Reactions of tert-Butyl Peroxy Esters, XIV. Further Observations on the Preparation of Dialkyl tert-Butylperoxy Phosphates

1975 ◽  
Vol 30 (9-10) ◽  
pp. 732-739 ◽  
Author(s):  
G. Sosnovsky ◽  
E. H. Zaret
Keyword(s):  
Potassium Hydroxide ◽  
Potassium Hydroxide Solution ◽  
Sodium Hydride ◽  
High Yield ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide ◽  
Aqueous Potassium Hydroxide ◽  
Butyl Peroxide

The preparation of dialkyl tert-butylperoxy phosphates (2, R = alkyl) has been achieved by the reaction of the corresponding dialkyl phosphorochloridates (1, R = alkyl) with tert-butyl hydroperoxide either in the presence of pyridine or in the presence of aqueous potassium hydroxide solution. Neither of these routes is suitable for the preparation of dialkyl tert-butylperoxy phosphates in quantity since they yield peroxyphosphates which are contaminated either with the corresponding tetraalkyl pyrophosphates or dialkyl phosphates; the contaminants cannot easily be removed by conventional means from the peroxyphosphates. The method of choice for the preparation in high yield of large quantities of pure dialkyl tert-butylperoxy phosphates involves the interaction of the corresponding dialkyl phosphorochloridate with sodium tert-butyl peroxide which has been prepared in situ from the reaction of tert-butyl hydroperoxide with sodium hydride.

scholarly journals α-Acetoxyarone synthesis via iodine-catalyzed and tert-butyl hydroperoxide-mediateded self-intermolecular oxidative coupling of aryl ketones

2017 ◽  
Vol 13 ◽  
pp. 1079-1084 ◽  
Author(s):  
Liquan Tan ◽  
Cui Chen ◽  
Weibing Liu
Keyword(s):  
Oxidative Coupling ◽  
Optimum Conditions ◽  
Butyl Hydroperoxide ◽  
Metal Free ◽  
Tert Butyl ◽  
Radical Intermediates ◽  
Tert Butyl Hydroperoxide ◽  
Aryl Ketones

We present a metal-free method for α-acetoxyarone synthesis by self-intermolecular oxidative coupling of aryl ketones using I2−tert-butyl hydroperoxide (TBHP). Under the optimum conditions, various aryl ketones gave the corresponding products in moderate to excellent yields. A series of control experiments were performed; the results suggest the involvement of radical pathways. Multiple radical intermediates were generated in situ and the overall process involved several different reactions, which proceeded self-sequentially in a single reactor. A labeling experiment using 18O-labeled H2O confirmed that the oxygen in the product was derived from TBHP, not from H2O in the TBHP solvent.

Copper-Catalyzed γ-Cyanation of Aza-Baylis–Hillman Adducts Using Trimethylsilyl Cyanide

Synlett ◽  
2015 ◽  
Vol 26 (08) ◽  
pp. 1026-1030 ◽  
Author(s):  
Lal Yadav ◽  
Arvind Yadav
Keyword(s):  
Nucleophilic Attack ◽  
Tertiary Amines ◽  
Butyl Hydroperoxide ◽  
Trimethylsilyl Cyanide ◽  
Tert Butyl ◽  
Ion Formation ◽  
Tert Butyl Hydroperoxide ◽  
Iminium Ion ◽  
In Situ Formation

A copper-catalyzed γ-cyanation of aza-Baylis–Hillman adducts via iminium ion formation adjacent to benzylic tertiary amines has been developed using tert-butyl hydroperoxide (TBHP) as the external oxidant. The protocol involves in situ formation of 4π-conjugated iminium ion intermediates that undergo nucleophilic attack by cyanide to provide valuable γ-cyanated α,β-unsaturated amines.

Reaction of Hypochlorous Acid with Hydrogen Peroxide and tert-Butyl Hydroperoxide. 1H NMR Spectroscopy and Chemiluminescence Analyses

1996 ◽  
Vol 51 (5-6) ◽  
pp. 386-394 ◽  
Author(s):  
Jürgen Arnhold ◽  
Oleg M. Panasenko ◽  
Jürgen Schiller ◽  
Klaus Arnold ◽  
Yurij A. Vladimirov ◽  
...  
Keyword(s):  
Hydrogen Peroxide ◽  
Light Intensity ◽  
Singlet Oxygen ◽  
Hypochlorous Acid ◽  
Red Light ◽  
Butyl Hydroperoxide ◽  
Reactant Concentration ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide ◽  
Butyl Peroxide

