123-05-7Relevant articles and documents
SELECTIVE TRIMERIZATION OF ALIPHATIC ALDEHYDES CATALYZED BY POLYNUCLEAR CARBONYLFERRATES
Ito, Keiji,Kamiyama, Nobuhiro,Nakanishi, Saburo,Otsuji, Yoshio
, p. 657 - 660 (1983)
Aliphatic aldehydes undergo a catalytic trimerization to give 1,3-diol monoesters upon treatment with Fe3(CO)12 in pyridine or with Fe3(CO)12-pyridine N-oxide in benzene.Polynuclear carbonylferrates serve as catalyst for this transformation.
Vapor-phase aldolization of n-butyraldehyde to 2-ethyl-2-hexenal over solid-base catalysts
Zhu, Wei-De,Ko, An-Nan
, p. 1237 - 1242 (2000)
Vapor-phase aldol condensation of n-butyraldehyde to 2-ethyl-2-hexenal was studied at 1 atm and 150~ 300°C in a fixed-bed, integral-flow reactor by using NaX, KX, γ-Al2O3 and Na/NaOH/γ-Al2O3 catalysts. Ion exchange of NaX zeolite with potassium acetate solution results in a decrease of crystallinity and apparent lowering of surface area, whereas the basic strength is enhanced. Treatment of γ-Al2O3 with NaOH and Na causes a large decrease of the surface area but strong enhancement of the catalyst basicity. The catalytic activity on the basis of unit surface area is in the order Na/NaOH/γ-Al2O3 > KXU > KXW > NaX>γ-Al2O3, in accordance with the relative catalyst basic strength. The molar ratio of trimeric to dimeric products increases with increasing the reaction temperature and the catalyst basic strength except for Na/NaOH/γ-Al2O3. Very high selectivity of 2-ethyl-2-hexenal (>98.5%) was observed for reactions over NaX zeolite at 150°C. Based on the FT-IR and the catalytic results, the reaction paths are proposed as follows: self-aldol condensation of n-butyraldehyde, followed by dehydration produces 2-ethyl-2-hexenal, which then reacts with n-butyraldehyde and successively dehydrates to 2,4-diethyl-2,4-octadienal and 1,3,5-triethylbenzene. For the reaction over NaX, the calculated Arrhenius frequency factor and activation energy are 314 mol/g-h and 32.6 kJ/mol, respectively.
Iron/ABNO-Catalyzed Aerobic Oxidation of Alcohols to Aldehydes and Ketones under Ambient Atmosphere
Wang, Lianyue,Shang, SenSen,Li, Guosong,Ren, Lanhui,Lv, Ying,Gao, Shuang
, p. 2189 - 2193 (2016)
We report a new Fe(NO3)3·9H2O/9-azabicyclo[3.3.1]nonan-N-oxyl catalyst system that enables efficient aerobic oxidation of a broad range of primary and secondary alcohols to the corresponding aldehydes and ketones at room temperature with ambient air as the oxidant. The catalyst system exhibits excellent activity and selectivity for primary aliphatic alcohol oxidation. This procedure can also be scaled up. Kinetic analysis demonstrates that C-H bond cleavage is the rate-determining step and that cationic species are involved in the reaction.
Enamines from terminal epoxides and hindered lithium amides
Hodgson, David M.,Bray, Christopher D.,Kindon, Nicholas D.
, p. 6870 - 6871 (2004)
A new reactivity mode of lithium amides with epoxides leads to hindered enamines. The reaction of some of these enamines with unactivated primary and secondary alkyl halides is described, which expands the range of electrophiles that one can use in the synthesis of mono-alkylated aldehydes. Copyright
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Curphey,T.J.,Chao-yu Hung,J.
, p. 510 (1967)
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Synthesis of renewable plasticizer alcohols by formal anti-Markovnikov hydration of terminal branched chain alkenes via a borane-free oxidation/reduction sequence
Harvey, Benjamin G.,Meylemans, Heather A.,Quintana, Roxanne L.
