- Reaction of zirconium alkoxides with tert-butyl hydroperoxide. Oxidative ability of the Zr(OBu-t)4-t-BuOOH system
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Oxidation of the isopropoxy group in the Zr(i-PrO)4·i- PrOH complex involves both direct reaction with tert-butyl hydroperoxide and intermediate formation of zirconium peroxy compound. Zirconium tetra-tert-butoxide reacts with tert-bytyl hydroperoxide to form metal-containing peroxide and trioxide. Decomposition of the latter leads to oxygen evolution and is accompanied by radical formation. The alkoxyl and peroxyl radicals formed were identified by ESR spectroscopy. The nature of the oxidant (oxygen, zirconium-containing peroxide and-trioxide) in the Zr(OBu-t)4-t-BuOOH system is determined by the structure of the substrate molecule. Pleiades Publishing, Inc., 2006.
- Gulenova,Stepovik,Cherkasov
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- Preassociating α-nucleophiles based on β-cyclodextrin. Their synthesis and reactivity
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Methods are reported for the attachment of α-nucleophiles to the primary and secondary sides of the cyclodextrin cavity. Six new materials have been prepared in which βCD has been modified by hydrazine, hydroxylamine, oxime, and hydroperoxide functionalities. Transacylating studies with p-NPA have demonstrated that the primary-side hydroxylamine shows the highest reactivity with a 1900-fold increase in rate over βCD at pH 6.5. Other α-nucleophiles show less remarkable rate increases in this system but, in some cases, demonstrate hydrogen-bonding to the cyclodextrin rim and inhibition kinetics.
- Martin, Kristy A.,Mortellaro, Mark A.,Sweger, Robert W.,Fikes, Lewis E.,Winn, David T.,Clary, Scott,Johnson, Morgan P.,Czarnik, Anthony W.
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- Oxidation of β-dicarbonyl compounds with tert-butyl hydroperoxide in the presence of vanadyl acetylacetonate
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Oxidation of β-dicarbonyl compounds with tert-butyl hydroperoxide in the presence of vanadyl acetylacetonate (benzene, 20°C) involves the activated methylene group with intermediate formation of trioxo derivatives and is accompanied by decomposition of carbon skeleton. The oxidation products are carbon dioxide, carboxylic acids, and tert-butyl and peroxy esters derived from the latter.
- Stepovik,Gulenova,Kalacheva,Potkina, A. Yu.
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- Reaction of triphenylantimony and triphenylbismuth with tert-butyl peracetate
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Triphenylantimony and triphenylbismuth diacetates, Ph3M(OAc)2 (M = Sb, Bi), were obtained in 50-95percent yields by the reaction of triphenylantimony and triphenylbismuth with tert-butyl peracetate in the presence of acetic acid or acetic anhydride (molar
- Gushchin, A. V.,Dyomina, E. E.,Dodonov, V. A.
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- New synthesis of tert-butyl peroxycarboxylates
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tert-Butyl peroxyacetate, tert-butyl peroxybutyrate, tert-butyl phenylperoxyacetate, and tert-butyl peroxyundecanoate were obtained in nearly quantitative yields by the esterification of the corresponding carboxylic acids with tert-butyl hydroperoxide in the presence of trifluoroacetic anhydride and pyridine in nonaqueous medium at 0-5°C. No tert-butyl peroxytrifluoroacetate was formed as a by-product during the process. A possible reaction mechanism is discussed. Pleiades Publishing, Inc., 2006.
- Donchak,Voronov,Yur'ev
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- Polymerization Mechanism of Styrene Initiated by 2,2-Bis(t-butyldioxy)alkanes
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The radical polymerization mechanism of styrene initiated by 2,2-bis(t-butyldioxy)alkanes (1) has been studied in benzene.The decomposition products of 1 are acetone, alkyl methyl ketone, t-butyl alcohol, and t-butyl peracetate.Styrene monomer converts to polystyrene along with styrene oxide.The peroxides 1 cleave homolytically at one of dioxy bonds to yield intermediate alkoxy radicals with α-t-butyldioxy group, which undergo β-scission to afford t-butyldioxy or alkyl radicals.The resulting t-butyldioxy radical reacts with styrene to form 2-(t-butyldiox)-1-phenylethyl radical, which decomposes subsequently to styrene oxide and t-butoxyl radical via γ-scission.Alternatively, a part of t-butyldioxy radical adds to styrene to afford polystyrene containing dioxy bond.
