3006-82-4Relevant articles and documents
Method for synthesizing alkyl peroxycarboxylate by using titanium silicalite molecular sieve composite catalyst
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Paragraph 0057-0062, (2021/04/10)
The invention relates to a method for synthesizing alkyl peroxycarboxylate by using a titanium silicalite molecular sieve composite catalyst, and belongs to the technical field of peroxide production. The method overcomes the defects in the prior art, and adopts the titanium silicalite molecular sieve and aluminosilicate molecular sieve composite catalyst to synthesize the alkyl peroxycarboxylate. In the chemical reaction process that tert-butyl hydroperoxide or tert-amyl hydroperoxide reacts with carboxylic acid to generate tert-butyl peroxycarboxylate or tert-amyl peroxycarboxylate, reaction water is generated. The reaction water needs to be removed from the reaction mixture in time. Azeotropic distillation and molecular distillation dehydration are generally adopted. However, these process operations require a high temperature, and are not conducive to the stabilization and safety of alkyl peroxycarboxylate. The catalyst disclosed by the invention contains the aluminosilicate molecular sieve, so that water generated by reaction can be adsorbed in time, and the synthesis reaction can be smoothly completed.
Bu4NI-Catalyzed, Radical-Induced Regioselective N-Alkylations and Arylations of Tetrazoles Using Organic Peroxides/Peresters
Ghosh, Subhendu,Mir, Bilal Ahmad,Patel, Bhisma K.,Rajamanickam, Suresh,Sah, Chitranjan,Sethi, Garima,Venkataramani, Sugumar,Yadav, Vinita
, p. 2118 - 2141 (2020/03/13)
Bu4NI-catalyzed regioselective N2-methylation, N2-Alkylation, and N2-Arylation of tetrazoles have been achieved using tert-butyl hydroperoxide (TBHP) as the methyl source, alkyl diacyl peroxides as the primary alkyl source, alkyl peresters as the secondary and tertiary alkyl sources, and aryl diacyl peroxides as the arylating source. These reactions proceed without pre-functionalization of tetrazole and in the absence of any metal catalysts. Here, peroxides serve the dual role of oxidants as well as alkylating or arylating agents. Based on DFT calculations, it was found that spin density, transition-state barriers (kinetic control), and thermodynamic stability of the products (thermodynamic control) play essential roles in the observed regioselectivity during N-Alkylation. This radical-mediated process is amenable to a broad range of substrates and provides products in moderate to good yields.
Iron-Catalyzed Radical Decarboxylative Oxyalkylation of Terminal Alkynes with Alkyl Peroxides
Zhu, Xiaotao,Ye, Changqing,Li, Yajun,Bao, Hongli
supporting information, p. 10254 - 10258 (2017/08/07)
An iron-catalyzed oxyalkylation of alkynes with alkyl peroxides as the alkylating reagents has been investigated. Alkyl peroxides are readily available from aliphatic acids and serve simultaneously as the alkylating reagents and internal oxidants. Primary, secondary, and tertiary alkyl groups of aliphatic acids were readily incorporated into C?C triple bonds and diverse α-alkylated ketones were synthesized. Mechanism studies revealed that this reaction involves highly reactive alkyl free radicals. A unique equilibrium between lauric acid and water catalyzed by the iron(III) catalyst was observed.