, p. 2450 - 2456 (2012)
An efficient method for the formal anti-Markovnikov hydration of 1,1-disubstituted alkenes has been developed. The utility of the process has been demonstrated by conversion of bio-derived butene oligomers into primary alcohols through initial oxidation to vicinal acetoxy-alcohols, diols, or diacetates, followed by selective dehydration/tautomerization of the diols, and hydrogenation of the intermediary aldehydes. This approach allows for the isolation of important industrial plasticizer alcohols from a renewable source. In a broader context, this pathway, which can be conducted with sustainable, conventional reagents under mild conditions, represents a unique alternative to hydroboration for a challenging subset of hindered olefins.
Oxidation of Primary Alcohols over Hydrous Zirconium(IV) Oxide
Kuno, Hideyuki,Shibagaki, Makoto,Takahashi, Kyoko,Matsushita, Hajime
, p. 312 - 314 (1991)
The oxidation of primary alcohols with quinone or benzophenone was carried out by catalysis with hydrous zirconium(IV) oxide in both batch and flow reaction systems.As a result, it was elucidated that a lot of primary alcohols can be efficiently oxidized over hydrous zirconium(IV) oxide.
Environmentally friendly approach to α-acyloxy carboxamides: Via a chemoenzymatic cascade
Paprocki, Daniel,Koszelewski, Dominik,Zad?o, Anna,Walde, Peter,Ostaszewski, Ryszard
, p. 68231 - 68237 (2016)
A new, green route for the synthesis of α-acyloxy carboxamides from an alcohol, a carboxylic acid and an isocyanide was developed. The reaction comprises the aerobic oxidation of an alcohol to the corresponding aldehyde, catalyzed by the Trametes versicolor laccase/TEMPO system, followed by a one pot Passerini reaction in an aqueous surfactant medium. The influence of different types of surfactants on the reaction efficiency was investigated. The best results were obtained by employing dioctadecyldimethylammonium bromide (DODAB), a known vesicle-forming cationic surfactant. Importantly, apart from the metalloenzyme used, the described procedure toward α-acyloxy carboxamides is metal-free and does not require hazardous organic solvents, what makes it environmentally friendly.
Effects of carboxylic acid adsorbates on CO adsorption and crotonaldehyde hydrogenation over Cu/Al2O3 catalyst
Rochester,Bailie,Richardson,Abdullah,Hutchings,Anderson
, p. 3925 - 3932 (2000)
A study was performed to determine how the adsorption of carboxylic acids (formic or acetic acid) would influence the surface character of alumina-supported Cu catalysts. IR spectra of adsorbed CO were used to probe the effect of the carboxylic acids on exposed Cu sites. The hydrogenation of crotonaldehyde was used as a test-reaction for catalytic behavior since it showed that surface modification of oxide-supported Cu catalysts with heterocyclic dopants may result in enhancements in selectivity to crotyl alcohol. Formic acid adsorption on reduced Cu0 sites generated adsorbed bidentate formate which blocked CO adsorption at many sites, induced cationic character at the remaining available sites, and partially poisoned hydrogenation reactions. Modification of the surface poisoned C=O hydrogenation more than C=C hydrogenation and promoted butanal as the main hydrogenation product. Desorption of formate by ″flashing″ at high temperature led to a partly reconstructed surface which yielded higher catalytic activities than an unmodified surface before formic acid treatment. The effects of acetic acid adsorption were similar to those for formic acid except that attempts at desorption of the modifier led to carbonaceous residues which partially poisoned CO adsorption and catalytic activity.
