- Synthesis of new azapolycyclic scaffolds via the domino aminolysis of dicyclopentadiene diepoxide in water
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A convenient method is reported for the multigram scale synthesis of compounds containing the novel octahydro-1H-2,5-epimino-4,7-methanoindene azapolycyclic system in good yields. This method involves the domino aminolysis of readily available dicyclopentadiene diepoxide in water at 165 °C. 2D NMR and XRD spectra of the products were studied in detail.
- Palchykov, Vitalii A.,Gaponova, Rita G.,Omelchenko, Iryna V.,Kasyan, Liliya I.
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supporting information
(2020/06/17)
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- Method for catalytically oxidizing dicyclopentadiene through solid acid (by machine translation)
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Compared. the prior art, the method disclosed by the invention adopts a supported heteropoly acid catalytic oxidation dicyclopentadiene technology, to carry out catalytic oxidation reaction through a fixed bed or a suspension bed reactor with dicyclopentadiene as a raw material, as an oxidant, through a fixed bed or a suspension bed reactor in the presence of a solvent to prepare a catalyst, for catalyzing and oxidizing by using a fixed bed or a suspension bed reactor in the presence of a solvent to prepare the dicyclopentadiene, by the method . The method is simple, and is easy to recover, environment-friendly, target product ratio 96%. (by machine translation)
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Paragraph 0024-0052
(2020/05/14)
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- Preparation method of dicyclopentadiene dioxide based on modified nano aluminum oxide loaded heteropolyacid type compound catalyst
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The invention discloses a method for preparing dicyclopentadiene dioxide by catalytic oxidation of dicyclopentadiene serving as a raw material in the presence of a solvent through a suspended bed or afixed bed reactor by taking a modified nano aluminum oxide loaded heteropolyacid type compound as a catalyst and hydrogen peroxide as an oxidant. Compared with the prior art, the preparation method provided by the invention has the advantages that the catalyst is long in service life, stable in performance, simple to separate and high in product yield, and the reaction yield of dicyclopentadienedioxide is greater than 96%.
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Paragraph 0033-0046
(2020/05/14)
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- Method for catalytic oxidation of dicyclopentadiene by supported heteropoly acid
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The invention provides a method for catalytic oxidation of dicyclopentadiene by a supported heteropoly acid. According to the method, a supported heteropoly acid catalytic oxidation dicyclopentadieneprocess is adopted; dicyclopentadiene is used as a raw material, hydrogen peroxide is used as an oxidizing agent, a quaternary phosphonium salt-containing silylation reagent grafted and modified nanoMgO loaded heteropoly acid or peroxyheteropoly acid is used as a catalyst, and a fixed bed or suspended bed reactor is adopted for catalytic oxidation reaction in the presence of a solvent to preparedicyclopentadiene dioxide. Compared with the prior art, the method is simple, the catalyst is good in heat resistance, stable in service life, easy to recycle and environmentally friendly, and the yield of the target product is larger than 96%.
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Paragraph 0022-0051
(2020/05/14)
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- COMPOSITION FOR CURABLE RESIN, CURED PRODUCT OF SAID COMPOSITION, PRODUCTION METHOD FOR SAID COMPOSITION AND SAID CURED PRODUCT, AND SEMICONDUCTOR DEVICE
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The invention relates to a curable resin composition containing (A) a multifunctional benzoxazine compound having two or more benzoxazine rings, (B) an epoxy compound having at least one norbornane structure and at least two epoxy groups, (C) a biphenyl type epoxy compound, and (D) a curing agent, and optionally (E) an inorganic filler and (F) a curing accelerator; a cured product thereof; methods of producing the curable resin composition and the cured product; and a semiconductor device in which a semiconductor element is disposed in a cured product obtained by curing a curable resin composition containing components (A) to (D), and optionally components (E) and (F).
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Paragraph 0158-0160
(2020/11/30)
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- Method for synthesizing dicyclopentadiene dioxide
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The present invention discloses a method for synthesizing dicyclopentadiene dioxide. According to the method, dicyclopentadiene is used as a reaction raw material, hydrogen peroxide is used as an oxidant, poly m-halogenated styrene-divinylbenzene quaternary phosphonium salt type anion exchange resin supported heteropoly acid or peroxoheteropolyacid is used as a catalyst, and an epoxidation reaction is performed by using a fixed bed or a batch tank reactor to obtain dicyclopentadiene dioxide. According to the present invention, the synthesis method is simple, the catalyst has advantages of goodheat resistance, stable service life and environmental friendliness, and the yield of the target product is more than 90%.
