3592-47-0Relevant articles and documents
Selective photocatalytic oxidation of benzyl alcohol and its derivatives into corresponding aldehydes by molecular oxygen on titanium dioxide under visible light irradiation
Higashimoto, Shinya,Kitao, Naoya,Yoshida, Norio,Sakura, Teruki,Azuma, Masashi,Ohue, Hiroyoshi,Sakata, Yoshihisa
, p. 279 - 285 (2009)
The photocatalytic oxidation of benzyl alcohol and its derivatives, such as 4-methoxybenzyl alcohol, 4-chlorobenzyl alcohol, 4-nitrobenzyl alcohol, 4-methylbenzyl alcohol, 4-(trifluoromethyl)benzyl alcohol, and 4-tertiary-butylbenzyl alcohol, into corresp
Regiospecific and Enantioselective Arylvinylcarbene Insertion of a C-H Bond of Aniline Derivatives Enabled by a Rh(I)-Diene Catalyst
Zhu, Dong-Xing,Xia, Hui,Liu, Jian-Guo,Chung, Lung Wa,Xu, Ming-Hua
, p. 2608 - 2619 (2021)
Asymmetric insertion of an arylvinylcarbenoid into the C-H bond for direct enantioselective C(sp2)-H functionalization of aniline derivatives catalyzed by a rhodium(I)-diene complex was developed for the first time. The reaction occurred exclusively at th
Kinetic study of 2-propanol and benzyl alcohol oxidation by alkaline hexacyanoferrate (III) catalyzed by a terpyridyl ruthenium complex
Kelson, Eric P.,Phengsy, Proma P.
, p. 760 - 770 (2000)
The complex (Trpy)RuCl3 (Trpy = 2,2′:6′,2″-terpyridine) reacts with alkaline hexacyanoferrate(III) to form a terpyridyl ruthenium(IV)-oxo complex that catalyzes the oxidation of 2-propanol and benzyl alcohol by alkaline hexacyanoferrate(III). The reaction kinetics of this catalytic oxidation have been studied photometrically. The reaction rate shows a first-order dependence on [Ru(IV)], a zero-order dependence on [hexacyanoferrate(III)], a fractional order in [substrate], and a fractional inverse order in [HO-]. The kinetic data suggest a reaction mechanism in which the catalytic species and its protonated form oxidize the uncoordinated alcohol in parallel slow steps. Isotope effects, substituent effects, and product studies suggest that both species oxidize alcohol through similar pericyclic processes. The reduced catalytic intermediates react rapidly with hexacyanoferrate(III) and hydroxide to reform the unprotonated catalytic species.
Outer-sphere reduction of hexacyanoferrate(III) by enolizable and nonenolizable aldehydes in alkaline medium
Bera, Ashok K.,Pal, Biswajit,Sen Gupta, Kalyan K.
, p. 494 - 505 (2012)
Outer-sphere reduction of hexacyanoferrate(III) by some enolizable/nonenolizable aldehydes (viz., aliphatic, heterocyclic, and aromatic aldehydes) in alkaline medium has been studied spectrophotometrically at λmax = 420 nm. The reactions are first order each in [aldehyde] and [Fe(CN)63-]. The rate increases with an increase in [OH-] in the oxidation of aliphatic and heterocyclic aldehydes, whereas it is independent of [OH-] in the reaction with aromatic aldehydes. The intervention of free radicals in the reaction mixture was carried out using both acrylonitrile and acrylamide scavenger in two different experiments. The kinetic results indicate that the oxidation of benzaldehyde in aqueous medium proceeds at a slower rate than the aliphatic aldehydes (other than formaldehyde) and furfural. The values of third-order rate constant (k3) at 308 K in the oxidations of some aliphatic aldehydes and furfural follow the order (CH3)2CH- > CH 3CH2- > CH3- > C4H 3O- > H-. The rate constants correlate with Taft's σ* value, the reaction constant being negative (-9.8). The pseudo-first-order rate constants in the oxidations of benzaldehyde and substituted benzaldehydes follow the order -NO2 > -H > -Cl > -OCH3. The Hammett plot is also linear with a ρ value (0.6488) for meta- and para-substituted benzaldehydes. The kinetic isotope effect for benzaldehyde (kH/k D = 1.93 at 303 K) was obtained. The rate-determining step is the outer-sphere formation of Fe(CN)64- and free radicals, which is followed by the rapid oxidation of free radicals by Fe(CN) 63- to give products. The kinetic data and hence thermodynamic parameters have been used to distinguish enolizable and nonenolizable aldehydes. An attempt has also been made to correlate kinetic data with hydration equilibrium constants of some aliphatic aldehydes. Copyright
Selective Aerobic Oxidation of Alcohols over Atomically-Dispersed Non-Precious Metal Catalysts
Xie, Jiahan,Yin, Kehua,Serov, Alexey,Artyushkova, Kateryna,Pham, Hien N.,Sang, Xiahan,Unocic, Raymond R.,Atanassov, Plamen,Datye, Abhaya K.,Davis, Robert J.
