1195-79-5Relevant academic research and scientific papers
Reaction of seleno- or thiofenchone with propiolic acid: Wagner-meerwein rearrangement
Okuma, Kentaro,Matsui, Hiroyuki,Mori, Yuichi
, p. 578 - 583 (2014)
A reaction of selenofenchone with propiolic acid in refluxing chloroform produced 1,3-oxaselenin-6-one, which further reacted with acid to afford the ring-opened product. A reaction of 1,3-oxathiin-6-one prepared from thiofenchone with trifluoroacetic acid gave a Wagner-Meerwein rearranged product. In the presence of AlCl3, thiofenchone reacted with methyl propiolate to afford the corresponding rearranged ester.
Copper(ii) and iron(iii) complexes with arylhydrazone of ethyl 2-cyanoacetate or formazan ligands as catalysts for oxidation of alcohols
Martins, Nuno M. R.,Mahmudov, Kamran T.,Guedes Da Silva, M. Fátima C.,Martins, Luísa M. D. R. S.,Pombeiro, Armando J. L.
, p. 10071 - 10083 (2016)
The aquasoluble [Cu(1κN,O2:2κO-HL1)(S)]2 [S = CH3OH (1), (CH3)2NCHO (2)] and [Cu(κN-HL1)(en)2]·CH3OH·H2O (3) CuII complexes were prepared by the reaction of CuII nitrate hydrate with the new ligand (E/Z)-4-(2-(1-cyano-2-ethoxy-2-oxoethylidene)hydrazinyl)-3-hydroxybenzoic acid (H3L1), in the presence (for 3) or absence (for 1 and 2) of ethylenediamine (en), while the FeIII complex [Fe(κN3-HL2)2] (4) was isolated by treatment of iron(III) chloride hexahydrate with the new ligand (1E,1E)-N′,2-di(1H-1,2,4-triazol-3-yl)diazenecarbohydrazonoyl cyanide (H3L2), and characterized by elemental analysis, IR spectroscopy and single crystal X-ray diffraction. Cooperative E,Z → E isomerization of H3L1, induced by coordination and ionic interactions, occurs upon interaction with CuII in the presence of en. Complexes 1-4 act as catalyst precursors for the solvent-free microwave (MW) assisted selective oxidation of primary or secondary alcohols and diols to the corresponding aldehydes, ketones and diketones, respectively, with yields in the 5-99% range (TONs up to 4.96 × 102) after 60 min of MW irradiation at 120 °C. The influence of temperature, time and organic radicals was studied and also the regioselective oxidation of the catalytic systems involving the primary and secondary alcohols.
Kinetics and mechanisms of the tropospheric reactions of menthol, borneol, fenchol, camphor, and fenchone with hydroxyl radicals (OH) and chlorine atoms (Cl)
Ceacero-Vega, Antonio A.,Ballesteros, Bernabe,Bejan, Iustinian,Barnes, Ian,Jimenez, Elena,Albaladejo, Jose
, p. 4097 - 4107 (2012)
Relative kinetic techniques have been used to measure the rate coefficients for the reactions of oxygenated terpenes (menthol, borneol, fenchol, camphor, and fenchone) and cyclohexanol with hydroxyl radicals (OH) and chlorine atoms (Cl) at 298 ± 2 K and atmospheric pressure. The rate coefficients obtained for the reactions of the title compounds with OH are the following (in units of 10-11 cm3 molecule-1 s-1): (1.48 ± 0.31), (2.65 ± 0.32), (2.49 ± 0.30), (0.38 ± 0.08), (0.39 ± 0.09) for menthol, borneol, fenchol, camphor, and fenchone, respectively. For the corresponding reactions with Cl atoms the rate coefficients are as follows (in units of 10-10 cm3 molecule-1 s-1): (3.21 ± 0.26), (3.40 ± 0.28), (2.72 ± 0.13), (2.93 ± 0.17), (1.59 ± 0.10), and (1.86 ± 0.29) for cyclohexanol, menthol, borneol, fenchol, camphor, and fenchone, respectively. The reported error is twice the standard deviation. Product studies of the reactions were performed using multipass in situ FTIR (Fourier transform infrared spectroscopy) and solid-phase microextraction (SPME) with analysis by GC-MS (gas chromatography-mass spectrometry). A detailed mechanism is proposed to justify the observed reaction products.
