112-41-4Relevant academic research and scientific papers
Formal hydrochromination of alkynes under nickel catalysis. Regioselective reductive coupling of alkynes and aldehydes leading to allylic alcohols
Takai, Kazuhiko,Sakamoto, Shuji,Isshiki, Takahiko,Kokumai, Tatsuya
, p. 7534 - 7539 (2006)
Formal hydrochromation of an alkyne leading to a 1-substituted ethenylchromium reagent is accomplished by addition of the alkyne and water to a mixture of low-valent chromium(II), a catalytic amount of nickel(II), and triphenylphosphine in DMF.
Effect of Alcohol Structure on the Kinetics of Etherification and Dehydration over Tungstated Zirconia
Rorrer, Julie,Pindi, Suresh,Toste, F. Dean,Bell, Alexis T.
, p. 3104 - 3111 (2018)
Linear and branched ether molecules have attracted recent interest as diesel additives and lubricants that can be produced from biomass-derived alcohols. In this study, tungstated zirconia was identified as a selective and green solid acid catalyst for the direct etherification of primary alcohols in the liquid phase, achieving ether selectivities of >94 % for C6–C12 linear alcohol coupling at 393 K. The length of linear primary alcohols (C6–C12) was shown to have a negligible effect on apparent activation energies for etherification and dehydration, demonstrating the possibility to produce both symmetrical and asymmetrical linear ethers. Reactions over a series of C6 alcohols with varying methyl branch positions indicated that substituted alcohols (2°, 3°) and alcohols with branches on the β-carbon readily undergo dehydration, but alcohols with branches at least three carbons away from the -OH group are highly selective to ether. A novel model compound, 4-hexyl-1dodecanol, was synthesized and tested to further demonstrate this structure–activity relationship. Trends in the effects of alcohol structure on selectivity were consistent with previously proposed mechanisms for etherification and dehydration, and help to define possible pathways to selectively form ethers from biomass-derived alcohols.
A new method for the preparation of olefins from vicinal diols
Adiyaman, Mustafa,Jung, Young-Ju,Kim, Seongjin,Saha, Goutam,Powell, William S.,FitzGerald, Garret A.,Rokach, Joshua
, p. 4019 - 4022 (1999)
A novel method is reported for the transformation of vicinal diols to olefins. This methodology consists in the conversion of iodothiocarbonates such as 16 to olefin 17 with phenyl lithium in excellent yield. Compounds 7 and 12 were prepared by this methodology in order to determine if they would be recognized by the enzymes, 5-lipoxygenase and 15-lipoxygenase, respectively.
Terminal olefins from aldehydes through enol triflate reduction
Pandey, Sushil K.,Greene, Andrew E.,Poisson, Jean-Francois
, p. 7769 - 7770 (2007)
(Chemical Equation Presented) The transformation of aldehydes into terminal olefins through reduction of the corresponding enol triflates is described. The method is effective with both linear and α-branched aldehydes.
Calcium Fluoride-supported Alkali Metal Fluorides. New Reagents for Nucleophilic Fluorine Transfer Reactions
Clark, James H.,Hyde, Andrew J.,Smith, David K.
, p. 791 - 793 (1986)
The reactivity of the alkali metal fluorides KF and CsF as sources of nucleophilic fluorine is appreciably enhanced by the presence of calcium fluoride and in particular by the use of the supported reagents KF-CaF2 and CsF-CaF2.
AN IMPROVED METHOD FOR OLEFIN SYNTHESIS USING PYRIDYLSELENO GROUP AS A LEAVING GROUP
Toshimitsu, Akio,Owada, Hiroto,Uemura, Sakae,Okano, Masaya
, p. 5037 - 5038 (1980)
Alkyl pyridyl selenides are oxidized by 1.5 equiv. of 30percent H2O2 in THF to give olefins in good to excellent yields.The yields are always higher than the case where alkyl phenyl selenides are used under the same conditions.
Reaction of lithium diethylamide with an alkyl bromide and alkyl benzenesulfonate: Origins of alkylation, elimination, and sulfonation
Gupta, Lekha,Ramirez, Antonio,Collum, David B.
, p. 8392 - 8399 (2010)
A combination of NMR, kinetic, and computational methods are used to examine reactions of lithium diethylamide in tetrahydrofuran (THF) with n-dodecyl bromide and n-octyl benzenesulfonate. The alkyl bromide undergoes competitive SN2 substitution and E2 elimination in proportions independent of all concentrations except for a minor medium effect. Rate studies show that both reactions occur via trisolvated-monomer-based transition structures. The alkyl benzenesulfonate undergoes competitive SN2 substitution (minor) and N-sulfonation (major) with N-sulfonation promoted at low THF concentrations. The SN2 substitution is shown to proceed via a disolvated monomer suggested computationally to involve a cyclic transition structure. The dominant N-sulfonation follows a disolvated-dimer-based transition structure suggested computationally to be a bicyclo[3.1.1] form. The differing THF and lithium diethylamide orders for the two reactions explain the observed concentration-dependent chemoselectivities.
Synthesis of amphiphilic thiatrimethinecyanines
Orlova,Kolchina,Shakirov,Gerasimova,Shelkovnikov
, p. 228 - 231 (2004)
Preparation conditions were optimized for 2-methyl-5-chlorobenzothiazolium quaternary salts with long-chain N-alkyl substituents (C12H 25, C15H31, C18H37). They were used in the synthesis of thiatrimethinecyanines conteining in the meso-position phenyl, p-chlorophenyl, or p-fluorophenyl groups.
A ZIRCONIUM-PROMOTED METHYLENATION OF ALDEHYDES, KETONES, AND ENONES
Tour, James M.,Bedworth, Peter V.,Wu, Ruilian
, p. 3927 - 3930 (1989)
Treatment of zirconocene dichloride with dibromomethane and zinc affords an organometallic intermediate which rapidly methylenates aldehydes, ketones, and enones at room temperature.
SmI2-Induced Deoxygenation of Epoxides and Its Application to Carbonyl Methylenation in Combination with Iodomethylation
Matsukawa, Mihaya,Tabuchi, Takanori,Inanaga, Junji,Yamaguchi, Masaru
, p. 2101 - 2102 (1987)
Deoxygenation of epoxides to olefins was effected by an efficient electron transfer system of SmI2-THF-HMPA in the presence of N,N-dimethylaminoethanol (DMAE) or glutaric anhydride.This procedure, in combination with the SmI2-induced iodomethylation, afforded a new, rapid and mild one-pot carbonyl methylenation method.