, p. 359 - 362 (2017)
Catalytic oxidation of alcohols often requires the presence of expensive transition metals. Herein, it is shown that earth-abundant Fe atoms dispersed throughout a nitrogen-containing carbon matrix catalyze the oxidation of benzyl alcohol and 5-hydroxymethylfurfural by O2in the aqueous phase. The activity of the catalyst can be regenerated by a mild treatment in H2. An observed kinetic isotope effect indicates that β-H elimination from the alcohol is the kinetically relevant step in the mechanism, which can be accelerated by substituting Fe with Cu. Dispersed Cr, Co, and Ni also convert alcohols, demonstrating the general utility of metal–nitrogen–carbon materials for alcohol oxidation catalysis. Oxidation of aliphatic alcohols is substantially slower than that of aromatic alcohols, but addition of 2,2,6,6-tetramethyl-1-piperidinyloxy as a co-catalyst with Fe can significantly improve the reaction rate.
Engineering the Oxidative Potency of Non-Heme Iron(IV) Oxo Complexes in Water for C-H Oxidation by a cis Donor and Variation of the Second Coordination Sphere
Wegeberg, Christina,Skavenborg, Mathias L.,Liberato, Andrea,McPherson, James N.,Browne, Wesley R.,Hedeg?rd, Erik D.,McKenzie, Christine J.
, p. 1975 - 1984 (2021)
A series of iron(IV) oxo complexes, which differ in the donor (CH2py or CH2COO-) cis to the oxo group, three with hemilabile pendant donor/second coordination sphere base/acid arms (pyH/py or ROH), have been prepared in water at pH 2 and 7. The νFe= O values of 832 ± 2 cm-1 indicate similar FeIV= O bond strengths; however, different reactivities toward C-H substrates in water are observed. HAT occurs at rates that differ by 1 order of magnitude with nonclassical KIEs (kH/kD = 30-66) consistent with hydrogen atom tunneling. Higher KIEs correlate with faster reaction rates as well as a greater thermodynamic stability of the iron(III) resting states. A doubling in rate from pH 7 to pH 2 for substrate C-H oxidation by the most potent complex, that with a cis-carboxylate donor, [FeIVO(Htpena)]2+, is observed. Supramolecular assistance by the first and second coordination spheres in activating the substrate is proposed. The lifetime of this complex in the absence of a C-H substrate is the shortest (at pH 2, 3 h vs up to 1.3 days for the most stable complex), implying that slow water oxidation is a competing background reaction. The iron(IV)= O complex bearing an alcohol moiety in the second coordination sphere displays significantly shorter lifetimes due to a competing selective intramolecular oxidation of the ligand.
PREPARATION OF 1-DEUTERIOALDEHYDES VIA THE USE OF DIISOBUTYLALUMINUM DEUTERIDE (DIBAL-D)
Kalvin, Douglas M.,Woodard, Ronald W.
, p. 3387 - 3392 (1984)
Deuterioaldehydes, essential precursors in the preparation of chiral primary deuterioalcohols, have been prepared in yields ranging from 55-75percent via reduction of methyl and ethyl esters at -78 oC with diisobutylaluminum deuteride (DIBAL-D).The stoich
Kinetics and Mechanism of the Oxidation of Aromatic Aldehydes by Hexachloroiridate(IV)
Gupta, Kalyan Kali Sen,Dey, Sanghamitra,Gupta, Shipra Sen,Banerjee, Amalendu
, p. 5054 - 5057 (1984)
The kinetics of oxidation of benzaldehyde and some substituted benzaldehydes by hexachloroiridate(IV) have been studied spectrophotometrically in the visible region.The reaction is first order in benzaldehyde and in iridium(IV).The influence of acidity on the reaction is small.The activation parameters of the reaction have been calculated.The oxidation reaction is found to have a deuterium isotope effect, kH/kD, of 7.0, indicating that the cleavage of the C-H bond of the aldehyde is the rate-determining step.The reaction appears to be of outer-sphere type and occurs through the intermediate formation of free radicals.
An efficient Pd@Pro-GO heterogeneous catalyst for the α, β-dehydrogenation of saturated aldehyde and ketones
Pan, Gao-Fei,Wang, Zhe,Chang, Yi-Yuan,Hao, Yue,Wang, Yi-Chen,Xing, Rui-Guang
supporting information, (2021/12/30)
An Efficient Pd@Pro-GO heterogeneous catalyst was developed that can promote the α, β-dehydrogenation of saturated aldehyde and ketones in the yield of 73% ? 92% at mild conditions without extra oxidants and additives. Pd@Pro-GO heterogeneous catalyst was synthesized via two steps: firstly, the Pro-GO was obtained by the esterification reaction between graphene oxide (GO) and N-(tert-Butoxycarbonyl)-L-proline (Boc-Pro-OH), followed by removing the protection group tert-Butoxycarbonyl (Boc), which endowed the proline-functionalized GO with both the lewis acid site (COOH) and the bronsted base site (NH), besides, the pyrrolidine of proline also can form imine with aldehydes to activate these substrates; Second, palladium was dispersed on the proline-functionalized GO (Pro-GO) to obtained heterogeneous catalyst Pd@Pro-GO. Mechanistic studies have shown that the Pd@Pro-GO-catalyzed α,β-dehydrogenation of saturated aldehyde and ketones was realized by an improved heterogeneously catalyzed Saegusa oxidation reaction. Based on the obove characteristics, the Pd@Pro-GO will be widely used in the transition metal catalytic field.
SYNTHESIS OF DEUTERATED ALDEHYDES
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Paragraph 0008; 0082, (2021/03/13)
Described are methods for preparing a deuterated aldehyde using N-heterocyclic carbene catalysts in a solvent comprising D2O. The methods may be used to convert a wide variety of aldehydes (e.g., aryl, alkyl, or alkenyl aldehydes) to C-1 deuterated aldehydes under mild reaction conditions without functionality manipulation.