Cobalt(II) Coordination Polymers Assembled from Unexplored Pyridine-Carboxylic Acids: Structural Diversity and Catalytic Oxidation of Alcohols
Gu, Jinzhong,Wen, Min,Cai, Yan,Shi, Zifa,Nesterov, Dmytro S.,Kirillova, Marina V.,Kirillov, Alexander M.
, p. 5875 - 5885 (2019)
New coordination polymers of cobalt(II), namely, [Co(μ4-cpna)(H2O)2]n (1), [Co(μ3-cpna)(phen)(H2O)]n·nH2O (2), [Co3(μ4-dppa)2(H2O)6]n·2nH2O (3), and [Co3(μ5-dppa)2(μ-4,4-bipy)(H2O)2]n·4nH2O (4), have been generated under hydrothermal conditions from CoCl2·6H2O, two different multifunctional pyridine-carboxylic acids {H2cpna: 5-(4-carboxyphenoxy)nicotinic acid; H3dppa: 5-(3,4-dicarboxylphenyl)picolinic acid}, and optional N,N-supporting ligands {phen: 1,10-phenanthroline; 4,4-bipy: 4,4-bipyridine} acting as mediators of crystallization. These Co(II) coordination polymers (CPs) have been obtained as stable crystalline materials and characterized by conventional solid-state techniques, including X-ray crystallography. The obtained products are 3D metal-organic frameworks (MOFs 1 and 4) or 2D coordination polymers (CPs 2 and 3). Analysis of the topologies of simplified nets has revealed the sra (1), fes (2), and 3,4L13 (3) networks, in addition to a very complex topologically unique framework in 4. An observed diversity of structures is driven by types of carboxylate building blocks and crystallization mediators. Thermal stability and magnetic and catalytic properties of 1-4 have also been studied. In fact, the Co(II) compounds act as heterogeneous catalysts for the oxidation of alcohols with tBuOOH (tert-butylhydroperoxide) under mild conditions. Compound 2 features a good catalytic activity (up to 45% yield) in the oxidation of 1-indanol to 1-indanone. Finally, products 1-4 broaden a still very small number of CPs or MOFs driven by the present type of multifunctional pyridine-carboxylic acids (H2cpna, H2dppa).
Aerobic Oxidation of Secondary Alcohols via Ruthenium-catalysed Hydrogen Transfer Involving a New Triple Catalytic System
Wang, Guo-Zhi,Andreasson, Ulrika,Baeckvall, Jan-E.
, p. 1037 - 1038 (1994)
Aerobic oxidation of secondary alcohols was performed employing a new triple catalytic system (Ru-catalyst 1, 2,6-di-tert-butylbenzoquinone 2, and Co-macrocycle 3) under a low concentration of molecular oxygen (air:nitrogen is between 1:3 and 1:20) at ambient pressure.
Mechanistic and Synthetic Aspects of Intramolecular Alkoxide-Allene Cyclizations
Magnus, Philip,Albaugh-Robertson, Pamela
, p. 804 - 806 (1984)
Intramolecular cyclization of the methoxyallene-alkoxide adducts (1a) proceeds along two different pathways via a methoxyallyl radical anion to give either a dihydrofuran, or vinyl epoxide, depending upon the steric environment of the radical anion.