- Watanabe, Yasumasa,Ishigaki, Hideyo,Okada, Hiroshi,Suyama, Shuji
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- Amide bond formation through iron-catalyzed oxidative amidation of tertiary amines with anhydrides
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A general and efficient method for amide bond synthesis has been developed. The method allows for synthesis of tertiary amides from readily available tertiary amines and anhydrides in the presence of FeCl2 as catalyst and tert-butyl hydroperoxide in water (T-Hydro) as oxidant. Mechanistic studies indicated that the in situ-generated α-amino peroxide of tertiary amine and iminium ion act as key intermediates in this oxidative transformation.
- Li, Yuanming,Ma, Lina,Jia, Fan,Li, Zhiping
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p. 5638 - 5646
(2013/07/26)
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- Specific features of the reaction of vanadyl acetylacetonate with tert-butyl hydroperoxide
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Reaction of vanadyl acetylacetonate with tert-butyl hydroperoxide (benzene, 20°C) at any molar ratio leads to the elimination of ligand and its oxidation mainly to CO2 and acetic acid. At the (acac)2VO: t-BuOOH ratio above 1:10 liberation of oxygen partially in the singlet state takes place.
- Stepovik,Gulenova
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scheme or table
p. 1663 - 1670
(2011/05/14)
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- 5-CYANO-10-HYDROXY-10,11-DIHYDRO-5H-DIBENZ[B,F]AZEPINE, THE PROCESSES FOR ITS PREPARATION AND FOR ITS CONVERSION INTO 5-CARBAMOYL-10-OXO-10, 11-DIHYDRO-5H-DIBENZ[B,F]AZEPINE OR INTO 5-CARBAMOYL-5H-DIBENZ[B,F]AZEPINE
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5-Cyano-10-Hydroxy-10,11-Dihydro-5H-Dibenzi[b,f]azepine and the process for its preparation.
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- Reaction of unsaturated esters with the oxidative system aluminum tri-tert-butoxide-tert-butyl hydroperoxide
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Unsaturated esters containing double bonds in the acyl (methyl acrylate) or in the alcohol (vinyl and allyl acetates) fragments are cleaved under mild conditions (20°C) by the system aluminum tri-tert-butoxide-tert-butyl hydroperoxide to give tert-butyl esters of peroxycarboxylic acids and unsymmetrical aluminum alkoxides. The double bond in the acyl fragment is inert to this oxidation system. Vinyloxy- and allyloxy derivatives are oxidized to hydroxyethanal and (hydroxymethyl)oxirane, respectively. Carbon-hydrogen bonds are oxidized only in allyl acetate.
- Stepovik,Martynova,Dodonov
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p. 1225 - 1229
(2007/10/03)
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- 5-Cyano-10-hydroxy-10,11-dihydro-5H-dibenz[b,f]azepine, processes for its preparation and for its conversion into 5-carbamoyl-10-oxo-10,11-dihydro-5H-dibenz[b,f]azepine or into 5-carbamoyl-5H-dibenz[b,f]azepine
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A process and intermediates useful for the preparation of carbamazepine and oxcarbamazepine are disclosed.
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- Oxidation of Esters with the Aluminum Tri-tert-butylate-tert-Butyl Hydroperoxide System
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The aluminum tri-tert-butylate-tert-butyl hydroperoxide system oxidizes under mild conditions (20°C) esters containing primary, secondary, and tertiary hydrogen atoms both in the acyl and alkoxy groups: isopropyl acetate, propionate, and chloroacetates, benzyl acetate and isobutyrate, and methyl and isobutyl phenylacetates. The reaction involves oxidation of the methylene and methine C-H bonds, nucleophilic addition to the carbonyl group, and ester interchange and is accompanied by cleavage of the carbon skeleton of the acyl group or the ester C-O bond.
- Zaburdaeva,Stepovik,Dodonov,Martynova
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p. 1902 - 1908
(2007/10/03)
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- Reactions of the System Aluminum Tri-tert-butylate-tert-Butyl Hydroperoxide with β-Dicarbonyl and β-Hydroxy Carbonyl Compounds
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2,4-Pentanedione is oxidized with the system aluminum tri-tert-butylate-tert-butyl hydroperoxide with intermediate formation of pentanetrione and subsequent cleavage of the carbon skeleton. tert-Butyl acetate and peracetate and acetic and pyruvic acids were isolated as the oxidation products. In the reaction of the same oxidizing system with 4-hydroxy-4-methyl-2-pentanone, the extent of oxidation does not exceed 10%, with the main pathway being depolymerization and dehydration of the substrate.
