96-04-8Relevant articles and documents
A Bifunctional Iron Nanocomposite Catalyst for Efficient Oxidation of Alkenes to Ketones and 1,2-Diketones
Ma, Zhiming,Ren, Peng,Song, Tao,Xiao, Jianliang,Yang, Yong,Yuan, Youzhu
, p. 4617 - 4629 (2020/05/19)
We herein report the fabrication of a bifunctional iron nanocomposite catalyst, in which two catalytically active sites of Fe-Nx and Fe phosphate, as oxidation and Lewis acid sites, were simultaneously integrated into a hierarchical N,P-dual doped porous carbon. As a bifunctional catalyst, it exhibited high efficiency for direct oxidative cleavage of alkenes into ketones or their oxidation into 1,2-diketones with a broad substrate scope and high functional group tolerance using TBHP as the oxidant in water under mild reaction conditions. Furthermore, it could be easily recovered for successive recycling without appreciable loss of activity. Mechanistic studies disclose that the direct oxidation of alkenes proceeds via the formation of an epoxide as intermediate followed by either acid-catalyzed Meinwald rearrangement to give ketones with one carbon shorter or nucleophilic ring-opening to generate 1,2-diketones in a cascade manner. This study not only opens up a fancy pathway in the rational design of Fe-N-C catalysts but also offers a simple and efficient method for accessing industrially important ketones and 1,2-diketones from alkenes in a cost-effective and environmentally benign fashion.
METHOD FOR PRODUCING OXIDE
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Paragraph 0090; 0097, (2018/10/16)
PROBLEM TO BE SOLVED: To provide a method for producing an oxide capable of easily producing an oxide excellent in substrate selectivity with a high yield, which allows the reaction to proceed without using a solvent under moderate conditions at 100°C or less. SOLUTION: There is provided a method for producing an oxide by oxidizing a substrate (A) in the presence of a compound selected from oxygen, ozone and a radical generator to obtain a corresponding oxide. The radical generator preferably includes at least one compound selected from a nitroxy-based radical generator and an azo-based radical generator. In addition, the oxidation reaction is preferably carried out in the presence of a metal compound containing at least one metal element selected from cobalt, manganese, zirconium and molybdenum. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPO&INPIT
Regiospecific synthesis of α-diones, α,α-dialkoxyketones and α-alkoxy-α-sulfenylated ketones
Tehrani,Boeykens,Tyvorskii,Kulinkovich,De Kimpe
, p. 6541 - 6548 (2007/10/03)
A convenient synthesis of α-diones and their monoprotected acetals, i.e. α-ketoacetals, was developed by mercury induced solvolysis of regiospecifically formed α-chloro-α-(alkylthio)ketones. Analogously, α-alkoxy-α-sulfenylated ketones were formed when reacting α-chloro-α-sulfenylated ketones with an alkaline alcoholic medium, α-Alkoxy-α-sulfenylated ketones themselves could be transformed into α-diones or ?-ketoacetals, which in turn were hydrolyzed under anhydrous conditions into the corresponding α-diones. (C) 2000 Elsevier Science Ltd.
Synthesis of α-diketones from α,β-dihydroxy ketones
Kang,Park,Rho,Han
, p. 2219 - 2224 (2007/10/02)
Treatment of α,β-dihydroxy ketones with carbonyldiimidazole resulted in the formation of α-diketones based on the elimination of the cyclic carbonates formed in situ.
Synthesis of α-Diketones by Direct, Low-temperature, in Situ Nucleophilic Acylation of Esters by Acyllithium Reagents
Seyferth, Dietmar,Weinstein, Robert M.,Hui, Richard C.,Wang, Wei-Liang,Archer, Colin M.
, p. 5768 - 5773 (2007/10/02)
Addition of n-, sec-, or tert-butyllithium to a CO-saturated solution of an ester, R'CO2R'' in a solvent system of 4:4:1 (by volume) THF/Et2O/pentane at -110 deg C (or at -135 deg C in 3:1 (by volume) Me2O/THF), followed by hydrolysis with saturated aqueous NH4Cl, results in the formation of α-diketones, BuC(O)C(O)R', yellow liquids, in good yield.Similar reactions with diethyl succinate gave in one instance both t-BuC(O)C(O)CH2CH2CO2Et and t-BuC(O)C(O)CH2CH2C(O)C(O)Bu-t.The monoacylation product of dimethyl oxalate, t-BuC(O)C(O)CO2Me, readily formed a crystalline hydrate, t-BuC(O)C(OH)2CO2Me.
Trimethylsilyl Cyanide - A Reagent for Umpolung, IX. Enol Esters of Acyl Cyanides: Syntheses and General Properties
Hertenstein, Ulrich,Huenig, Siegfried,Reichelt, Helmut,Schaller, Rainer
, p. 699 - 721 (2007/10/02)
According to Scheme 1 acyl cyanide-enol sulfonates 3-5, carboxylates 7-9, and phosphates 12 are synthesized on routes A-D in generally good yields.Judged by 13C NMR chemical shifts of C-3, the donor effect of the enol groups on the C=C bond decreases slightly in the order OP(O)(OEt)2 > OCO2Et > OCOCH3 > OCOCF3 > OSO2Me OSO2Ph > OSO2C4F9, but being always larger than the acceptor effect of the CN group.Reactions with nucleophiles to give 1,2-diketones (29, 30) and with radicals to form adducts 32 and 35 are described.Depending on the substituent pattern , and cycloadditions can be performed with 2f, 5f, and 12f.Different cyclopropanes 54 can be prepared from 5f.
High-Yield Acyl Anion Trapping Reactions: Syntheses of α-Hydroxy Ketones and 1,2-Diketones
Seyferth, Dietmar,Weinstein, Robert M.,Wang, Wei-Liang
, p. 1144 - 1146 (2007/10/02)
The in situ generation of n-C4H9C(O)Li by the reaction of n-C4H9Li with CO at -110 deg C in the presence of ketones gives good (50-90percent) yields of α-hydroxy ketones.When the n-C4H9C(O)Li reaction is carried out in the presence of esters, good (65-80percent) yields of α-diketones are obtained, thus demonstrating that RC(O)Li can be reagents of practical utility.Similar reactions were observed with sec-C4H9Li and tert-C4H9Li.