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Paragraph 0024; 0030-0033
(2019/05/16)
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- Method for preparing dicyclopentadiene dioxide through epoxidation of dicyclopentadiene
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The invention discloses a method for preparing dicyclopentadiene dioxide through epoxidation of dicyclopentadiene. According to the method, dicyclopentadiene is used as a reaction raw material, poly o-halogenated styrene-divinylbenzene quaternary phosphonium salt type anion exchange resin supported heteropoly acid or peroxoheteropolyacid is used as a catalyst, and an epoxidation reaction is performed by using a fixed bed or a batch tank reactor to obtain dicyclopentadiene dioxide. According to the present invention, the method is simple, the catalyst has advantages of good heat resistance, stable service life and environmental friendliness, and the yield of the target product is high, and is more than 90%.
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Paragraph 0028-0031
(2019/05/16)
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- Catalytic oxidation synthesis method of dicyclopentadiene dioxide
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The invention discloses a catalytic oxidation synthesis method of dicyclopentadiene dioxide. According to the method, dicyclopentadiene is used as a reaction raw material, hydrogen peroxide is used asan oxidant, poly o-halogenated styrene-divinylbenzene quaternary phosphonium salt type anion exchange resin supported heteropoly acid or peroxoheteropolyacid is used as a catalyst, and an epoxidationreaction is performed by using a fixed bed or a batch tank reactor to obtain dicyclopentadiene dioxide, wherein the reaction temperature of the epoxidation reaction is 30-80 DEG C, the reaction pressure is 0.1-6.0 MPa, the reaction time is 8-20 h, and a molar ratio of dicyclopentadiene to hydrogen peroxide is 1:2-1:4. According to the present invention, the method is simple, the catalyst has advantages of good heat resistance, stable service life and environmental friendliness, and the yield of the target product is more than 90%.
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Paragraph 0029-0031
(2019/05/16)
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- Method for preparing dicyclopentadiene dioxide
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The present invention discloses a method for preparing dicyclopentadiene dioxide. According to the method, dicyclopentadiene is used as a reaction raw material, poly m-halogenated styrene-divinylbenzene quaternary phosphonium salt type anion exchange resin supported heteropoly acid or peroxoheteropolyacid is used as a catalyst, and under the action of an oxidizing agent, in a solvent, an epoxidation reaction is performed by using a fixed bed or a batch tank reactor to obtain dicyclopentadiene dioxide. According to the present invention, the synthesis method is simple, the catalyst has advantages of good heat resistance, stable service life and environmental friendliness, and the yield of the target product is high, and is more than 80%.
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Paragraph 0022; 0028-0032
(2019/05/16)
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- Method for catalytically oxidizing dicyclopentadiene by using supported solid acid
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The invention discloses a method for catalytically oxidizing dicyclopentadiene by using a supported solid acid. According to the method, dicyclopentadiene is used as a raw material, hydrogen peroxideis used as an oxidant, poly p-halogenated styrene-divinylbenzene quaternary phosphonium salt type anion exchange resin supported heteropoly acid or peroxoheteropolyacid is used as a catalyst, and an epoxidation reaction is performed by using a fixed bed or a batch tank reactor to obtain dicyclopentadiene dioxide. According to the present invention, the method is simple, the catalyst has advantagesof good heat resistance, stable service life and environmental friendliness, and the yield of the target product is high.
