation is the rate-determining step of the HYD path as its rate is significantly lower than those of subsequent steps. The apparent activation energy of the DDO path is 49.7 kJ mol-1 but the activation energy is negative for the HYD path. Therefore, higher temperatures lead to the DDO path becoming the dominant path to toluene, whereas the HYD path, followed by fast equilibration to toluene, is less dominant, owing to the inhibition of the initial hydrogenation of m-cresol.
Avoiding olefin isomerization during decyanation of alkylcyano α,ω-dienes: A deuterium labeling and structural study of mechanism
Rojas, Giovanni,Wagener, Kenneth B.
, p. 4962 - 4970 (2008/12/20)
(Chemical Equation Presented) A two-step synthetic pathway involving decyanation chemistry for the synthesis of pure alkyl α,ω-dienes in quantitative yields is presented. Prior methodologies for the preparation of such compounds required 6-9 steps, sometimes leading to product mixtures resulting from olefin isomerization chemistry. This isomerization chemistry has been eliminated. Deuteration labeling and structural mechanistic investigations were completed to decipher this chemistry. Deuterium labeling experiments reveal the precise nature of this radical decyanation chemistry, where an alcohol plays the role of hydrogen donor. The correct molecular design to avoid competing intramolecular cyclization, and the necessary reaction conditions to avoid olefin isomerization during the decyanation process are reported herein.
