Oxidation of Heteroleptic Diarylpalladium Compounds withtert-Butyl Hydroperoxide. Substituent Effects in Aromatic Oxidation Reactions

1996 ◽  
Vol 15 (21) ◽  
pp. 4366-4372 ◽  
Author(s):  
Jean-Marc Valk ◽  
Jaap Boersma ◽  
Gerard van Koten
Keyword(s):  
Substituent Effects ◽  
Oxidation Reactions ◽  
Butyl Hydroperoxide

Oxidation reactions of acetylenic fatty esters with selenium dioxide/tert-butyl hydroperoxide

Lipids ◽  
1997 ◽  
Vol 32 (10) ◽  
pp. 1119-1123 ◽  
Author(s):  
Marcel S. F. Lie Ken Jie ◽  
Mohammed Khysar Pasha ◽  
Mohammad Shahin Alam
Keyword(s):  
Selenium Dioxide ◽  
Oxidation Reactions ◽  
Fatty Esters ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide

Substituent Effects in Dioxovanadium(V) Schiff-base Complexes: Tuning the Outcomes of Oxidation Reactions

Polyhedron ◽  
2021 ◽  
pp. 115268
Author(s):  
Vanessa P. McCaffrey ◽  
Olivia Q. Conover ◽  
Michael A. Bernard ◽  
Jonathan T. Yarranton ◽  
Nicholas R. Lessnau ◽  
...  
Keyword(s):  
Schiff Base ◽  
Substituent Effects ◽  
Schiff Base Complexes ◽  
Oxidation Reactions

The photochemical decomposition of t -butyl hydroperoxide in solution

1953 ◽  
Vol 220 (1142) ◽  
pp. 322-339 ◽  
Keyword(s):  
Quantum Yield ◽  
Wave Length ◽  
Butyl Alcohol ◽  
Quantum Yields ◽  
Oxidation Reactions ◽  
Butyl Hydroperoxide ◽  
Acetone Water ◽  
Photochemical Decomposition ◽  
Solvent Molecules ◽  
A Chain

The photochemical decomposition of t -butyl hydroperoxide by light of wave-length 3130 Å has been investigated in three solvents. Reaction mechanisms are elucidated by consideration of the products and the quantum yields of decomposition. In carbon tetrachloride a chain reaction occurs in which the quantum yield of 3.2 at 20° C increases to 5.3 at 50° C. The main products are t -butyl alcohol and oxygen with smaller amounts of acetone, water and compounds arising from the oxidation of methyl radicals. The same series of reactions takes place in n -hexane, but superimposed are oxidation reactions involving solvent molecules which ultimately lead to the formation of alcohols. The quantum yield in this solvent is 3.9 and independent of temperature. When the peroxide is irradiated in dioxan solution immediate hydrogenation of the radicals produced in the primary photo-chemical act prevents the formation of reaction chains and the quantum yield is unity. The interaction of the radicals with solvent molecules is such that some of the etheric oxygen of the dioxan is transformed into alcoholic hydroxyl during the course of the reaction, and the fragmentation of dioxan gives formaldehyde Experiments with a dioxan solution using light of wave-length 2450 to 2800 Å show no fundamental change in the mode of decomposition of the peroxide, but an increase in concentration of the products of dioxan decomposition indicates a more vigorous attack by the radicals on the solvent.

Dioxotungsten(vi) complexes with isoniazid-related hydrazones as (pre)catalysts for olefin epoxidation: solvent and ligand substituent effects

RSC Advances ◽  
2016 ◽  
Vol 6 (43) ◽  
pp. 36384-36393 ◽  
Author(s):  
Višnja Vrdoljak ◽  
Jana Pisk ◽  
Biserka Prugovečki ◽  
Dominique Agustin ◽  
Predrag Novak ◽  
...  
Keyword(s):  
Substituent Effects ◽  
Olefin Epoxidation ◽  
Butyl Hydroperoxide ◽  
Catalytic Performances

The catalytic performances (activity and selectivity) of the mononuclear dioxotungsten(vi) complexes [WO2(LR)(D)] towards alkene epoxidation by tert-butyl hydroperoxide (TBHP) were investigated under different conditions.

Fluorous biphasic catalysis. 2. Synthesis of fluoroponytailed amine ligands along with fluoroponytailed carboxylate synthons, [M(C8F17(CH2)2CO2)2] (M = Mn2+ or Co2+): Demonstration of a perfluoroheptane soluble precatalyst for alkane and alkene functionalization in the presence of tert-butyl hydroperoxide and oxygen gas

2001 ◽  
Vol 79 (5-6) ◽  
pp. 888-895 ◽  
Author(s):  
Jean-Marc Vincent ◽  
Alain Rabion ◽  
Vittal K Yachandra ◽  
Richard H Fish
Keyword(s):  
Oxidation Reactions ◽  
Biphasic Catalysis ◽  
Alkene Oxidation ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide ◽  
Spin Resonance ◽  
Soluble Ligand ◽  
Fluorous Biphasic Catalysis

Fluorous biphasic catalysis (FBC) is a relatively new concept for homogeneous catalysis where the fluorocarbon soluble catalyst resides in a separate phase from the substrate and products. Therefore, separation of the catalyst and the products occurs by a facile decantation process. In this contribution, we present the synthesis of new Rf-fluoroponytailed synthons, 2-iodo-1-perfluorooctyl-3-propanol (1), 3-perfluorooctyl-1-propanol (2), and 3-perfluorooctyl-1-iodopropane (3), a variety of new Rf-fluoroponytailed ligands (4–8), with starting amines, 1,4,7-triazacyclononane, bis-picolylamine, and bis-picolylaminoethylenediamine, as well as new RfMn2+ and RfCo2+ fluoroponytailed carboxylate synthons, [Mn(O2C(CH2)2C8F17)2] (9), and [Co(O2C(CH2)2C8F17)2] (10), where Rf is C8F17. The only totally perfluoralkane soluble ligand we found was 1,4,7-tris-N-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecyl)-1,4,7-triazacyclononane (RfTACN, 4), and it was utilized, along with synthons 9 and 10, to generate in situ RfMn2+–RfTACN and RfCo2+–RfTACN complexes as precatalysts for functionalization of alkanes and alkenes. We will demonstrate that indeed this novel FBC approach for the separation of the precatalyst from the substrates and (or) products is viable for oxidation of alkanes and alkenes in the presence of the necessary oxidants, tert-butyl hydroperoxide (TBHP), and O2 gas. We will also show that these oxidation reactions occur via an autoxidation mechanism under our FBC conditions, while using electron spin resonance (ESR) techniques to ascertain the redox chemistry occurring with the starting mononuclear RfMn2+–RfTACN complex.Key words: fluorous solvents, biphasic catalysis, alkane/alkene oxidation.

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