107-87-9Relevant articles and documents
Isobutanol and methanol synthesis on copper catalysts supported on modified magnesium oxide
Xu, Mingting,Gines, Marcelo J. L.,Hilmen, Anne-Mette,Stephens, Brandy L.,Iglesia, Enrique
, p. 130 - 147 (1997)
Alcohols are selectively produced from CO/H2 on K-CuMgCeOx catalysts, but synthesis rates are strongly inhibited by CO2 formed during reaction. Reaction pathways involve methanol synthesis on Cu, chain growth to C2+ alcohols, and metal-base bifunctional coupling of alcohols to form isobutanol. Ethanol reactions on K-Cu0.5Mg5CeOx show that Cu catalyzes both alcohol dehydrogenation and aldol condensation reactions. CeO2 increases Cu dispersion and MgO surface area and K decreases Cu dispersion, but increases the density of basic sites. Reactions of acetaldehyde and 13C-labeled methanol lead to 1-13C-propionaldehyde, a precursor to isobutanol. The density and strength of basic sites were measured using a 12CO2/13CO2 isotopic jump method that probes the number and chemical properties of basic sites available at typical isobutanol synthesis temperatures. K or CeO2 addition to CuMgOx increases the density and strength of basic sites and the rates of base-catalyzed ethanol condensation reactions leading to acetone and n-butyraldehyde. The presence of CO in the He carrier during temperature-programmed surface reactions of ethanol preadsorbed on Cu0.5Mg5CeOx decreases the rate of base-catalyzed condensation reactions of preadsorbed ethanol, possibly due to the poisoning of basic and Cu sites by the CO2 formed from CO via water-gas shift reactions.
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Van Volkenburgh et al.
, p. 3595 (1949)
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SOME THERMAL TRANSFORMATION CHARACTERISTICS OF DIHYDROSYLVAN
Karakhanov, E. A.,Karzhavina, N. P.,Brezhnev, L. Yu.
, p. 191 - 192 (1982)
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Catalytic aerobic oxidation of alcohols by Fe(NO3)3-FeBr3
Martín, Sandra E,Suárez, Darío F
, p. 4475 - 4479 (2002)
Selective aerobic oxidation of secondary and benzylic alcohols was efficiently accomplished by the binary catalyst system Fe(NO3)3-FeBr3 under air at room temperature. The oxidation developed in mild conditions and showed
Relative and absolute kinetic studies of 2-butanol and related alcohols with tropospheric Cl atoms
Ballesteros, Bernabe,Garzon, Andres,Jimenez, Elena,Notario, Alberto,Albaladejo, Jose
, p. 1210 - 1218 (2007)
A newly constructed chamber/Fourier transform infrared system was used to determine the relative rate coefficient, ki, for the gas-phase reaction of Cl atoms with 2-butanol (k1), 2-methyl-2-butanol (k 2), 3-methyl-2-butanol (k3), 2,3-dimethyl-2-butanol (k4) and 2-pentanol (k5). Experiments were performed at (298 ± 2) K, in 740 Torr total pressure of synthetic air, and the measured rate coefficients were, in cm3 molecule-1 s -1 units (±2σ): k1 = (1.32 ± 0.14) × 10-10, k2 = (7.0 ± 2.2) × 10 -11, k3 = (1.17 ± 0.14) × 10-10, k4 = (1.03 ± 0.17) × 10-10 and k5 = (2.18 ± 0.36) × 10-10, respectively. Also, all the above rate coefficients (except for 2-pentanol) were investigated as a function of temperature (267-384 K) by pulsed laser photolysis-resonance fluorescence (PLP-RF). The obtained kinetic data were used to derive the Arrhenius expressions: k1(T) = (6.16 ± 0.58) × 10 -11exp[(174 ± 58)/T], k2(T) = (2.48 ± 0.17) × 10-11exp[(328 ± 42)/T], k3(T) = (6.29 ± 0.57) × 10-11exp[(192 ± 56)/T], and k 4(T) = (4.80 ± 0.43) × 10-11exp[(221 ± 56)/T] (in units of cm3 molecule-1 s-1 and ±σ). Results and mechanism are discussed and compared with the reported reactivity with OH radicals. Some atmospheric implications derived from this study are also reported. This journal is the Owner Societies.
Developing an efficient catalyst for controlled oxidation of small alkanes under ambient conditions
Nagababu, Penumaka,Yu, Steve S.-F.,Maji, Suman,Ramu, Ravirala,Chan, Sunney I.