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Paragraph 0022; 0024-0037
(2019/05/16)
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- Highly selective and efficient olefin epoxidation with pure inorganic-ligand supported iron catalysts
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Over the past two decades, there have been major developments in the transition iron-catalyzed selective oxidation of alkenes to epoxides; a common structure found in drug, isolated natural products, and fine chemicals. Many of these approaches have enabled highly efficient and selective epoxidation of alkenes via the design of specialized ligands, which facilitates to control the activity and selectivity of the reactions catalyzed by iron atom. Herein, we report the development of the olefin epoxidation with inorganic-ligand supported iron-catalysts using 30% H2O2 as an oxidant, and the mechanism is similar to iron-porphyrin type. With the catalyst 1, (NH4)3[FeMo6O18(OH)6], various aromatic and aliphatic alkenes were successfully transformed into the corresponding epoxides with excellent yields as well as chemo- and stereo-selectivity. This catalytic system possesses the advantages of being able to avoid the use of expensive, toxic, air/moisture sensitive and commercially unavailable organic ligands. The generality of this methodology is simple to operate and exhibits high catalytic activity as well as excellent stability, which gives it the potential to be used on an industrial scale, and maybe opens a way for the catalytic oxidation reaction via inorganic-ligand coordinated iron catalysis.
- Zhou, Zhuohong,Dai, Guoyong,Ru, Shi,Yu, Han,Wei, Yongge
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supporting information
p. 14201 - 14205
(2019/10/02)
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- Highly selective epoxidation of cycloaliphatic alkenes with aqueous hydrogen peroxide catalyzed by [PO4{WO(O2) 2}4]3-/imidazole
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In the presence of imidazole as an additive, a phosphorus-containing tetranuclear peroxotungstate, THA3[PO4{WO(O 2)2}4] (I, THA=tetra-n-hexylammonium), could act as an efficient catalyst for epoxidation of cycloaliphatic alkenes with 30% aqueous hydrogen peroxide (H2O2). Compound I showed higher catalytic activity and selectivity to epoxide than other tungstates. By using the I/imidazole system, various kinds of cycloaliphatic alkenes could be highly selectively converted into the acid-sensitive epoxides including industrially important diepoxides in high to excellent yields under the almost stoichiometric conditions. The 1H NMR spectroscopy showed that imidazole would work not only as a proton acceptor but also as a Lewis base to remarkably suppress the acid-catalyzed ring opening of epoxides.
- Kamata, Keigo,Sugahara, Kosei,Ishimoto, Ryo,Nojima, Susumu,Okazaki, Motoya,Matsumoto, Takaya,Mizuno, Noritaka
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p. 2327 - 2332
(2014/08/18)
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- Highly efficient and selective oxidation of various substrates under mild conditions using a lanthanum-containing polyoxometalate as catalyst
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A lanthanum-containing polyoxometalate (POM) of DA11[La(PW 11O39)2] (denoted as DA-La(PW 11)2; DA = Decyltrimethylammonium cation) is highly efficient and selective for oxidation of various substrates including alkenes, alkenols, sulfides, silane and alcohol with only one equiv. H2O 2 as oxidant at 25 °C, and the POM catalyst can be easily recovered and reused for ten times without obvious decrease of catalytic activity and the yields for catalyst recovery are all above 95%. The epoxidation of cis-cyclooctene proceeds efficiently in 98% yield with only 0.08 mol% of DA-La(PW11)2, and the turnover number (TON) can reach as high as 1200 at 25 °C.
- Zhao, Shen,Jia, Yueqing,Song, Yu-Fei
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p. 188 - 194
(2013/03/28)
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- A highly active protonated tetranuclear peroxotungstate for oxidation with hydrogen peroxide
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Acid assists: The reaction of [{WO(O2)2} 2(μ-O)]2- with 0.5 equivalents of HNO3 gave a tetranuclear peroxotungstate (1; see picture) that has a dramatically enhanced activity for the epoxidation of cyclooctene with H2O2 compared to various peroxotungstates. The 1-catalyzed system was applicable to the selective oxidation of various kinds of substrates with 1.0-1.5 equivalents of H2O2. Copyright
- Ishimoto, Ryo,Kamata, Keigo,Mizuno, Noritaka
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experimental part
p. 4662 - 4665
(2012/06/30)
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- Efficient heterogeneous epoxidation of alkenes by a supported tungsten oxide catalyst
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Oxidation optimization: A combination of tungsten and zinc oxides on a SnO2 support (W-Zn/SnO2) is a heterogeneous and reusable solid catalyst for selective oxidation with aqueous H2O2. With it, various substrates, such as alkenes, amines, silanes, and sulfides, were oxidized into the corresponding products in high yields (see scheme). The catalyst can be reused several times without an appreciable loss in catalytic performance. Copyright
- Kamata, Keigo,Yonehara, Koji,Sumida, Yasutaka,Hirata, Kazuhisa,Nojima, Susumu,Mizuno, Noritaka
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supporting information; scheme or table
p. 12062 - 12066
(2012/02/03)
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- SOLID PHASE REACTION SYSTEM FOR OXIDATION
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A solid phase reaction system for oxidation of an organic compound, having high industrial value in which an organic solvent exerting a reverse influence on earth environments is not necessary, reuse of a catalyst is possible, and high yield can be attained, comprising a mixture of a powdery dispersion medium and a powder of a solid catalyst for the above-described oxidation reaction, and the above-described organic compound and aqueous hydrogen peroxide,wherein the above-described organic compound, the above-described solid catalyst and the above-described aqueous hydrogen peroxide are dispersed in the above-described mixture so that they get into contact mutually.
