scholarly journals Influence of hydroperoxide epoxidation reaction conditions of octen-1 on the process of Mo2B activation and on the selectivity of epoxide formation

2020 ◽  
Vol 3 (2) ◽  
pp. 7-10
Author(s):  
Z. М. Коmarenska ◽  
◽  
М. V. Nykypanchuk ◽  
О. І. Маkota ◽  
L. P. Оliynyk ◽  
...  
Keyword(s):  
Butyl Alcohol ◽  
Reaction Products ◽  
Reaction Conditions ◽  
Initial Concentration ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide ◽  
Tert Butyl Alcohol ◽  
Epoxidation Reaction ◽  
Over Time

A study of the process of activation of molybdenumboride catalyst in the reaction of epoxidation of octene-1 with tert-butyl hydroperoxide and the effect on this process of the initial concentration of octene-1, tert-butyl hydroperoxide and the amount of catalyst in the reaction mixture. As well as reaction products (tert-butyl alcohol and epoxy). It is shown that over time a new amorphous phase is formed on the surface of Mo2B, which actually catalyzes the epoxidation reaction of octene-1 with tert-butyl hydroperoxide. The formation of this phase is the reason for the acceleration of the rate of consumption of hydroperoxide and the selectivity of the formation of epoxide over time.

scholarly journals Mechanism of protection of adenosine from tert-butoxyl radicals and repair of adenosine radicals by α-tocopherol in aqueous solution

2014 ◽  
Vol 7 (1) ◽  
Author(s):  
G. Vijayalakshmmi ◽  
M. Adinarayanna ◽  
P. Jayaprrakash Rao
Keyword(s):  
Aqueous Solution ◽  
Rate Constant ◽  
Butyl Alcohol ◽  
Quantum Yields ◽  
Oh Radicals ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide ◽  
Tert Butyl Alcohol

The rates of oxidation of adenosine and α-tocopherol by tert-butoxyl radicals (t-BuO•) were studied spectrophotometrically. Radicals (t-BuO•) were generated by the photolysis of tert-butyl hydroperoxide (t-BuOOH) in presence of tert-butyl alcohol to scavenge •OH radicals. The rates and the quantum yields () of oxidation of α-tocopherol by t-BuO• radicals were determined in the absence and presence of varying concentrations of adenosine. An increase in the concentration of adenosine was found to decrease the rate of oxidation of α-tocopherol, suggesting that adenosine and α-tocopherol competed for t-BuO• radicals. From competition kinetics, the rate constant of α-tocopherol reaction with t-BuO• was calculated to be 7.29 x 108 dm3 mol-1 s-1. The quantum yields expt and cal values suggested that α-tocopherol not only protected adenosine from t-BuO• radicals, but also repaired adenosine radicals, formed by the reaction of adenosine with t-BuO• radicals.

Influence of tungsten compounds on reaction of 1-octene epoxidation by tert-butyl hydroperoxide and hydroperoxide decomposition

2021 ◽  
Vol 4 (2) ◽  
pp. 23-27
Author(s):  
O. I. Makota ◽  
◽  
L. P. Oliynyk ◽  
Z. М. Komarenska ◽  
◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Tungsten Carbide ◽  
Decomposition Reaction ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Hydroperoxide Decomposition ◽  
Tert Butyl Hydroperoxide ◽  
Epoxidation Reaction ◽  
Tungsten Boride

Catalytic ability of tungsten compounds in the reaction of hydroperoxide epoxidation of 1- octene and tert-butyl hydroperoxide decomposition was investigated. It is shown that the nature of ligand has significant effect on the catalytic activity of tungsten compounds in these reactions. It is established that boride and silicide of tungsten are the best choice for epoxidation reaction, whereas tungsten carbide exhibits poor activity. Tungsten boride is also the most active in the hydroxide decomposition reaction.

Absolute rate constants for hydrocarbon autoxidation. 24. Rate constants and Arrhenius parameters for reaction of tert-butylperoxy radicals with 3-methylpentane

1978 ◽  
Vol 56 (2) ◽  
pp. 170-175 ◽  
Author(s):  
J. A. Howard ◽  
J. H. B. Chenier ◽  
D. A. Holden
Keyword(s):  
Rate Constants ◽  
Arrhenius Equation ◽  
Absolute Rate ◽  
Reaction Products ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
A Value ◽  
Tert Butyl Hydroperoxide ◽  
Reduction With Triphenylphosphine ◽  
Major Reaction

Autoxidation of 3-methylpentane in the presence of tert-butyl hydroperoxide gives, after reduction with triphenylphosphine, 3-methyl-3-pentanol and 3-methyl-2-pentanol as the major reaction products. The overall rate constant for reaction of (CH3)3COO· with this substrate at 30 °C is 0.008 ± 0.001 M−1 s−1 which consists of k/tertiary C—H = 0.007 ± 0.001 M−1 s−1 and k/secondary C—H = 0.0002 ± 0.0001 M−1 s−1. The products from cooxidation of cumene and 3-methylpentane in the presence of tert-butyl hydroperoxide are formed in yields which are consistent with these rate constants relative to a value of 0.16 M−1 s−1 for cumene. The Arrhenius equations for reaction of (CH3)3COO• with the t-C—H and s-C—H of 3-methylpentane relative to the Arrhenius equation for reaction of (CH3)3COO• with cumene (log (k10/M−1 s−1) = (8.7 ± 0.3) − (13.2 ± 0.4)/θ) are[Formula: see text]respectively, where θ = 2.303 RT kcal mol−1.