, p. 930 - 935 (2014)
The tricopper complex [CuICuICuI(7-N- Etppz)]1+, where 7-N-Etppz denotes the ligand 3,3′-(1,4- diazepane-1,4-diyl)bis[1-(4-ethyl piperazine-1-yl)propan-2-ol], is capable of mediating facile conversion of methane into methanol upon activation of the tricopper cluster by dioxygen and/or HO at room temperature. This is the first molecular catalyst that can catalyze selective oxidation of methane to methanol without over-oxidation under ambient conditions. When this CuICu ICuI tricopper complex is activated by dioxygen or H 2O2, the tricopper cluster harnesses a "singlet oxene", the strongest oxidant that could be used to accomplish facile O-atom insertion across a C-H bond. To elucidate the properties of this novel catalytic system, we examine here methane oxidation over a wider range of conditions and extend the study to other small alkanes, including components of natural gas. We illustrate how substrate solubility, substrate recognition and the amount of H2O2 used to drive the catalytic oxidation can affect the outcome of the turnover, including regiospecificity, product distributions and yields of substrate oxidation. These results will help in designing another generation of the catalyst to alleviate the limitations of the present system. This journal is the Partner Organisations 2014.
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Grove,J.F.
, p. 2261 - 2263 (1971)
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Enantioselective oxidation of secondary alcohols by the flavoprotein alcohol oxidase from Phanerochaete chrysosporium
Tjallinks, Gwen,Martin, Caterina,Fraaije, Marco W.
, (2021)
The enantioselective oxidation of secondary alcohols represents a valuable approach for the synthesis of optically pure compounds. Flavoprotein oxidases can catalyse such selective transformations by merely using oxygen as electron acceptor. While many flavoprotein oxidases preferably act on primary alcohols, the FAD-containing alcohol oxidase from Phanerochaete chrysosporium was found to be able to perform kinetic resolutions of several secondary alcohols. By selective oxidation of the (S)-alcohols, the (R)-alcohols were obtained in high enantiopurity. In silico docking studies were carried out in order to substantiate the observed (S)-selectivity. Several hydrophobic and aromatic residues in the substrate binding site create a cavity in which the substrates can comfortably undergo van der Waals and pi-stacking interactions. Consequently, oxidation of the secondary alcohols is restricted to one of the two enantiomers. This study has uncovered the ability of an FAD-containing alcohol oxidase, that is known for oxidizing small primary alcohols, to perform enantioselective oxidations of various secondary alcohols.
Wet carbon-based solid acid/potassium bromate as an efficient heterogeneous reagent for oxidation of alcohols under mild conditions
Zali, Abbas,Shokrolahi, Arash
, p. 1064 - 1069 (2008)
Wet carbon-based solid acid and potassium bromate were used as new reagent for oxidation of alcohols to their corresponding aldehyde or ketone derivatives in dichloromethane with good yields. Copyright Taylor & Francis Group, LLC.
Bifunctional condensation reactions of alcohols on basic oxides modified by copper and potassium
Gines, Marcelo J. L.,Iglesia, Enrique
, p. 155 - 172 (1998)
Alcohol dehydrogenation and condensation reactions are involved in chain growth pathways on Cu/MgCeOx promoted with potassium. These pathways lead to the formation of isobutanol with high selectivity via reactions of higher alcohols with methanol-derived C1 species in reaction steps also relevant to higher alcohol synthesis from CO/H2 mixtures at higher pressures on K-Cu/MgCeOx catalysts. Ethanol reactions on K-CUyMg5CeOx show that both Cu and basic sites participate in alcohol dehydrogenation and aldol condensation steps leading to n-butyraldehyde and acetone. Chain growth occurs by condensation reactions involving a metal-base bifunctional aldol-type coupling of alcohols. Reactions of 12C2H5OH-13C2H 4O mixtures show that direct condensation reactions of ethanol can occur without requiring the intermediate formation of gas phase acetaldehyde. Reactions of C2H5OH/D2 mixtures show that Cu sites increase the rate of aldol condensation by introducing recombinative desorption sites that remove hydrogen atoms formed in C-H activation steps leading to the unsaturated aldol-type species required for chain growth. Reactions of acetaldehyde and 13C-labeled methanol lead predominantly to 1-13C-propionaldehyde and 2-13C-isobutyraldehyde, both of which lead to isobutanol during CO/H2 reactions. Mixtures of propionaldehyde and 13C-labeled methanol lead to singly-labeled isobutyraldehyde. Chain growth to C2+ alcohols occurs via addition of a methanol-derived C1 species to adsorbed oxygen-containing intermediates. The gradual appearance of 13C in the unlabeled reactant within these mixtures shows that aldol coupling reactions are reversible. Reverse aldol condensation reactions after intramolecular hydride transfer lead to the formation of acetone from ethanol. Isobutyraldehyde is a preferred end-product of aldol-type chain growth reactions of alcohols because it lacks the two α-hydrogens required for subsequent chain growth. 998 Academic Press.
