- Aryl acyl peroxides for visible-light induced decarboxylative arylation of quinoxalin-2(1: H)-ones under additive-, metal catalyst-, and external photosensitizer-free and ambient conditions
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Aryl radicals were generated for the first time from cheap and easily available aryl acyl peroxides in eco-friendly ethyl acetate under ambient conditions and visible-light illumination in the absence of any additive, metal catalyst, or external photosensitizer. The present arylation of quinoxalin-2(1H)-ones was chemo- and regioselective, and provided good access to various 3-arylquinoxalin-2(1H)-ones. This journal is
- Xie, Long-Yong,Peng, Sha,Yang, Li-Hua,Peng, Cun,Lin, Ying-Wu,Yu, Xianyong,Cao, Zhong,Peng, Yu-Yu,He, Wei-Min
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supporting information
p. 374 - 378
(2021/01/28)
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- External-oxidant-free amino-benzoyloxylation of unactivated alkenes of unsaturated ketoximes with: O -benzoylhydroxylamines
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A new copper-catalyzed two-component amino-benzoyloxylation of unactivated alkenes of unsaturated ketoximes with O-benzoylhydroxylamines as the benzoyloxy sources is developed. Chemoselectivity of this method toward amino-benzoyloxylation or oxy-benzoyloxylation of alkenyl ketoximes relies on the position of the tethered olefins, and provides an external-oxidant-free alkene difunctionalization route that directly utilizes O-benzoylhydroxylamines as the benzoyloxy radical precursors and internal oxidants for the divergent synthesis of cyclic nitrones and isoxazolines.
- Chen, Jiangfei,Zhu, Yan-Ping,Li, Jin-Heng,Wang, Qiu-An
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supporting information
p. 5215 - 5218
(2021/05/31)
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- Palladium-Catalyzed C-H Amination/[2 + 3] or [2 + 4] Cyclization via C(sp3or sp2)-H Activation
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This report describes a palladium-catalyzed Catellani reaction consisting of amination/[2 + 3] or [2 + 4] cyclization via a carboxylate ligand-exchange strategy. This method effectively activates ortho-substituents that avoid a second C-H palladation. The scope of substrates was broad, o-methyl-substituted iodoarenes were applied to the reaction smoothly, and o-phenyl-substituted iodoarenes can also be obtained by this method. In terms of mechanism, density functional theory calculations proved the sequence of the key five-membered aryl-norbornene-palladacycle intermediate formation and C(sp3 or sp2)-H activation.
- An, Yang,Ding, Ya-Nan,Gou, Xue-Ya,Li, Qiao,Li, Yuke,Liang, Yong-Min,Zhang, Xiao-Yan,Zhang, Zhe
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p. 7961 - 7965
(2021/10/25)
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- A carboxylate-assisted amination/unactivated C(sp2)-H arylation reactionviaa palladium/norbornene cooperative catalysis
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This report describes a carboxylate-assisted palladium-catalysed Catellani reaction, which is compatible withortho-amination and unactivated C(sp2)-H arylation. This method was used to synthesize a series of 1-amino substituted dihydrophenanthridines, phenanthridines and 6H-benzo[c]chromenes. Based on kinetic isotope experiments, the kinetic curve proves that pivalic acid accelerates the reaction rate of unactivated C(sp2)-H activation, and thus this rate can keep up with the five membered aryl-norbornene-palladacycle (ANP) intermediate.
- An, Yang,Zhang, Bo-Sheng,Zhang, Zhe,Liu, Ce,Gou, Xue-Ya,Ding, Ya-Nan,Liang, Yong-Min
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supporting information
p. 5933 - 5936
(2020/06/04)
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- An unprecedented cobalt-catalyzed selective aroylation of primary amines with aroyl peroxides
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A novel and facile cobalt-catalyzed selective aroylation of primary amines with aroyl peroxides was developed for the synthesis of aryl amides. It was unprecedented that C[sbnd]N bond formation product was selectively generated without the common N[sbnd]O bond formation product. Aroyl peroxides act as the sole aroylation reagent without additional base or oxidant. The reactions proceeded under mild conditions and showed broad substrates scope with a series of primary amines and aroyl peroxides.