Oxidation of alcohol by lipopathic Cr(VI): A mechanistic study
Patel, Sabita,Mishra
, p. 6759 - 6766 (2006)
The oxidation kinetics of various aliphatic primary and secondary alcohols having varied hydrocarbon chain length were studied using cetyltrimethylammonium dichromate (CTADC) in dichloromethane (DCM) in the presence of acetic acid and in the presence of a cationic surfactant. The rate of the reaction is highly sensitive to the change in [CTADC], [alcohol], [acid], [surfactant], polarity of the solvents, and reaction temperature. A Michaelis-Menten type kinetics was observed with respect to substrate. The chemical nature of the intermediate and the reaction mechanism were proposed on the basis of (i) observed rate constant dependencies on the reactants, that is, fractional order with respect to alcohol and acid and a negative order with respect to oxidant, (ii) high negative entropy change, (iii) inverse solvent kinetic isotope effect, k(H 2O)/k(D2O) = 0.76, (iv) low primary kinetic isotope effect, kH/kD = 2.81, and (v) the kobs dependencies on solvent polarity parameters. The observed experimental data suggested the self-aggregation of CTADC giving rise to a reverse micellar system akin to an enzymatic environment, and the proposed mechanism involves the following: (i) formation of a complex between alcohol and the protonated dichromate in a rapid equilibrium, equilibrium constant K = 5.13 (±0.07) dm3 mol-1, and (ii) rate determining decomposition (k 2 = (7.6 ± 0.7) × 10-3 s-1) of the ester intermediate to the corresponding carbonyl compound. The effect of [surfactant] on the rate constant and the correlation of solvent parameters with the rate constants support the contribution of hydrophobic environment to the reaction mechanism.
A Kinetic Study of 2-Ethyl-1-hexanol Oxidation by Dichromate Using Clay-Supported 1-Butyl 4-aza-1-azonia Bicyclo[2.2.2]octane Chloride as the Phase-Transfer Catalyst
Ghiaci,Kalbasi,Sedaghat
, p. 936 - 938 (2003)
Selective oxidation of primary alcohols to aldehydes is a long-standing problem of organic chemistry (Bueler, C. A.; Pearson, D. E. Survey of Organic Synthesis; Wiley-Interscience: New York, 1977; Vol. 2, p 480; House, H. O. Modern Synthetic Reactions, 2nd. ed.; W. A. Benjamin: Menlo Park, California, 1972; p 257; Epstein, W. W.; Sweet, F. W. Chem. Rev. 1967, 67, 247; Landini, D. ; Montanari, F.; Rolla, F. Synthesis 1979, 134). The use of potassium dichromate as a synthetically useful oxidizing agent is reported for the oxidation of an industrially important lipophilic alcohol, employing modified clay as the phase-transfer catalyst. The phase-transfer catalysis results in nearly complete oxidation of the 2-ethylhexanol in 40 min at room temperature, with high selectivity to the 2-ethylhexanal, compared to 48 h in its absence. Kinetic studies show the reaction occurs via transfer of Cr2O 72- into the organic phase. The emphasis will be on simplicity of the condition as a preparative organic method, selectivity with regard to over-oxidation, efficiency, and mildness of conditions.
Preparation and catalytic performance of NiO-MnO2/Nb2O5-TiO2 for one-step synthesis of 2-ethylhexanol from n-butyraldehyde
An, Hualiang,Li, Sibo,Wang, Yanji,Zhang, Jiaxun,Zhao, Xinqiang
, (2020/12/02)
One-pot synthesis of 2-ethylhexanol(2EHO) from n-butyraldehyde is of commercialimportance. The promotion of 2EHO selectivity requires suppressing direct hydrogenation of n-butyraldehyde. In this work, a series of NiO-MOx/Nb2O5-TiO2 catalysts were prepared and utilized by means of reduction-in-reaction technique, aiming at delaying the formation of metal sites and suppressing the direct hydrogenation. NiO-MnO2/Nb2O5-TiO2 with a Ni/Mn mass ratio of 10 and NiO-MnO2 loading of 14.3 wt% shows the best catalytic performance; 2-EHO selectivity could reach 90.0% at a complete conversion of n-butyraldehyde. Furthermore the catalyst could be used for four times without a substantial change in its catalytic performance.
Practical catalytic nitration directly with commercial nitric acid for the preparation of aliphatic nitroesters
An, Jichao,He, Pan,Li, Wenhao,Liu, Peipei,Si, Mengyuan,Yang, Bo,Yang, Guanyu
, p. 6612 - 6616 (2020/09/21)
To pursue a sustainable and efficient approach for aliphatic nitroester preparation from alcohol, europium-triflate-catalyzed nitration, which directly uses commercial nitric acid, has been successfully developed. Gram scalability with operational ease showed its practicability.