- Copper-catalyzed method for preparing aldehyde or ketone compound by oxidizing alcohol with oxygen as oxidizing agent and application
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The invention discloses a copper-catalyzed method for preparing an aldehyde or ketone compound by oxidizing alcohol with oxygen as an oxidizing agent. Reaction is performed in an organic solvent for 4-48 hours at room temperature by using copper salt and nitroxide free radicals as catalysts and oxygen or air as an oxidizing agent to efficiently oxidize an alcohol compound into the corresponding aldehyde or ketone compound. The method is simple to operate, free of chlorides corrosive to equipment, available in raw materials and reagents, mild in reaction conditions, wide in substrate universality, good in functional group compatibility, convenient in separation and purification, environmentally friendly in the whole process and free of pollution, and is a method suitable for industrial production.
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Paragraph 0028-0030; 0160-0162
(2020/08/18)
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- A new organo-ruthenium substituted tungstotellurate: Synthesis, structural characterization and catalytic properties
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Reaction of [RuC6H6Cl2]2 with TeO2 and Na2WO4·2H2O in aqueous solution (pH 4.7) yielded a novel organo-ruthenium supported tungstotellurate polyanion, [Te2W20O70(RuC6H6)2]8- (Ru-1), which is composed of two [RuC6H6]2+ units linked to a [Te2W20O70]12- fragment through Ru-O(W) bonds resulting in an assembly with idealized C2h symmetry. Furthermore, the polyanion Ru-1 was anchored on 3-aminopropyltriethoxysilane (apts)-modified SBA-15 to prepare new catalysts (SBA-15-apts-Ru-1) containing different amounts of Ru-1, which were characterized using powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2-adsorption measurement and Fourier transform infrared reflectance (FT-IR) spectroscopy. Finally, the catalytic activity of SBA-15-apts-Ru-1 was evaluated for the aerobic oxidation of n-tetradecane using air as the oxidant in the absence of any additives or solvents. In addition, the optimum catalytic reaction conditions were also determined.
- Zheng, Da-Ming,Wang, Rui-Qiang,Du, Yu,Hou, Guang-Feng,Wu, Li-Xin,Bi, Li-Hua
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p. 8829 - 8836
(2016/10/11)
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- A general method for the direct transformation of common tertiary amides into ketones and amines by addition of Grignard reagents
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The direct transformation of amides into ketones by addition of organometallic reagents has attracted the attention of organic chemists for a long time. However limited methods are reliable for common amides and have found synthetic applications. Here we report a method featuring in situ activation of tertiary amides with triflic anhydride (Tf2O) followed by addition of Grignard reagents. The method displays a good generality in scope for both amides and Grignard reagents, and it can be viewed as the acylation of Grignard reagents using amides as stable and selective acylating agents. Moreover, this deaminative alkylation reaction provides a mild method for the N-Deacylation of amides to give free amines.
- Huang, Pei-Qiang,Wang, Yu,Xiao, Kai-Jiong,Huang, Ying-Hong
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p. 4248 - 4254
(2015/06/02)
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- Convenient Synthesis of Functionalized Dialkyl Ketones and Alkanoylsilanes: 1-(Benzotriazol-1-yl)-1-phenoxyalkanes as Alkanoyl Anion Equivalents
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(Benzotriazol-1-yl)-1-phenoxyalkanes 10, prepared by two-step transformations of the corresponding aldehydes, are readily deprotonated at the methine group by BuLi.Subsequent reactions with alkyl halides, aldehydes, ketones, and imines yield the corresponding substituted derivatives that undergo hydrolysis under acidic conditions to afford the expected functionalized ketones 13, 15, 17, 19, 21, 24 and 25.Two successive lithiations of (benzotriazolyl)phenoxymethane, each followed by reaction with a trialkylsilyl chloride, alkyl halide, aldehyde, or ketone, generate similar intermediates 27, 39, 31, 33, and 36.Subsequent hydrolyses of 27, 29, 31, 33, and 36 yield the functionalized ketones 28, 30, and 32 and the alkanoylsilanes 34 and 37 in good yields.