- Li, Dong,Li, Jiale,Li, Juanjuan,Yuan, Songdong,Zhang, Qian
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supporting information
(2020/09/16)
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- PROCESS FOR PREPARING A POWDERY ORGANIC PEROXIDE FORMULATION
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Process for preparing a powdery organic peroxide formulation, said process comprises the following steps: a) preparing a reaction mixture comprising: - 40-80 wt% water - 10-25 wt% of an acid chloride or chloroformate, - 1 -4 wt% hydrogen peroxide, - 2-8 wt% alkali metal hydroxide, - 1 -25 wt% of a phlegmatizer selected from the group consisting of ethylene glycol dibenzoate, phenyl benzoate, trimethylol propane tribenzoate, glyceryl tribenzoate, ethylene glycol ditoluate, 1,3-propanediol ditoluate, ethylene glycol 4-tert-butylbenzoate, ethylene glycol monobenzoate monotoluate, 2,3- butanediol dibenzoate, 4-methylphenyl benzoate acid ester, trimethylolpropane dibenzoate, and combinations thereof - 0.002-0.20 wt% of a surfactant, and - 0.25-5.0 wt% of an inert organic solvent, all percentages based on the weight of the reaction mixture, b) heating the reaction mixture at a temperature in the range 5-50°C.
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Page/Page column 10-15
(2019/07/13)
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- Uncatalyzed, on water oxygenative cleavage of inert C-N bond with concomitant 8,7-amino shift in 8-aminoquinoline derivatives
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Oxygenative cleavage of an inert CAr-NH2 bond with concomitant 1,2 amine migration in 8-aminoquinoline derivatives is reported in water at room temperature. The reaction is highly atom- and step-economical as both C- and N-containing fragments of the C-N bond cleavage are incorporated into the target molecule and is effected without the need for N-oxide. The reaction is scalable to gram level, and the products are useful as electrophilic partners for coupling reactions, ligands in catalysis and bioactive compounds.
- Botla, Vinayak,Pilli, Navyasree,Malapaka, Chandrasekharam
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supporting information
p. 1735 - 1742
(2019/04/08)
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- Method for preparing aroyl peroxide
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The invention discloses a method for preparing an aroyl peroxide. Aryl formic acid is uses as a starting material, and the raw material is easy to get, and is of many types; products obtained by the method disclosed by the invention are of various types and are widely used; furthermore, the method disclosed by the invention has the advantages of mild reaction condition, high yield of the target product, less pollution, and simple reaction operation and post-treatment process, and is suitable for industrial production.
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Paragraph 0016; 0017
(2019/10/01)
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- Transition metal free oxygenation of 8-aminoquinoline amides in water
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The oxygenation of 8-aminoquinoline amides by benzoyl peroxide at the C5 position in water is developed in the absence of a transition metal catalyst, affording the desired products in moderate to good yields of up to 88%. Mechanism studies reveal that the reaction would involve a radical process.
- Yao, Xinghui,Weng, Xin,Wang, Kaixuan,Xiang, Haifeng,Zhou, Xiangge
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supporting information
p. 2472 - 2476
(2018/06/11)
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- Thermoinduced Free-Radical C-H Acyloxylation of Tertiary Enaminones: Catalyst-Free Synthesis of Acyloxyl Chromones and Enaminones
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In this paper, the direct acyloxylation of the α-C(sp2)-H bond in tertiary β-enaminones is accomplished under catalyst-free conditions and ambient temperature by using aroyl peroxides as coupling partners. By means of a thermoinduced free-radical pathway, the present method enables facile and efficient synthesis of both acyloxylated chromones and enaminones.
- Guo, Yanhui,Xiang, Yunfeng,Wei, Li,Wan, Jie-Ping
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supporting information
p. 3971 - 3974
(2018/07/15)
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- Preparation method of high-purity benzoyl peroxide
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The invention discloses a preparation method of high-purity benzoyl peroxide. The high-purity benzoyl peroxide is prepared through a synthesis process and a purification process. Alkali selected in the synthesis process is ammonium hydrogen carbonate, so that reaction safety is high, overall reaction is mild and control, and product purity can reach 99.5% and higher. A solvent selected in the purification process is safe and has lower toxicity than chloroform and methanol, operation is easy, and obtained crystal particles are large.
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Paragraph 0014; 0015; 0016; 0017; 0018; 0019
(2017/04/28)
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- Mechanochemically-assisted solid-state photocatalysis (MASSPC)
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In this proof-of-concept study, we demonstrate the first successful transfer of transition metal-free photocatalysis from the conventional solution environment into the solid state, which is enabled by simultaneous irradiation with visible light and mecha
- ?trukil, Vjekoslav,Sajko, Igor
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supporting information
p. 9101 - 9104
(2017/08/18)
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- Method for synthesizing benzoyl peroxide and benzoyl peroxide synthesized with method
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The invention provides a method for synthesizing benzoyl peroxide. According to the method for synthesizing benzoyl peroxide, benzoyl chloride, hydrogen peroxide, sodium hydroxide and a surfactant serve as raw materials, the raw materials are subjected to a one step reaction to obtain the product, the method is simple in technology, safe in operation, low in production cost, high in yield and the like, and is suitable for industrial production and wide application. According to the method, in the feeding process, the surfactant is dissolved into a reaction solvent before the sodium hydroxide is added, and therefore the solution overflowing phenomenon when the surfactant is dissolved is effectively avoided. The benzoyl peroxide synthesized with the method has the advantages of being free of blocking, even in granularity, easy to wash and the like, and meets the bulk-pharmaceutical-chemical quality standard recorded by the Chinese pharmacopoeia and the European pharmacopoeia.
