33046-21-8Relevant academic research and scientific papers
Metal-Organic Architectures Assembled from Multifunctional Polycarboxylates: Hydrothermal Self-Assembly, Structures, and Catalytic Activity in Alkane Oxidation
Gu, Jinzhong,Wen, Min,Cai, Yan,Shi, Zifa,Arol, Aliaksandr S.,Kirillova, Marina V.,Kirillov, Alexander M.
, p. 2403 - 2412 (2019/02/28)
A three-component aqueous reaction system comprising copper(II) acetate (metal node), poly(carboxylic acid) with a phenylpyridine or biphenyl core (main building block), and 1,10-phenanthroline (crystallization mediator) was investigated under hydrothermal conditions. As a result, four new coordination compounds were self-assembled, namely, {[Cu(μ3-cpna)(phen)]·H2O}n (1), {[Cu(μ-Hbtc)(phen)]·H2O}n (2), {[Cu(μ3-Hcpic)(phen)]·2H2O}n (3), and [Cu6(μ-Hcptc)6(phen)6]·6H2O (4), where H2cpna = 5-(2′-carboxylphenyl)nicotinic acid, H3btc = biphenyl-2,4,4′-tricarboxylic acid, H3cpic = 4-(5-carboxypyridin-2-yl)isophthalic acid, H3cptc = 2-(4-carboxypyridin-3-yl)terephthalic acid, and phen = 1,10-phenanthroline. Crystal structures of compounds 1-3 reveal that they are 1D coordination polymers with a ladder, linear, or double-chain structure, while product 4 is a 0D hexanuclear complex. All of the structures are extended further [1D a?' 2D (1 and 2), 1D a?' 3D (3), and 0D a?' 3D (4)] into hydrogen-bonded networks. The type of a multicarboxylate building block has a considerable effect on the final structures of 1-4. The magnetic behavior and thermal stability of 1-4 were also investigated. Besides, these copper(II) derivatives efficiently catalyze the oxidation of cycloalkanes with hydrogen peroxide under mild conditions. The obtained products are the unique examples of copper derivatives that were assembled from H2cpna, H3btc, H3cpic, and H3cptc, thus opening up their use as multicarboxylate ligands toward the design of copper-organic architectures.
Oxidations catalyzed by osmium compounds. Part 1: Efficient alkane oxidation with peroxides catalyzed by an olefin carbonyl osmium(0) complex
Shul'pin, Georgiy B.,Kudinov, Aleksandr R.,Shul'pina, Lidia S.,Petrovskaya, Elena A.
, p. 837 - 845 (2007/10/03)
A carbonyl osmium(0) complex with π-coordinated olefin, (2,3-η-1,4-diphenylbut-2-en-1,4-dione)undecacarbonyl triangulotriosmium (1), efficiently catalyzes oxygenation of alkanes (cyclohexane, cyclooctane, n-heptane, isooctane, etc.) with hydrogen peroxide, as well as with tert-butyl hydroperoxide and meta-chloroperoxybenzoic acid in acetonitrile solution. Alkanes are oxidized to corresponding alcohols, ketones (aldehydes) and alkyl hydroperoxides. Thus, heating cyclooctane with the 1-H2O2 combination at 70 °C gave products with turnover number as high as 2400 after 6 h. The maximum obtained yield of all products was equal to 20% based on cyclohexane and 30% based on H2O2. The oxidation of linear and branched alkanes exhibits very low regio- and bond-selectivity parameters and this testifies that the reaction proceeds via attack of hydroxyl radicals on C-H bonds of the alkane. The oxygenation products were not formed when the reaction was carried out under argon atmosphere and it can be thus concluded that the oxygenation occurs via the reaction between alkyl radicals and atmospheric oxygen. In summary, the Os(0) complex is much more powerful generator of hydroxyl radicals than any soluble derivative of iron (which is an analogue of osmium in the Periodic System).
Efficient method for the preparation of pinacols derived from aromatic and aliphatic ketones by using low-valent titanium reagents in dichloromethane-pivalonitrile
Kagayama,Igarashi,Mukaiyama
, p. 657 - 665 (2007/10/03)
The reductive coupling reaction of aldehydes and ketones, including unsymmetrical aliphatic ketones, proceeded smoothly to give the corresponding pinacols in good to high yields under mild conditions by using combination of titanium(II) chloride and zinc or titanium(IV) chloride and zinc in dichloromethane-pivalonitrile. Meso-selective formation of the coupling products was observed in the cases of some aliphatic ketones. The diastereoselectivities of coupling products depend on both difference of bulkiness of 2-, and 2'-substituents of carbonyl group of the reactant, and overall steric effect around the carbonyl groups.
Aqueous permanganate oxidations of cycloalkenes to cis-glycols and cis to trans conversions
Taylor, Jay E.,Janini, Thomas E.,Elmer, Otto C.
, p. 147 - 150 (2013/09/08)
A series of cis-glycols including 1,2-cyclopentanediol, 1-methyl-1,2-cyclopentanediol, 1,2-dimethyl-1,2-cyclopentanediol, 1,2-cyclohexanediol, 1-methyl-1,2-cyclohexanediol, 1,2-dimethyl-1,2-cydohexanediol, 1,2-cycloheptanediol, 1,2-cyclooctanediol, exo,exo-bicyclo[2.2.1]heptane-2,3-diol, and bicyclo[2.2.2]octane-2,3-diol have been prepared by permanganate oxidations of cycloalkenes using a turbulent stirring technique. Conditions for the reactions, methods of purification, and yields are presented. Both hydroxide ion and an aqueous environment are highly essential to the formation of glycols. Excessive solvent decreases yields. A procedure for converting certain cis- to trans-glycols is given. A preparation for very pure Δ9,10-octalin is included.
Oxidation by cobalt(III)acetate. Part 9. Effect of substituents on the oxidative Cleavage of glycols in acetic acid
Gunji, Tomokazu,Hirano, Masao,Morimoto, Takashi
, p. 1827 - 1832 (2007/10/02)
The kinetics of oxidative cleavage of glycols by obalt(III) acetate in acetic acid have been studied.The substrates examined include cis- and trans-cyclopentane- and cyclohexane-1,2-diols and their mono- and dimethyl derivatives.The rates were first-order in both cobalt(III)acetate and substrate in all cases.In the oxidation of five-membered ring diols, cis-diols were generally oxidized faster than the trans-isomers.Complex results were obtained in the case of six-membered ring diols.Thermodynamic parameters were calculated for all the substrates.A mechanism involving a bidente complex of cobalt(III) acetate dimer and glycol is sugge sted, except for the case of trans-cyclopentane-1,2-diols, for which a monodentate intermediate is proposed.
