Peresters. V.<sup>1</sup> Di-t-butylperoxyoxalate

Bartlett, Paul D.; Benzing, Erhard; Pincock, Richard E.

doi:10.1021/ja01492a055

Cited by 215 publications

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“…The effect of discounting [4] and substituting [5] Using the published value of k6 ( G ) , plotting [ROOH] vs. e-hsl gives straight lines for all of the runs (Fig. 1) and the slopes are proportional to [P]o, the initial concentration of peroxalate (Fig.…”

Section: Resultsmentioning

confidence: 99%

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THE INDUCED DECOMPOSITION OF tert-BUTYL HYDROPEROXIDE

Hiatt¹,

Clipsham²,

Visser³

1964

Can. J. Chem.

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111 a study of the "induced" decomposition of hydroperoxides by allcoxy radicals, tert-butyl hydroperoxide has been decomposed by the action of di-tert-butyl peroxyoxalate a t 45' . The homolytic cleavage of peroxalate to tert-butoxy was unaffected by the presence of hydroperoxide and 7 to 10 molecules of hydroperoxide were destroyed for each radical thus produced. The kinetics have been analyzed and a mechanism developed which has significance for any system containing peroxy radicals.

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Section: Resultsmentioning

confidence: 99%

“…Di-tert-butyl peroxyoxalate decomposes thermally a t low temperatures to tert-butoxy radicals and carbon dioxide (5). At 45 "C, where tert-butyl hydroperoxide is indefinitely stable, the peroxalate has a half-life of about 45 inin.…”

Section: Introductionmentioning

confidence: 99%

THE INDUCED DECOMPOSITION OF tert-BUTYL HYDROPEROXIDE

Hiatt¹,

Clipsham²,

Visser³

1964

Can. J. Chem.

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“…Although the formation of alkyl radicals could not be confirmed by trapping with Tempo, (FeII converts Tempo to the parent hydroxylamine on the FeII-TBHP time scale), the product distributions are again indicative of the intermediacy of 2 O and 3O-adamantyl radicals. [26] When tert-butoxy radicals were generated at 40'C in pyridine by decomposition of pre-formed di-t-butylperoxalate [30] under argon in the presence of adamantane, all the adamantyl radicals were captured by pyridine with a C2/C3 selectivity of 0.28. The same ratio was seen in the presence of oxygen.…”

Section: Use Of T -Butizhydroperoxide (7bhp)mentioning

confidence: 99%

Models for non-heme oxidation enzymes

Barton¹,

Taylor²

1996

Pure and Applied Chemistry

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The Gif systems for the selective functionalization of saturated hydrocarbons based on the reactions of superoxide with Feu and of hydrogen peroxide with FelI1 are described. [l] Both systems are relatively efficient, but not nearly so efficient as the electrochemical system developed in collaboration with Prof. G.Balavoine and Dr. Aurore Gref (Universite de Paris-Sud-Orsay, France).[2] All systems afford main1 ketones. This is an unusual selectivity which implies a non-radical mechanism. It has been proven for the FeIIl H202 system that the activation of the Fe*II is independent of the formation of ketone which comes from oxygen. The intermediate for the ketone is a hydroperoxide (derived from oxygen). [3] Recent mechanistic studies are reported. INI1pODUClTONThere is universal acceptance that the selective functionalization of saturated hydrocarbons is a research challenge of major proportions. Although paraffins are, as their name implies, usually considered to be inert, Nature has solved the problem of their functionalization using complexes of iron and, to a lesser extent of copper. The iron complexes are either heme based, as in the ubiquitous P450 enzymes, or non-heme based, as in the vitally important roline-4-hydroxylase and in the fascinating enzyme, methane monooxygenase. These enzymes contain one FJ1, or two FelI1 atoms bridged by an 0x0 bridge, respectively. Although the protein in these enzymes is responsible for their chemo-and stereo-selectivity, the fundamental activation of the iron should be seen also in appropriate models. Models of P450 enzymes have been known for decades and the work of J.T.Groves is particularly noteworthy in this respect. Models of non-heme iron enzymes are much less familiar and, until our publications on Gif type Chemistry, not efficacious.[5] USE OF SUPEROXIDE AND OF HKDROGEN PEROXIDEOur work started with the assumption that when, 3 billion years ago, the blue-green algae started to make oxygen, a unicellular form of life started to concert the oxidation of iron with the oxidation of saturated hydrocarbons. It is agreed that after 1 billion years of life under reductive conditions, the world was full of saturated hydrocarbons, FeI1 compounds and metallic iron, as well as, an abundance of hydrogen sulfide, since life was using the reduction of sulfate to sulfide as an energy source.So our first experiment to test our hypothesis was the oxidation of adamantane in pyridine with some acetic acid in the presence of iron powder, hydrogen sulfide and oxygen. Surprisingly, a major amount of adamantanone was formed and there was only minor formation of the tertiary alcohol. Later, we obtained the same results when we replaced the iron powder with zinc powder and added a catalytic amount of an FdI salt. This showed the unusual power of the iron species formed to make ketones as principal products. During systematic studies on adamantane oxidation, we examined the effect of reducing oxygen pressure. We were surprised to find that lowering the oxy en pressure increased th...