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Paragraph 0045-0048
(2017/04/06)
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- Copper-catalyzed Csp3-O cross-coupling of unactivated alkyl halides with organic peroxides
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An efficient Cu-catalyzed Csp3-O coupling of peroxides with haloalkanes is described. High yields of products were achieved under mild conditions. Significantly, in addition to primary alkyl halides, secondary alkyl halogenated hydrocarbons could also be applied to this system. The new reaction system could tolerate a wide range of organic peroxides.
- Chen, Huan-Huan,Wang, Guang-Zu,Han, Jin,Xu, Meng-Yu,Zhao, Yong-Qiang,Xu, Hua-Jian
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p. 212 - 217
(2014/01/06)
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- Benzoyl Peroxide Composition, Methods for Making Same, and Pharmaceutical or Cosmetic Formulations Comprising Same, and Uses Thereof
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The present invention relates to the preparation of compositions comprising benzoyl peroxide, with or without other additional active ingredients. The process involves introducing benzoyl peroxide, along with any other active ingredients present, into a fatty substance that contains and protects the ingredients that would otherwise be unstable when in contact with one another. The composition is designed to allow all ingredients to become available for skin contact or skin absorption when the fatty substance softens and/or melts as the composition is applied to the skin. The benzoyl peroxide may be pre-micronized to a particle distribution size of about d90 of 0.1 to 150 microns, preferably d90 of 10 to 15 microns. Further, pharmaceutical or cosmetic ingredients may be contained within the fatty substances, with or without, benzoyl peroxide therein or may be present outside of the fatty substance but elsewhere within formulated pharmaceutical or cosmetic products using the active ingredients protected by the fatty substance. These compositions are useful in aqueous-based formulations to treat diseases by topical, transdermal and/or subcutaneous administration.
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- Patch and patch preparation
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Provided is a patch having good adhesion property, which stably maintains the quality for a long time. A patch containing a support and an adhesive layer formed on at least one surface of the support, wherein the adhesive layer contains an elastomer obtained by crosslinking a polymer having a butadiene skeleton in the presence of organic peroxide.
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- Preparation of liquid substituted benzoyl peroxide mixtures
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A series of alkyl substituted benzoyl peroxide mixtures were synthesised from two or three acid chloride combination in aqueous sodium peroxide and butanone solutions in the presence of 0.5 percent stearyltrimethylammonium chloride. Some of these benzoyl peroxide mixtures were found to be liquids at -10 deg C.
- Moorhoff, Cornelis M.,Braybrook, Carl
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p. 339 - 361
(2007/10/03)
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- Topical anti-acne composition
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The present invention is directed towards a topical composition for the treatment of acne comprising water, an organic peroxide, an alpha hydroxy acid, a moisturizer, an isosorbide and a detergent. This invention also is directed to a method of making the composition of this invention. The method involves (1) heating water to between 60° C. and 70° C.; (2) adding a detergent base to the water and mixing the solution; (3) cooling the solution and adding an alpha hydroxy acid, an isosorbide and sodium pyrollidone carboxylate; (4) continuing to cool the solution to between 25° C. and 35° C. and then adding benzoyl peroxide and a preservative to the solution; (5) mixing and milling the product until smooth; and (6) adjusting the pH of the product to a pH of 3-5 with a base. This invention also is directed towards a method for treating a patient afflicted with acne by applying the composition of this invention to the affected areas of the patient's skin.
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- Compound and surfactant
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A novel polymerizable surfactant represented by the general formula (1): STR1 (wherein, R1 represents a hydrogen atom or a methyl group, Rf represents a hydrocarbon group in which one or more hydrogen atoms are replaced by a fluorine atom or atoms, or an acyl group in which one or more hydrogen atoms are replaced by a fluorine atom or atoms, AO and AO' represent a group selected from an oxyalkylene group having 2-4 carbon atoms or a styrene oxide residue, m and m' are 0 or a number between 1 and 1,000, X represents a hydrogen atom or a hydrophilic group).