- Stepovik,Zaburdaeva,Dodonov
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p. 1104 - 1109
(2007/10/03)
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- Reactions of Ketones with the Oxidizing System Aluminum Tri-tert-butylate-tert-Butyl Hydroperoxide
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Oxidation of ketones containing primary, secondary, and tertiary carbon atoms at the α-position [dialkyl ketones, alkyl aryl ketones, and alkyl (aryl) benzyl ketones] with the system aluminum tri-tert-butylale-tert-butyl hydroperoxide is accompanied by cleavage of the carbon skeleton of the substrate via formation of α-hydroxy carbonyl and α-dicarbonyl compounds. The qualitative and quantitative composition of the reaction products indicates that the oxidation involves free radicals. Simultaneously, the oxidizing system adds across the carbonyl group of the substrate, which is followed by decomposition of aluminum-containing peroxides.
- Stepovik,Zaburdaeva,Dodonov
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p. 264 - 269
(2007/10/03)
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- OXIDATION OF α-DIKETONES BY THE SYSTEM ALUMINUM TRI-tert-BUTYLATE-tert-BUTYL HYDROPEROXIDE
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α-Diketones (butanedione, 2,3-pentanedione, benzil) react with tert-butyl hydroperoxide to form the corresponding anhydrides and tert-butyl alcohol.In the reaction of α-diketones with an oxidative system including aluminum tri-tert-butylate and tert-butyl hydroperoxide, tert-butylacylates and peracylates of the corresponding carboxylic acids are formed as the major reaction products.
- Stepovik, L. P.,Dodonov, V. A.,Smyslova, G. N.
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p. 102 - 106
(2007/10/02)
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- Addition radicalaire au peroxyde d'allyle et de t-butyle: synthese d'epoxydes fonctionnels
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The free radical addition of labile hydrogen solvents to allyl and t-butyl peroxide led to 2,3-epoxypropanation of such compounds with yield over 50percent.
- Montaudon, E.,Rakotomanana, F.,Maillard, B.
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p. 198 - 202
(2007/10/02)
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- DEPLACEMENTS HOMOLYTIQUES INTRAMOLECULAIRES : V - EPOXY-2,3 PROPANATION DES ACIDES ET DERIVES PAR THERMOLYSE DU PEROXYDE D'ALLYLE ET DE t-BUTYLE
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The thermolysis of the allyl t-butylperoxide has been performed in esters, acids, anhydrides, nitriles and amides.Only esters and acetonitrile have been 2,3-epoxy propanated.With acids, the reaction product is the alkanoate of the hydroxymethyl-γ-butyrolactone corresponding to the cyclization of the expected epoxyacid and it is isolated with a good yield; the same compound is obtained putting the anhydride in place of the acid.
- Montaudon, E.,Rakotomanana, F.,Maillard, B.
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p. 2727 - 2736
(2007/10/02)
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- Peroxy Esters. 8. Base-Catalyzed Rearrangement of Peroxy Esters: Formation of Alkoxyacetic Acid Derivatives
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p-Peroxyquinol esters derived from base-catalyzed oxygenation of 4-alkyl-2,6-tert-butylphenols followed by Schotten-Baumann acylation undergo a novel base-catalyzed rearrangement with t-BuOK in N,N-dimethylformamide to give p-quinoxyacetic acid derivatives in excellent yield.The same base-catalyzed rearrangement was also observed with tert-butyl peroxy esters.The base-catalyzed reaction of peroxy esters depended strongly on the nature of the acyl group in the esters and the base used and is suggested to involve homolysis of the peroxy bond.
- Nishinaga, Akira,Nakamura, Koichi,Matsuura, Teruo
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p. 3696 - 3700
(2007/10/02)
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- REACTIVITY OF CARBOXYLIC ACID ANHYDRIDES IN THE ACYLATION OF TERT-BUTYL HYDROPEROXIDE IN BENZENE
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The kinetics of the acylation of tert-butyl hydroperoxide with carboxylic acid anhydrides (RCO2)O (R = C5H11, CH3, C6H5, CH2Cl) in benzene were studied by GLC from the accumulation of tert-butylperoxy esters.Increase in the electron-withdrawing characteristics of the substituent R in the aliphatic series leads to an increase in the reactivity of the anhydride.The steric effect of the group R does not show up appreciably.The enthalpy and entropy of activation were determined.
- Antonovskii, V. L.,Zhitina, L. V.,Emelin, Yu. D.,Komarova, V. I.
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p. 623 - 626
(2007/10/02)
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