Oxidation of Alcohols with H2O2 Catalyzed by Titanium Silicalite-1
Maspero, Federico,Romano, Ugo
, p. 476 - 482 (1994)
Primary and secondary alcohols are oxidised by H2O2 in the presence of titanium silicalite-1 to carbonylic compounds.Reaction rates follow the general trend secondary primary methanol.Rates are sensitive to position effects of the OH group, to chain branching effects, and to molecular size of the alcohol.Kinetic orders with respect to H2O2 are generally close to zero, while those with respect to the alcohol are strongly affected by the solvent used.The kinetic pattern is interpreted in terms of an interaction of the lattice titanium atom of titanium silicalite-1 with H2O2.The kinetic order with respect to the alcohol can be interpreted either in terms of titanium-alcohol adducts or with a selective alcohol sorption in the catalyst pores.The reaction pattern is consistent with a process taking place essentially inside the zeolite channels, with a transition-state-restricted shape-selectivity.The nature of the titanium hydroperoxide involved in the intermediate complex is discussed.
New efficient aerobic oxidation of some alcohols with dioxygen catalysed by N-hydroxyphtalimide with vanadium co-catalysts
Figiel, Pawel J.,Sobczak, Jaroslaw M.,Ziolkowski, Jozef J.
, p. 244 - 245 (2004)
New efficient vanadium co-catalysts have been developed for the oxidation of some alcohols with O2 catalysed by N-hydroxyphthalimide (NHPI). Various alcohols (primary and secondary) were selectively oxidized by O 2 under mild conditions in the presence of a catalytic amount of NHPI as a radical-producing agent combined with small amounts of vanadium complexes with or without the addition of a simple salt (e.g. LiCl) or base (e.g. pyridine).
Photodecomposition of iodopentanes in air: Product distributions from the self-reactions of n-pentyl peroxyl radicals
Heimann, Gerald,Benkelberg, Heinz-Jrgen,Bge, Olaf,Warneck, Peter
, p. 126 - 138 (2002)
Product distributions from the 254-nm photooxidation of the three iodopentane isomers were explored as a technique for studying the self-reactions of individual pentyl peroxyl radicals (in air at ambient temperature and pressure). Pentanols and the associated carbonyl compounds (pentanal or pentanones) were major products as expected. Other major products resulted from the isomerization of pentan-1-oxyl and pentan-2-oxyl radicals, but their nature could not be identified. Minor products were alcohols and carbonyl compounds arising from the decomposition of pentoxyl radicals. Diols and mixed hydroxycarbonyl compounds from cross-combination reactions were essentially absent, in contrast to expectation. The observed product distributions were evaluated to derive branching ratios for the radical-preserving pathways of the self-reactions, 0.42 ± 0.17, 0.46 ± 0.10, 0.39 ± 0.08, for pentan-1-yl peroxyl, pentan-2-yl peroxyl, and pentan-3-yl peroxyl, respectively. Rate coefficients derived for the decomposition of the corresponding pentoxyl radicals, relative to their reaction with oxygen, are (5.1 ± 0.5) × 1018, (1.0 ± 0.2) × 1018, and (3.2 ± 0.3) × 1018 molecule cm-3, respectively. Rate constants for the isomerization of pentan-1-oxyl and pentan-2-oxyl were estimated from the contributions of isomerization products to the total amounts of products as (4.0 ± 1.1) × 105 s-1 and (1.0 ± 2.0) × 105 s-1, respectively.
A novel method for the synthesis of aldehydes and ketones
Pérez G.,Pérez G.,Zavala S.,Pérez G.,Guadarrama M.
, p. 3011 - 3014 (1998)
A new method for the preparation of aldehydes and ketones from alkylnitrites and BF2.Et2O or anhydrous ZnCl2 is described. Twelve different nitrites were tested obtaining yields over 90%. When these Lewis acids were substituted by anhydrous AlCl3, the yield decreased to a value below 20%.
A series second-first-order mechanism for the oxidation of primary and secondary alcohols by Cr(VI) reagents
Agarwal, Seema,Tiwari,Sharma
, p. 1963 - 1974 (1990)
Based on the experimental data, a definite mechanism for the oxidation of primary and secondary alcohols with PCC and two newly synthesized Cr(VI) reagents has been proposed. The reaction has been shown to be a series reaction rather than a simple one step reaction as reported in the literature. The mechanism proposed has been exemplified by taking 2-pentanol as an example. The kinetic isotope studies have also been performed.