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- Enhancer tolerant pressure sensitive adhesives for transdermal drug delivery
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Pressure sensitive adhesive compositions for use in transdermal drug delivery systems comprising an adhesive composition which is tolerant to plasticization by cutaneous penetration enhancers contained in the transdermal drug formulation are disclosed. Specifically, the pressure sensitive adhesive composition of the present invention comprises an acrylic copolymer prepared from (i) at least 40% by weight of th total monomer composition of alkyl acrylate monomers with a Tg of -90 to 0°C, (ii) 0-15% by weight of the total monomer composition of monomers with a Tg of 0 to 250°C, and (iii) 10-60% by weight of the total monomer composition of substituted acrylamides or methacrylamides having the structural formula: wherein R1isH or CH3, R2isH or CH3, and R3is(a) CH3,(b) C(CH3)2-(CH2)n-CH3where n is 0 through 17, or, (c) substituents of the formula: where m is 0 through 10,and optionally ???(iv) at least 0.2% by weight of acrylic monomers containing at least one group having a reactive hydrogen, and (v) 0.01-2% by weight of a chelated metal alkoxide crosslinker to (i), (ii) and (iii).
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- Process for preparing peroxides
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A process for the faster manufacturing of hydrocarbon, fluorocarbon and chlorocarbon acyl peroxides is disclosed wherein a hydroxide, a peroxide and an acyl halide are reacted under continuous vigorous agitation conditions so as to bring the reaction to substantial completion is less than one minute.
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- Dental composite resin composition
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A dental composite resin composition is disclosed, which comprises as main components a polymerizable monomer, an inorganic and/or organic filler, a gold powder and/or a gold-color alloy powder, and a polymerization catalyst. The dental composite resin composition of the present invention is useful as a filling material for repairing a tooth cavity, which has a gold-color luster and exhibits an excellent abrasion resistance as well as an excellent x-ray contrast.
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- DECOMPOSITION OF PEROXOBENZOIC ACID IN BENZENE CATALYZED BY TRANSITION METAL 2,4-PENTANEDIONATES
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The decomposition of peroxobenzoic acid in benzene was studied, and catalytic effects of Fe(III), Mn(III), Co(II), Co(III), and Cr(III) on the reaction rate and the composition of the reaction mixture were investigated.An analogous experiment carried out in perdeuterobenzene and determination of the distribution of deuterium in the reaction products provided evidence for the participation of the solvent in peroxobenzoic acid decomposition.
- Lederer, Pavel,Macova, Eva,Veprek-Siska, Josef
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p. 673 - 679
(2007/10/02)
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- One-electron Oxidation of Closed-shell Molecules. Part 3. Oxidative Cleavage of 1,2,2,2-Tetrakis-(p-methoxyphenyl)ethanone with Dibenzoyl and Bis(3,5-dinitrobenzoyl) Peroxides: Mechanistic Changeover of the Peroxide Function from Radical to Molecular Oxidation
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1,2,2,2-Tetrakis-(p-methoxyphenyl)ethanone (anispinacolone) (1) is cleaved by dibenzoyl peroxide (2) or bis-(3,5-dinitrobenzoyl) peroxide (3), affording tris-(p-methoxyphenyl)methyl benzoate (or 3,5-dinitrobenzoate) and benzoic (or 3,5-dinitrobenzoic) p-methoxybenzoic anhydride as the principal cleavage products. 13C N.m.r.CIDNP studies by use of labelled anispinacolone (An3*C-*COAn ; *C 90percent 13C) indicated that p-methoxybenzoyl radical is formed, presumably by way of the radical cation +. which is produced by a single-electron transfer (s.e.t.) mechanism.The formation of the p-methoxybenzoyl radical was also indicated by spin-trapping experiments.The decomposition rates of (2) at 50.0 deg C are unaltered on addition of (1) in nonpolar solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and benzene, whereas those of (3) are markedly accelerated.The cleavage of (1) by (2) is supressed by added 3,4-dichlorostyrene by a factor of 6.7, whereas that of (1) by (3) is almost unaffected.These results suggest that in the case of dibenzoyl peroxide (2) the thermally produced benzoyloxyl radical works as a one-electron acceptor (or oxidant) upon (1), whereas when bis-(3,5-dinitrobenzoyl) peroxide (3) is used the peroxide molecule oxidizes (1), probably by way of an s.e.t. mechanism even in such nonpolar solvents.On the other hand, in polar solvents such as (CF3)2CHOH, teramethylene sulphone, and acetonitrile the decomposition of (2) is accelerated by added anispinacolone, suggesting that the intermolecular s.e.t. reaction is partially involved in such polar solvents.Consequently, the oxidative cleavage of anispinacolone (1) by diaroyl peroxides provides the first example of dichotomy in the s.e.t. reaction of diaroyl peroxides, which can be considered a counterpart of the SN1-SN2 dichotomy in nucleophilic substitution, as far as the molecularity of the peroxide is concerned.