Molybdenum complexes with a μ-O{MoO2}2 core: their synthesis, crystal structure and application as catalysts for the oxidation of bicyclic alcohols using N-based additives
Maurya, Mannar R.,Rana, Lata,Avecilla, Fernando
, p. 724 - 734 (2017)
Three binuclear μ-oxidobis{dioxidomolybdenum(vi)} complexes, [(μ-O){MoVIO2(MeOH)}2(L1)] 1, [(μ-O){MoVIO2(MeOH)}2(L2)] 2, and [(μ-O){MoVIO2(MeOH)}2(L3)] 3 with potential dibasic tetradentate azine ligands [H2L1 = azine of salicylaldehyde, H2L2 = azine of 3-methoxysalicyaldehyde and H2L3 = azine of 3,5-ditertiarybutylsalicylaldehyde] are reported. The complexes are characterized via elemental analysis, various spectroscopic techniques (FT-IR, UV-Vis, 1H and13C NMR), thermogravimetric analysis and single-crystal X-ray diffraction (2 and 3) studies. These complexes are binuclear having a μ-O{MoO2}2 core where ligands coordinate through a set of phenolic oxygen and azine nitrogen to each molybdenum, thus behaving as bis(bidentate). These complexes are investigated as catalysts for the oxidation of two bicyclic alcohols (fenchyl alcohol and isoborneol) using 30% H2O2 as the oxidant in the presence of NEt3 as the additive. The conversion of bicyclic alcohols within the additives follows the order: NEt3 > py > NH3 > K2CO3 > KOH. In the presence of an N-based additive, fenchyl alcohol and isoborneol selectively give high yields of fenchone and camphor, respectively, while in the absence of the additive the conversion is relatively low.
Palladium(II)-catalyzed ring expansion of a 1-alkenyl cyclopentanol
García Martínez, Antonio,Teso Vilar, Enrique,García Fraile, Amelia,De La Moya Cerero, Santiago,Lora Maroto, Beatriz
, p. 3509 - 3511 (2005)
7,7-Dimethyl-2-methylenenorbornan-1-ol, a strained bicyclic 1-alkenyl cyclopentanol, undergoes Wagner-Meerwein rearrangement to fenchone under treatment with a catalytic amount of PdCl2(PPh3) 2 in refluxing N-methylpyrrolidin-2-one. The described reaction constitutes the first example of the palladium(II)-catalyzed ring expansion of 1-alkenyl cyclopentanols to the corresponding cyclohexanones.
Effect of N-based additive on the optimization of liquid phase oxidation of bicyclic, cyclic and aromatic alcohols catalyzed by dioxidomolybdenum(VI) and oxidoperoxidomolybdenum(VI) complexes
Maurya, Mannar R.,Saini, Neeraj,Avecilla, Fernando
, p. 101076 - 101088 (2015/12/09)
Two dioxidomolybdenum(vi) complexes, [MoVIO2(L1)(MeOH)] (1) and [MoVIO2(L2)(MeOH)] (2) and their corresponding oxidoperoxidomolybdenum(vi) complexes, [MoVIO(O2)(L1)(MeOH)] (3) and [MoVIO(O2)(L2)(MeOH)] (4) with ONO tridentate ligands, 4-[3,5-bis(2-hydroxyphenyl)-1,2,4-triazol-1-yl]benzoic acid (H2L1, I) and 3,5-bis(2-hydroxyphenyl)-1-phenyl-1,2,4-triazole (H2L2, II) have been synthesized and characterized by elemental analysis, spectroscopic techniques (infrared, UV-Vis, 1H and 13C NMR) and thermogravimetric analysis. Structures of 1a (DMSO coordinated) and 2 (methanol coordinated) confirmed by single crystal X-ray study reveal that the tridentate ligands bind to the metal center through two oxygen atoms and a ring nitrogen atom. These complexes have been tested as catalysts for the homogeneous oxidation of bicyclic (isoborneol and fenchyl alcohol), aromatic (benzyl alcohol and cumic alcohol) and cyclic (cyclohexanol) alcohols, using 30% H2O2 as an oxidant. Various parameters such as amounts of catalyst, oxidant, solvent and temperature of the reaction mixture have been taken into consideration for the maximum conversion of substrates. Effect of N-based additive (NEt3) on the conversion of substrates as well as selectivity of the corresponding product(s) under the optimized reaction conditions has also been checked and obtained results suggest that addition of an additive reduces time to achieve equilibrium and increases conversion of alcohols.
METHOD FOR OXIDIZING ALCOHOLS
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Paragraph 0045, (2013/06/05)
A method for oxidizing an alcohol, wherein oxidation is performed in the presence of a compound represented by the following formula (I) and a bulk oxidant, which enables efficient oxidation of secondary alcohols as well as primary alcohols, and can attain high reaction efficiency even when air is used as a bulk oxidant.