Sato,Cvetanovic
, p. 953,955 (1959)
TRANSFORMATION OF ORGANIC COMPOUNDS IN THE PRESENCE OF METAL COMPLEXES I. TRANSFORMATION OF UNSATURATED ALCOHOLS WITH METAL COMPLEX CATALYSTS
Felfoeldi, K.,Bartok, M.
, p. C37 - C40 (1985)
The transformations of unsaturated alcohols (2-hexen-3-ol, 1-penten-4-ol, 1-penten-4-ol and 2-methylenecyclohexanol) were studied under identical experimental conditions in the presence of various Rh and Ru complexes (RhCl(PPh3)3, RhH(PPh3)4, RhCl3*3H2O, RhCl3*3H2O + PPh3, Rh(COD)Cl2, Rh(COD)Cl2 + PPh3, RhCl2(PPh3)3 and RuH2(PPh3)4).Several aspects of both the unsaturated alcohol and the complex exertconsiderable effects on the extent of the main reactions; isomerization to ketone and double-bond migration.
Reaction of metal alkoxides with 3-alkyl-substituted acetylacetone derivatives - Coordination vs. hydrodeacylation
Puchberger, Michael,Rupp, Wolfgang,Bauer, Ulrike,Schubert, Ulrich
, p. 1289 - 1294 (2004)
Reaction of Ti(OiPr)4 or Zr(OPr)4 with 1 or 2 molar equiv of the 3-alkyl-substituted acetylacetone derivatives 3-acetyl-6-trimethoxysilylhexane-2-one or 3-acetylpentane-2-one not only gives the corresponding β-diketonate complexes but also results in about 15% hydrodeacylation of the β-diketone. With the stronger Lewis acid Al(O sBu)3 hydrodeacylation prevails. Hydrodeacylation is suppressed when a 1:5 ratio of metal alkoxide and β-diketone is reacted.
Zeolite supported permanganate: An efficient catalyst for selective oxidation of enamines, alkylarenes and unsaturated alcohols
Sreekumar,Padmakumar, Raghavakaimal
, p. 5143 - 5146 (1997)
Potassium permanganate supported on zeolite can be used for the selective oxidation of various enamines, alkylarenes and unsaturated alcohols to the corresponding ketones, in good yield. Arenes were selectively oxidized at the benzylic position. If the benzylic carbon is secondary, ketones are obtained, and alcohols are produced if the benzylic position is tertiary. In contrast unsaturated secondary alcohols selectively undergo oxidation to the corresponding olefinic ketones without affecting the carbon-carbon double bonds.
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Meerwein
, p. 249 (1913)
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Controlled Monooxygenation of n- and Isoalkanes with Molecular Oxygen Catalyzed in Nonheme Iron Complex/Hydroquinone Systems
Funabiki, Takuzo,Kashiba, Koji,Toyoda, Takehiro,Yoshida, Satohiro
, p. 2303 - 2306 (1992)
Linear and branched alkanes are monooxygenated with O2 in nonheme iron complex/hydroquinone systems.Selectivity to form either alcohols or carbonyl compounds was controlled by the pyridine concentration.Reactivity of dfferent types of C-H bonds was affected by the substituents of hydroquinones, suggesting that hydroquinones are located in the vicinity of an active center in the product formation step.
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Djerassi et al.
, (1960)
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A direct imaging of amphiphilic catalysts assembled at the interface of emulsion droplets using fluorescence microscopy
Gao, Jinbo,Zhang, Yongna,Jia, Guoqing,Jiang, Zongxuan,Wang, Shouguo,Lu, Hongying,Song, Bo,Li, Can
, p. 332 - 334 (2008)
An amphiphilic fluorescent catalyst Q9[EuW10O 36] (Q = [(C18H37)2N +(CH3)2]), assembled in the interface of emulsion systems, was directly imaged by fluores
Decarboxylation and simultaneous reduction of silver(I) β-ketocarboxylates with three types of coordinations
Hatamura, Mariko,Yamaguchi, Shunro,Takane, Shin-Ya,Chen, Yu,Suganuma, Katuaki
, p. 8993 - 9003 (2015)
A series of silver(I) β-ketocarboxylates were prepared by reaction of β-ketocarboxylic acids with silver nitrate in the presence of diethanolamine. The silver(I) β-ketocarboxylates decomposed over a narrow temperature range to form metallic silver, CO2, and the corresponding ketones. In addition, products derived from radical intermediates were detected by mass spectroscopic analysis for some silver(I) β-ketocarboxylates. Infrared and solid state 13C-NMR spectra of silver(I) β-ketocarboxylates suggested the presence of two types of structures involving a carbonyl group in addition to the dimeric eight-membered ring structure as in the structure of silver(I) stearate. The silver(I) β-ketocarboxylate model compound used was HCOCH2COOAg and its structures were determined using density functional theory (DFT) and atoms-in-molecules (AIM) methods. Three types of coordinations around the Ag ion differing significantly in Ag-O bond strengths were found. Based on the calculated structures and experimental results, the relationships between the structures and decomposition temperatures are discussed in terms of the thermal decomposition process.