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Page/Page column 7
(2010/05/13)
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- OXIDIZING AGENT COMPOSITION FOR EPOXIDATION AND OXIDATION METHOD THEREOF
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Disclosed is a method for epoxidizing olefins, which enables an epoxy compound containing no halogen atom with high yield. Specifically disclosed is an oxidizing agent composition for epoxidation of olefins, which is characterized by containing peroxide which exhibits basicity when dissolved in water and an acid anhydride.
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Page/Page column 5
(2010/06/17)
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- BICYCLOHEPTANE-BASED COMPOUND, A CETANE NUMBER IMPROVER CONTAINING THE SAME, AND DIESEL FUEL
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Disclosed is a novel bicycloheptane-based compound. A cetane number improver containing the bicycloheptane-based compound and diesel fuel containing the cetane number improver are also provided. This cetane number improver has lower toxicity and superior stability, compared to a conventional cetane number improver, and can greatly improve the cetane number of fuel oil such as diesel, thus increasing combustion efficiency of fuel oil.
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Page/Page column 8
(2010/12/18)
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- OXIDIZING AGENT COMPOSITION FOR THE EPOXIDATION OF OLEFINS AND PROCESS FOR THE EPOXIDATION OF OLEFINS
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The invention aims at providing an oxidizing agent composition capable of producing halogen-free epoxy compounds in high yield; and a process for the epoxidation of olefins with the composition. In order to attain the aim, the invention provides an oxidizing agent composition for the epoxidation of olefins which is characterized by containing an acid anhydride and a solid hydrogen peroxide adduct; and a process for the epoxidation of olefins which is characterized by reacting an olefin with a mixture obtained by mixing an acid anhydride with a solid hydrogen peroxide adduct.
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Page/Page column 4
(2009/12/07)
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- Poly(per)fluoroalkanesulfonyl fluoride promoted olefin epoxidation with 30% aqueous hydrogen peroxide
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Epoxidation of various electron rich olefins with a novel oxidation system of poly(per)fluoroalkanesulfonyl fluoride/hydrogen peroxide/base is reported.
- Yan, Zhaohua,Tian, Weisheng
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p. 2211 - 2213
(2007/10/03)
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- Substrate-induced diastereoselectivity in the dimethyldioxirane epoxidation of simple alkenes and dienes
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Various alkenes and dienes, such as (R)- or (S)-limonene 2, 2-carene 6, 3-carene 8, (R)-α-pinene 10, (S)-α-pinene 12, and endo-dicyclopentadiene 14 were transformed into the corresponding mono- and bis-epoxides by epoxidation with dimethyldioxirane (as an acetone solution). The selectivity observed in these epoxidations is explained by the assumption of hydrogen bonding between bridge protons and the dioxirane.
- Asouti,Hadjiarapoglou
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p. 1847 - 1850
(2007/10/03)
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- Regioselective and diastereoselective dimethyldioxirane epoxidation of substituted norbornenes and hexamethyl Dewar benzene
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Various substituted norbornenes, such as endo-dicyclopentadiene 1, exo- dicyclopentadiene 5, 5-methylenebicyclo[2.2.1]hept-2-ene 8 and hexamethyl Dewar benzene 10 were transformed into the corresponding mono- and bis- epoxides by epoxidation with dimethyldioxirane (as an acetone solution).
- Asouti, Amalia,Hadjiarapoglou, Lazaros P.