- Katritzky, Alan R.,Lang, Hengyuan,Wang, Zuoquan,Lie, Zhu
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p. 7551 - 7557
(2007/10/03)
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- Hyperfine Structures of Doxyl-Labeled n-Alkyl Chains by NMR and EPR
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The proton hyperfine coupling constants in a series of n-alkyl chains with a doxyl group attached at various points from the end of the chain have been measured by NMR and EPR spectroscopies.The hyperfine structure shows no further change when the attachment point is four or more carbon-carbon bonds from the end of the chain.The high resolution afforded by 500 MHz NMR reveals small magnetic inequivalencies in the chain methylene hyperfine coupling constants located at the same distance from the attachment point.Protons in the same chain methylene group are shown to have different hyperfine coupling constants while protons on different chain methylene groups, symmetrically placed with respect to attachment point, are the same, in every case except one.EPR spectra simulated from hyperfine coupling constants derived from NMR are in excellent agreement with experiment.Inhomogeneous EPR line broadening is found to be in excellent agreement with a previously derived universal hyperfine pattern (B.L.Bales, in "Biological Magnetic Resonance" (L.J.Berliner and J.Reuben, Eds.), Vol. 8, p. 77, Plenum, New York, 1989), so no new correction procedures are necessary.Strategies for selectively deuterating n-alkyl spin probes are developed and compared with some results taken from the literature.Deuterating the chain methylene groups two to three carbon-carbon bonds from the attachment point is necessary for the maximum gain in resolution and sensitivity.
- Bales, Barney L.,Mareno, Donna,Harris, Francis L.
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- Chemoselectivity in the ruthenium-catalyzed redox isomerization of allyl alcohols
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Adjustment of oxidation level by internal hydrogen reorganization represents a highly efficient synthetic protocol. Cyclopentadienylbis(triphenylphosphine)ruthenium chloride in the presence of triethylammonium hexafluorophosphate catalyzes the redox isomerization of allyl alcohols to their saturated aldehydes or ketones. High chemoselectivity is observed since simple primary and secondary alcohols and isolated double bonds are not affected by this catalyst. The reaction is sensitive to the degree of substitution on the double bond and requires relatively unhindered olefins. Switching to indenylbis(triphenylphosphine)ruthenium chloride in the presence of triethylammonium hexafluorophosphate significantly expands the scope of the reaction to substrates bearing more substituted olefinic linkages and to cyclic substrates of rings containing eight or more members. The mechanism is probed by deuterium labeling, which shows that the metal catalyzes an intramolecular 1,3-hydrogen shift of the carbinol hydrogen to the terminal olefinic position.
- Trost, Barry M.,Kulawiec, Robert J.
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p. 2027 - 2036
(2007/10/02)
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- A chemoselective internal redox of allyl alcohols to saturated aldehydes or ketones
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Cp(Ph3P)2RuCl efficiently isomerizes allyl alcohols to saturated aldehydes or ketones even in the presence of other olefins and saturated alcohols.
- Trost, Barry M.,Kulawiec, Robert J.
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p. 3039 - 3042
(2007/10/02)
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- A SIMPLE WAY TO SOME KETONE HOMOENOLATES
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Under basic conditions 1-alkene-3-ols were converted into ketone homoenolates which led to β-alkylated ketones.
- Cuvigny, Therese,Julia, Marc,Jullien, Ludovic,Rolando, Christian
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p. 2587 - 2590
(2007/10/02)
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- Alkylidenation of Ester Carbonyl Groups by means of a Reagent Derived from RCHBr2, Zn, TiCl4, and TMEDA. Stereoselective Preparation of (Z)-Alkenyl Ethers
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Reagents prepared by reduction of 1,1-dibromoalkanes (R3CHBr2) with zinc and TiCl4 in the presence of N,N,N',N'-tetramethylethylenediamine in THF are effective in the conversion of esters (R1CO2R2) to the corresponding alkenyl ethers (R1(R2O)C=CHR3) with high Z selectivity.
- Okazoe, Takashi,Takai, Kazuhiko,Oshima, Koichiro,Utimoto, Kiitiro
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p. 4410 - 4412
(2007/10/02)
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