PALLADIUM AND PHASE TRANSFER CATALYZED OXIDATION OF OLEFINS TO KETONES. SENSITIVITY OF THE REACTION TO THE NATURE OF THE PHASE TRANSFER AGENT.
Januszkiewicz, Krzysztof,Alper, Howard
, p. 5159 - 5162 (1983)
Terminal olefins can be converted to ketones in good yields, and under mild conditions, using phase transfer catalysis; the quaternary ammonium salt governs the course of the react ion.
Production of renewable 1,3-pentadiene over LaPO4 via dehydration of 2,3-pentanediol derived from 2,3-pentanedione
Bai, Chenxi,Cui, Long,Dai, Quanquan,Feng, Ruilin,Liu, Shijun,Qi, Yanlong
, (2022/02/07)
1,3-Pentadiene plays an extremely important role in the production of polymers and fine chemicals. Herein, the LaPO4 catalyst exhibits excellent catalytic performance for the dehydration production of 1,3-pentadiene with 2,3-pentanediol, a C5 diol platform compound that can be easily obtained by hydrogenation of bio-based 2,3-pentanedione. The relationships of catalyst structure-acid/base properties-catalytic performance was established, and an acid-base synergy effect was disclosed for the on-purpose synthesis of 1,3-pentadiene. Thus, a balance between acid and base sites was required, and an optimized LaPO4 with acid/base ratio of 2.63 afforded a yield of 1,3-pentadiene as high as 61.5% at atmospheric pressure. Notably, the Br?nsted acid sites with weak or medium in LaPO4 catalyst can inhibit the occurrence of pinacol rearrangement, resulting in higher 1,3-pentadiene production. In addition, the investigation on reaction pathways demonstrated that the E2 mechanism was dominant in this dehydration reaction, accompanied by the assistance of E1 and E1cb.
Hydration of Alkynes to Ketones with an Efficient and Practical Polyoxomolybdate-based Cobalt Catalyst
Xie, Ya,Wang, Jingjing,Wang, Yunyun,Han, Sheng,Yu, Han
, p. 4985 - 4989 (2021/10/12)
Hydration of alkynes to ketones is one of the most atom economical and universal methods for the synthesis of carbonyl compounds. However, the basic reaction usually requires organic ligand catalysts or harsh reaction conditions to insert oxygen into the C≡C bond. Here, we report an inorganic ligand supported cobalt (III) catalyst, (NH4)3[CoMo6O18(OH)6], which is supported by a central cobalt (III) mononucleus and a ring-shaped pure inorganic ligand composed of six MoVIO6 octahedrons to avoid the disadvantages of expensive and unrecyclable organic ligand catalysts or noble metal catalysts. Under mild conditions, the cobalt (III) catalyst can be used for the hydration of alkynes to ketones. The catalyst is non-toxic, green, and environment friendly. The catalyst can be recycled at least six times with high activity. According to control experiments, a reasonable mechanism is provided.
Chemoselective and Site-Selective Reductions Catalyzed by a Supramolecular Host and a Pyridine-Borane Cofactor
Morimoto, Mariko,Cao, Wendy,Bergman, Robert G.,Raymond, Kenneth N.,Toste, F. Dean
supporting information, p. 2108 - 2114 (2021/02/06)
Supramolecular catalysts emulate the mechanism of enzymes to achieve large rate accelerations and precise selectivity under mild and aqueous conditions. While significant strides have been made in the supramolecular host-promoted synthesis of small molecules, applications of this reactivity to chemoselective and site-selective modification of complex biomolecules remain virtually unexplored. We report here a supramolecular system where coencapsulation of pyridine-borane with a variety of molecules including enones, ketones, aldehydes, oximes, hydrazones, and imines effects efficient reductions under basic aqueous conditions. Upon subjecting unprotected lysine to the host-mediated reductive amination conditions, we observed excellent ?-selectivity, indicating that differential guest binding within the same molecule is possible without sacrificing reactivity. Inspired by the post-translational modification of complex biomolecules by enzymatic systems, we then applied this supramolecular reaction to the site-selective labeling of a single lysine residue in an 11-amino acid peptide chain and human insulin.