- Takeuchi, Ken'ichi,Murai, Osamu,Matsui, Shin,Inoue, Takeshi,Kitagawa, Toshikazu,Okamoto, Kunio
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p. 1301 - 1310
(2007/10/02)
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- OXYGEN ATOM TRANSFER REACTION. THE REACTION OF CARBONYL COMPOUNDS WITH DIOXYGEN COMPLEXES
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The reaction of peroxobis(triphenylphosphine)platinum with benzil or benzoic anhydride gave benzoic anhydride or benzoyl peroxide respectively.The scope of the above reactions is described.
- Aida, Shun'ichi,Ohta, Hiroyuki,Kamiya, Yoshio
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p. 1639 - 1642
(2007/10/02)
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- INVESTIGATION IN THE REGION OF FUNCTIONAL ORGANIC PEROXIDES. XV. SYNTHESIS AND CHEMICAL CHARACTERISTICS OF BENZOYL PEROXIDES WITH FLUORINE-CONTAINING SUBSTITUENTS
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The synthesis of benzoyl peroxides with fluorine-containing substituents at various positions in the benzene ring was realized by the acylation of an alkali-metal peroxide by fluorine-substituted benzoyl chlorides and also by the reaction of the fluorine-substituted benzoic acids with hydrogen peroxide in the presence of N,N'-dicyclohexylcarbodiimide.A mechanism is proposed for the production of the peroxides by the carbodiimide method.The rate constants and activation energies were determined for the thermal decomposition of the synthesized peroxides in chlorobenzene.The rate constants for the decomposition of the substituted aromatic peroxides correlate with the Hammett ? constants on the fluorine-containing substituents.
- Rakhimov, A. I.,Androsyuk, E. R.,Shelyazhenko, S. V.,Yagupol'skii, L. M.
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p. 1470 - 1475
(2007/10/02)
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- Stereochemistry and Mechanisms of Reactions of Dioxygen Complexes with Organic Electophiles as Studied by Use of Chiral Reagents and Isotopic Labeling
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From reactions of PtO2L2 (L = PPh3, P(c-C6H11)3) with 1 mol of triphenylmethyl bromide or benzoyl bromide the corresponding (alkylperoxo)platinum(II) complexes L2PtBr(OOR) (1a, L = PPh3, R = CPh3; 1b, L = P(c-C6H11)3, R = CPh3; 2, L = PPh3, R = COPh) were isolated, which were well characterized by elemental analysis and IR spectroscopy.The complex 1a,b or 2 was treated with another mole of organic halides to give the corresponding dialkyl peroxides (Ph3COOCPh3, PhC(O)OOC(O)Ph) in good yields.Thus, the stepwise mechanism proposed previously for "metal-assisted peroxidations" was verified.A similar reaction of PtO2(PPh3)2 with an optically active (S)-(-)-α-phenethyl bromide produced a peroxoplatinum(II) complex, PtBr(OOCH(CH3)Ph)(PPh3)2 (3), which gave upon acidolysis (R)-(+)-α-phenethyl hydroperoxide.Reductive cleavage of 3 with NaBH4 gave (R)-(+)-α-phenethyl alcohol.Hence, it can be concluded that the reaction of PtO2L2 with organic halides proceeds via the SN2-type transition state.From the IR 18O isotopic shifts the O-O stretching band was assigned for the products from the reactions of PtO2L2 with acetone (4), benzophenone (5), 1,1-dicyano-2-methylpropene (8), and tetracyanoethylene (9).The 18O IR study also shows that the peroxy bond involved in these products is derived from PtO2L2.The reaction product (10a, L = PPh3; 10b, L = P(c-C6H11)3) obtained from PtO2L2 and CH3OOCCCCOOCH3 was also studied by 18O isotopic IR and 13C NMR spectra.Acidolysis of 10b gave dimethyl dihydroxymaleate ina good yield.Thus it was established that the reaction of an electrophilic acetylene with PtO2L2 results in the O-O bond cleavage.
- Tatsuno, Y.,Otsuka, Sei
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p. 5832 - 5839
(2007/10/02)
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- Derivatives of 2H-pyran-2-one
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Processes for producing a (1α, 4α, 5α)-6,6-dimethyl-4-halo-substituted-methyl-3-oxabicyclo[3.1.0]hexan-2-one and its novel intermediates from known and inexpensive starting materials are described and exemplified.
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