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p. 539 - 542
(2007/10/03)
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- Effect Of The Medium On The Methanolysis Of Dicyclopentadiene Diepoxide
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The reaction of dicyclopentadiene diepoxide with methanol was studied by molecular mechanics and semiempirical quantum-chemical calculations.It was shown that the nature of the medium has an effect on the rate and direction of the reaction.In the presence of sodium methoxide chemo-, regio-, and stereoselective opening of the epoxycyclopentane fragment occurs; the direction of the reaction is controlled by the steric factor.In the case of acid-catalyzed methanolysis the reaction rate is increased, and both epoxide fragments are transformed; methanolysis is accompanied by intramolecular cyclization as a result of nucleophilic attack by the methoxy group from the endo region of the norbornane fragment.
- Kas'yan, L. I.,Gaponova, R. G.,Okovityi, S. I.
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p. 733 - 740
(2007/10/02)
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- Oxidation of Organic Substrates by Molecular Oxygen/Aldehyde/ Heteropolyoxometalate System
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Heteropolyoxometalate-catalyzed oxidations of organic compounds such as olefins and cyclic ketones with molecular oxygen in the presence of an aldehyde were examined.Olefins were epoxidized with dioxygen in the presence of 2 equiv of 2-methylpropanal under the influence of a catalytic amount of the mixed heteropolyoxometalate NPV6Mo6 (3) to give the corresponding epoxides in moderate to good yields.This catalytic oxidation method was also applied to the epoxidation of allylic and homoallylic alcohols.In the absence of olefins, the aldehydes were efficiently convertedinto the corresponding carboxylic acids.In addition, the Baeyer-Villiger oxidation of cyclic ketones was accomplished by using benzaldehyde instead of 2-methylpropanal as the aldehyde.
- Hamamoto, Masatoshi,Nakayama, Kouichi,Nishiyama, Yutaka,Ishii, Yasutaka
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p. 6421 - 6425
(2007/10/02)
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- SODIUM PERBORATE OXIDATIONS OF CYCLIC AND ACYCLIC ALKENES TO OXIRANES OR VICINAL ACETOXY ALCOHOLS
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Under different reaction conditions, sodium perborate/acetic anhydride oxidizes alkenes into oxiranes or vicinal acetoxy alcohols in good yields.
- Xie, Gaoyang,Xu, Linxiao,Hu, Jun,Ma, Shiming,Hou, Wei,Tao, Fenggang
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p. 2967 - 2968
(2007/10/02)
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- Dicyclopentadiene Oxidation. II. Catalyzed Liquid-Phase Oxidation of Dicyclopentadiene
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The liquid-phase oxidation of dicyclopentadiene 1 by molecular oxygen was studied in the presence of MoO2(acac)2 as a typical epoxidation catalyst.The yield of the mono-epoxides 2 and 3 is increased to 56.4 percent (uncatalyzed reaction: 43.6 percent).The ratio of the two mono-epoxides is decreased to 2/3 = 2.6 in relation to the uncatalyzed reaction 2/3 = 7.1).The influence of temperature, conversion and solvents is described.The bisepoxide 4 is formed at lower conversions than in the uncatalyzed reaction.But also at higher conversion of 1 not more than 10 percent of the bisepoxide 4 is formed.
- Schnurpfeil, D.
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p. 842 - 847
(2007/10/02)
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- Dicyclopentadiene Oxidation I. Uncatalyzed Liquid-Phase Oxidation of Dicyclopentadiene
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Dicyclopentadiene is oxidized by molecular oxygen to a mixture of the monoepoxides 2 and 3.The identification of the epoxides 2, 3 and 4 was executed with authentic samples prepared by epoxidation with peracetic acid or with tert-butylhydroperoxide in the presence of MoO2(acac)2.The main product is the substituted norbornene oxide 2.Allylic oxidation is also observed.Remarkable amounts of hydroperoxides can be determined iodometrically.The formation of allylic oxidation products 7, 8, 9 and 10 was proved by GC-MS-analysis.It is shown that in the uncatalyzed liquid phase oxidation of dicyclopentadiene no more than 50 percent of epoxides are formed.The bisepoxide 4 was found in small amounts only at higher conversions of the dicyclopentadiene.
- Schnurpfeil, D.
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p. 481 - 488
(2007/10/02)
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