The reactions of acetone, 2,2,2-trifluoroacetone and hexafluoroacetone in methanesulfonic (MSA) and triflic acids (TFSA) with benzene have been studied at M06-2X/6-311+G(d,p) level using cluster-continuum model, where the carbonyl group is explicitly solvated by acid molecules. The introduction of a trifluoromethyl group into the ketone structure reduces the activation energy of the tetrahedral intermediates formation due to an increase of the electrophilicity of the carbonyl group and raises the activation and the reaction energies of the C-O bond cleavage in formed carbinol due to the destabilization of the corresponding carbocation. The introduction of the second trifluoromethyl group inhibits the hydroxyalkylation reaction due to a very strong increase of the reaction and activation energies of the C-O bond cleavage which becomes the rate determining step. The most important catalytic effect of TFSA compared to MSA is not the protonation of the ketone carbonyl, but the reduction of the activation and reaction energies of the carbinol C-O bond cleavage due to better protosolvation properties. Even for TFSA no complete proton transfer to carbonyl oxygen has been observed for free ketones. Therefore, the protonation energies of free ketones cannot be considered as a measure of ketone reactivity in the hydroxyalkylation reaction.
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http://dx.doi.org/10.1007/s00894-012-1610-1 | DOI Listing |
Nat Commun
December 2024
State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao, China.
Catalytic upcycling of polyethylene terephthalate (PET) into high-value oxygenated products is a fascinating process, yet it remains challenging. Here, we present a one-step tandem strategy to realize the thermal catalytic oxidation upcycling of PET to terephthalic acid (TPA) and high-value glycolic acid (GA) instead of ethylene glycol (EG). By using the Au/NiO with rich oxygen vacancies as catalyst, we successfully accelerate the hydrolysis of PET, accompanied by obtaining 99% TPA yield and 87.
View Article and Find Full Text PDFEnviron Technol
December 2024
School of Environmental Science and Engineering, Southwest Jiaotong University, Chengdu, People's Republic of China.
Ascorbic acid (AA) was used as a reducing agent to improve the Fe(III)-activated peracetic acid (PAA) system for the removal of sulfamethoxazole (SMX) in this work. The efficiency, influencing factors and mechanism of SMX elimination in the AA/Fe(III)/PAA process were studied. The results exhibited that AA facilitated the reduction of Fe(III) to Fe(II) and subsequently improved the activation of PAA and HO.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
East China Normal University, School of Chemistry and Molecular Engineering, 3663 N. Zhongshan Rd., 200062, Shanghai, CHINA.
We present a novel electrochemical dicarboxylation of epoxides with CO2, characterized by the cleavage of two C-O single bonds. Not only are vinyl epoxides viable, but cyclic carbonates also serve as effective substrates, facilitating the synthesis of E-configured adipic and octanedioic acids with high chemo-, regio-, and stereoselectivity. The synthetic practicality is further highlighted by the diverse functionalizations of the resulting multifunctional diacids.
View Article and Find Full Text PDFSoins Psychiatr
December 2024
Un chez-soi d'abord 92, c/o Soins Psychiatrie, 65 rue Camille-Desmoulins, 92442 Issy-les-Moulineaux, France.
The "Un chez-soi d'abord" scheme aims to provide independent housing for homeless people diagnosed with psychosis. The "tenants" are supported by a medical-social team, who come to meet them on a weekly basis to help them access and maintain their home. While psychiatric pathology is taken into account, the approach is essentially focused on recovery.
View Article and Find Full Text PDFOrg Lett
December 2024
University of Belgrade, Faculty of Chemistry, Studentski trg 16, P.O. Box 51, 11158 Belgrade 118, Serbia.
A rhodium-catalyzed reaction of thioesters with diazo reagents was recognized as a powerful and unprecedented tool for single-atom molecular editing by the insertion of a single carbon atom into the C(O)─S thioester bond, thereby leading to various α-thioketones possessing a quaternary carbon atom. A selective and precise defunctionalization of the polyfunctionalized products further demonstrated the synthetic utility of the reaction for the synthesis of more common structural classes of compounds.
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