Abstract In contrast to the well-known reaction of hypochlorous acid with hydrogen peroxide, no singlet oxygen is formed as the result of reaction between hypochlorous acid and tert -butyl hydroperoxide. The reaction with hydrogen peroxide yielded a quadratic dependence of light intensity on reactant concentration, a drastic enhancement of luminescence yield using D2O as solvent and only an emission of red light, that are typical characteristics of emission result­ing from two molecules of delta singlet oxygen. Other chemiluminescence properties were observed using tert-butyl hydroperoxide. There was a linear dependence of light intensity on reactant concentration using rm-butyl hydroperoxide in excess with a decline of emission at higher concentrations. 1H-NMR spectroscopic analysis revealed di-tert-butyl peroxide, tert -butanol and also tert-butyl hypochlorite, acetone and acetate as products of the reaction between hypochlorous acid and tert -butyl hydroperoxide. The formation of di-tert-butyl peroxide is only possible assuming a tert-butyloxy radical as primary intermediate product of this reaction. Our results demonstrate that alkoxy radicals derived from organic hydroperoxides can participate in lipid peroxidation induced by hypochlorous acid. On the other hand, singlet oxygen did not influence the yield of peroxidation products. Changing H2O for D2O in suspension of egg yolk phosphaditylcholine no differences in accumulation of thiobarbituric acid reactive products were observed.

La réaction du diazométhane avec les phénylsulfonyl-4, tert-butyl-4, et phénylthio-4 cyclohexanones

1971 ◽  
Vol 49 (19) ◽  
pp. 3097-3106 ◽  
Author(s):  
H. Favre ◽  
D. Gravel ◽  
Z. Hamlet ◽  
M. Ménard ◽  
J. Temler
Keyword(s):  
Potassium Hydroxide ◽  
Potassium Hydroxide Solution ◽  
Dimethyl Acetal ◽  
Ex Situ ◽  
Epoxide Ring ◽  
Tert Butyl ◽  
First Case ◽  
In Situ Reactions ◽  
In Cis

This paper describes the reaction of diazomethane generated in situ, methanolic potassium hydroxide solution, on 4-phenylsulfonyl, 4-tert-butyl, and 4-phenylthio-cyclohexanones. In the latter two cases, the reaction leads to mixtures containing mostly the enlarged ketones along with minor quantities of the corresponding epoxides. In the first case, the enlarged ketone and the corresponding epoxides are formed in equal amounts. This marked increase in the production of epoxides is indicative of transannular interactions between the sulfonyl group and the intermediate betaine. In the ex situ reactions, methanolic solutions without potassium hydroxide, phenylsulfonylcyclohexanone yields the corresponding dimethyl acetal almost exclusively whereas the tert-butyl and phenylthioketones follow the same course as in the in situ reactions. Furthermore, it has been observed in all cases that, under the conditions used, the potassium hydroxide leads to opening of the epoxide rings to yield hydroxy-ethers of the type [Formula: see text]CH2—O—CH3. This epoxide-ring-opening was advantageously used in the preparation of pure epoxides from epimeric mixtures. The epoxides generated from the three ketones studied are mixtures of cis-trans isomers, rich in cis epimer.

Epoxidation of Soybean Oil with Tert-Butyl Hydroperoxide over Manganese (III) Tetraphenylporphyrin Chloride Catalyst

2012 ◽  
Vol 486 ◽  
pp. 328-333
Author(s):  
Ping Ping Jiang ◽  
Wei Jie Zhang ◽  
Ping Bo Zhang
Keyword(s):  
Soybean Oil ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide ◽  
Acid Effect ◽  
Vis Spectroscopy ◽  
Chloride Catalyst ◽  
Optimum Reaction ◽  
High Valent

A new catalytic route was reported for the epoxidation of soybean oil (SBO) with tert-butyl hydroperoxide (TBHP, 65 wt. %) as the clean oxidant over manganese (III) tetraphenylporphyrin chloride (Mn (TPP) Cl) catalyst without carboxylic acid. Effect of tetraphenylporphyrin chloride with various metals (Mn, Fe, Co, Ni and Zn) on SBO epoxidation has been investigated. As biomimetic catalysts, the optimum reaction temperature of the system existed for catalytic activity, which was about 40 °C. The optimum reaction time was 6 h and the suitable promoter was pyrrole considering various factors. The suitable oxidant was TBHP of 65 wt. %. A mechanism for SBO epoxidation was discussed, and a role for high-valent metal peroxide intermediate with double bond directly as part of this mechanism was proposed, which was verified by in situ UV-Vis spectroscopy. The optimized reaction conditions were acquired.

Heterogeneous oxidation catalysts formed in situ from molybdenum tetracarbonyl complexes and tert-butyl hydroperoxide

2011 ◽  
Vol 395 (1-2) ◽  
pp. 71-77 ◽  
Author(s):  
Patrícia Neves ◽  
Tatiana R. Amarante ◽  
Ana C. Gomes ◽  
Ana C. Coelho ◽  
Sandra Gago ◽  
...  
Keyword(s):  
Oxidation Catalysts ◽  
Heterogeneous Oxidation ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide

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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