Metal-Free Oxidative Coupling of Tetrahydroisoquinolines and 3-Fluorooxindoles on Water

Synthesis ◽  
2019 ◽  
Vol 52 (03) ◽  
pp. 471-478
Author(s):  
Jian Ji ◽  
Ling-Yan Chen ◽  
Zi-Bin Qiu ◽  
Xinfeng Ren ◽  
Ya Li
Keyword(s):  
Oxidative Coupling ◽  
Reaction Conditions ◽  
Butyl Hydroperoxide ◽  
Metal Free ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide

An efficient, metal-free oxidative coupling of tetrahydroisoquinolines and 3-fluorooxindoles on water has been developed. Using aqueous tert-butyl hydroperoxide as the oxidant, Et3N as the base, and water as the sole solvent, a variety of 3-fluorooxindoles fully substituted at the 3-position and containing a tetrahydroisoquinoline fragment has been successfully prepared in yields of up to 93% with an anti/syn stereo­selectivity of up to 99:1 under very mild and safe reaction conditions.

Tetrabutylammonium Iodide Catalyzed Epoxidation of Naphthoquinone Derivatives with tert-Butyl Hydroperoxide as an Oxidant

Synthesis ◽  
2017 ◽  
Vol 49 (17) ◽  
pp. 4017-4024 ◽  
Author(s):  
Bai-Ru Ai ◽  
Xu-Ling Chen ◽  
Yu Dong ◽  
Lei Tang ◽  
Ji-Yu Wang
Keyword(s):  
Reaction Time ◽  
Silicon Dioxide ◽  
Environmentally Benign ◽  
Reaction Conditions ◽  
Short Reaction Time ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide ◽  
Tetrabutylammonium Iodide ◽  
High Yields

An efficient and environmentally benign procedure has been developed for the epoxidation of naphthoquinone derivatives by using tetrabutylammonium iodide as a catalyst and tert-butyl hydroperoxide as an oxidant in the presence of silicon dioxide. This protocol, which provides a facile base-free methodology for the synthesis of some new naphthoquinone-based epoxides, features mild reaction conditions, high yields, remarkably short reaction time, and broad substrate scope

Research on Oxidation of Phenanthrene to Phenanthrenequinone with TBHP

2013 ◽  
Vol 690-693 ◽  
pp. 1256-1260
Author(s):  
Ying Ji Luo ◽  
Zu Yu Liu
Keyword(s):  
Reaction Time ◽  
Butyl Alcohol ◽  
Orthogonal Test ◽  
Molar Ratio ◽  
Optimum Conditions ◽  
Reaction Conditions ◽  
Technical Parameters ◽  
Tert Butyl ◽  
Preparation Conditions ◽  
Tert Butyl Alcohol

The oxidation of phenanthrene with TBHP into phenanthrenequinone has been studied. Reaction conditions were investigated by orthogonal test, and main technical parameters optimized. The optimum preparation conditions of TBHP were as follows: molar ratio of H2O2 to tert-butyl alcohol: 2:1; molar ratio of H2SO4 to tert-butyl alcohol: 0.4:1; reaction temperature: 60°C; reaction time: 4 h. And for the preparation of phenanthrenequinone the optimum conditions: molar ratio of TBHP to phenanthrene: 5:1; MoO2(acac)2 (catalyster) content: 0.05g(per 5g phenanthrene); reaction time: 4h.

Carbaporphyrins, porphyrin isomers and the legacy of Emanuel Vogel

2012 ◽  
Vol 16 (05n06) ◽  
pp. 423-433 ◽  
Author(s):  
Timothy D. Lash
Keyword(s):  
Strong Support ◽  
Butyl Alcohol ◽  
Electron Delocalization ◽  
Cope Rearrangement ◽  
Tert Butyl ◽  
New Class ◽  
Tert Butyl Hydroperoxide ◽  
Tert Butyl Alcohol ◽  
Carbocyclic Rings ◽  
The Impact

Vogel discovered a large number of bridged annulene structures, including constitutional porphyrin isomers, heteroporphyrinoid species such as the tetraoxaporphyrin dication, corrole isomers and novel expanded porphyrinoid systems. In this review, the impact of Vogel's work on the author's research program is discussed. Carbaporphyrinoid systems with one or two carbocyclic rings replacing the usual pyrrole subunits have been synthesized and their diatropic characteristics can be related to the presence of 18π electron delocalization pathways within these macrocycles. The preparation of a dideazaporphyrin also provides strong support for the concept, espoused by Vogel, that porphyrins are examples of bridged annulenes. Ring contractions of azuliporphyrins to benzocarbaporphyrins with tert-butyl hydroperoxide in the presence of base have been proposed to involve a Cope rearrangement where a cycloheptatriene unit rearranges to give a norcaradiene-fused carbaporphyrinoid, followed elimination of tert-butyl alcohol, and Vogel's investigations into these types of valence tautomerization processes provides insights into these unusual transformations. In addition, a new class of porphyrin isomers has been synthesized and these porphyrin analogs extend the observations previously made for N-confused porphyrins and Vogel's constitutional isomers.

Metal-Free Ammonium Iodide Catalyzed Oxidative Dehydrocoupling of Silanes with Alcohols

Synlett ◽  
2017 ◽  
Vol 28 (13) ◽  
pp. 1620-1623 ◽  
Author(s):  
Pailla Kumar ◽  
Sheng-rong Guo ◽  
Yan-qin Yuan
Keyword(s):  
Transition Metal ◽  
Oxidative Coupling ◽  
Ammonium Iodide ◽  
Reaction Conditions ◽  
Butyl Hydroperoxide ◽  
Metal Free ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide ◽  
Free Ammonium

An ammonium iodide catalyzed direct oxidative coupling of silanes with alcohols to give various alkoxysilane derivatives was discovered. tert-Butyl hydroperoxide proved to be an efficient oxidant for this transformation. Attractive features of this protocol include its transition-metal-free nature and the mild reaction conditions.

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