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“…Di-tert-butyl diperoxyoxalate (DBDP) was obtained by the reported method. 12 1-(4-Hydroxymethylphenyl)-1-(2,2,6,6-tetramethyl-1-piperidinyloxyl) ethane (3) was prepared by our previous procedure. 13 Column chromatographic purification was carried out on silica gel 60 N (Kanto Chemical Co., Inc.).…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Six-Arm Star Polymer by Nitroxide-Mediated “Living” Radical Polymerization

Miura

Yoshida

2002

Polym J

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ABSTRACT:A dendritic multifunctional initiator with 6 TEMPO-based alkoxyamine moieties was prepared from 4-bromophenylethylbenzene in 7 steps and 6-arm star polymers were prepared by the radical polymerization of styrene (St) using the dendritic alkoxyamine as an initiator. The St polymerizations were carried out at 120• C using the dendritic alkoxyamine concentrations of 5.0, 12.8, and 18.8 mmol L −1 . When the alkoxyamine concentration was 5.0 mmol L −1 , the polydispersity indexes of the resulting star polymers increased with conversion and that of the star polymer at 72% conversion was 1.59. On the other hand, when the alkoxyamine concentrations were 12.8 and 18.8 mmol L −1 , the polymerization was well controlled to give star polymers with a low polydispersity index even at high conversion. The side reactions disturbing the "living" fashion were discussed on the basis of the SEC elution curves of the star polymers obtained. KEY WORDS Star Polymer / Living Radical Polymerization / Nitroxide / Alkoxyamine / Polydispersity Index / Since nitroxide-mediated "living" radical polymerization provides well-defined polymers with a low polydispersity index, this technique has attracted much attention from the view of points of both polymer chemistry and polymer industry. [1][2][3][4] In this polymerization system the propagating radical chains are capped by nitroxides, giving deactivated (dormant) species, and the resultant dormant species are reactivated via the homolytic C-O bond dissociation at high temperature (usually above 110 • C) to give propagating radical chain and nitroxide. Since the equilibrium for the C-O bond dissociation and reformation shifts to the bond formation side, most of the propagating radical chains exist as the dormant species, leading to a very low concentration of the propagating radical compared with the conventional radical polymerization system. This characteristic of the nitroxide-mediated "living" radical polymerization is favorable to syntheses of well-defined star polymers because intermolecular and intramolecular coupling reactions between the propagating radicals must be suppressed. In a previous paper we reported the syntheses of well-defined 3-arm star polymers with a low polydispersity index using 1,3,5-tris(alkoxyamino)benzenes as an initiator. 5 Since the 1,3,5-tris(alkoxyamino)benzenes have no chemically labile bonds, the resultant star polymers are very stable under the strongly acidic or basic conditions. This characteristic makes a wide variety of applications of the resulting star polymers possible. In a continuing synthetic study of star polymers, we synthesized 6-arm † To whom correspondence should be addressed star polymers using Star-6, a dendritic TEMPO-based alkoxyamine. Herein we wish to report the synthesis of Star-6 and the TEMPO-mediated "living" radical polymerization of styrene (St) initiated with Star-6 giving a well defined 6-arm star polymer.Although many star polymers have so far been prepared by the nitroxide-mediated polymerization, 4 ATRP, 6 and RAFT ...

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Peresters. V.¹ Di-t-butylperoxyoxalate

Cited by 215 publications

References 0 publications

THE INDUCED DECOMPOSITION OF tert-BUTYL HYDROPEROXIDE

THE INDUCED DECOMPOSITION OF tert-BUTYL HYDROPEROXIDE

Models for non-heme oxidation enzymes

Synthesis of Six-Arm Star Polymer by Nitroxide-Mediated “Living” Radical Polymerization

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Peresters. V.1 Di-t-butylperoxyoxalate

Cited by 215 publications

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THE INDUCED DECOMPOSITION OF tert-BUTYL HYDROPEROXIDE

THE INDUCED DECOMPOSITION OF tert-BUTYL HYDROPEROXIDE

Models for non-heme oxidation enzymes

Synthesis of Six-Arm Star Polymer by Nitroxide-Mediated “Living” Radical Polymerization

Contact Info

Product

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About

Peresters. V.¹ Di-t-butylperoxyoxalate