- POTASSIUM FLUORIDE ON ALUMINA AS BASE FOR CROWN ETHER SYNTHESIS
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Alumina coated with potassium fluoride was found to be an effective and practical reagent for the synthesis of some simple crown ethers.
- Yamawaki, Junko,Ando, Takashi
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- H2-Free Selective Dehydroxymethylation of Primary Alcohols over Palladium Nanoparticle Catalysts
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The dehydroxymethylation of primary alcohols is a promising strategy to transform biomass-derived oxygenates into hydrocarbon fuels. In this study, a novel, highly efficient, and reusable heterogeneous catalyst system was established for the H2-free dehydroxymethylation of primary alcohol using cerium oxide-supported palladium nanoparticles (Pd/CeO2). A wide range of aliphatic and aromatic alcohols including biomass-derived alcohols were converted into the corresponding one-carbon shorter hydrocarbons in high yields in the absence of any additives, accompanied by the production of H2 and CO. Pd/CeO2 was easily recovered from the reaction mixture and reused, retaining its high activity, thus, providing a simple and sustainable methodology to produce hydrocarbon fuels from biomass-derived oxygenates.
- Yamaguchi, Sho,Kondo, Hiroki,Uesugi, Kohei,Sakoda, Katsumasa,Jitsukawa, Koichiro,Mitsudome, Takato,Mizugaki, Tomoo
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p. 1135 - 1139
(2020/12/29)
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- PROCESSES FOR FORMING GLYCOLS
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This disclosure provides processes for forming glycols by upgrading hydrocarbons. In one embodiment, a process for forming a glycol includes introducing a first ether to a dihydrocarbyl peroxide to form a diether and a first alcohol. The process includes introducing the diether to water to form a glycol and a second alcohol. Processes of this disclosure may include one or more of: introducing a hydrocarbyl hydroperoxide to a third alcohol to form the dihydrocarbyl peroxide; oxidizing a first feed stream comprising a branched hydrocarbon to form the hydrocarbyl hydroperoxide and the first alcohol; and/or introducing the second alcohol to a catalyst to form a second ether.
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Paragraph 0096
(2020/05/28)
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- Method for hydrogenation synthesis of ethylene glycol from oxalate
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The invention relates to a method for catalytic hydrogenation synthesis of ethylene glycol from oxalate. The method mainly solves the problem that the existing catalytic reaction process for oxalate hydrogenation synthesis of ethylene glycol has low selectivity and a short catalyst life. Metal copper or copper oxide is used as an active component in the catalyst, hydrophilic silica or modified hydrophilic silica is used as a carrier and an appropriate metal oxide assistant is used. The catalyst has high reaction performances and reaction stability.
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Paragraph 0060-0064; 0066-0067; 0070-0071; 0074-0076
(2018/04/02)
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- Method and catalyst for hydrogenating oxalate to produce methyl glycolate
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The invention relates to a method and a catalyst for hydrogenating oxalate to produce methyl glycolate. The problems of low selectivity of glycolate in hydrogenation products and high catalyst cost existing in previous technologies are mainly solved. In the invention, metal copper or an oxide thereof is adopted as an active component, a silica-containing composite oxide, such as SBA-15 and a molecular sieve, is adopted as a carrier, and an appropriate metal or an oxide assistant is added. The structure characteristic of the silicon-containing composite oxide molecular sieve is adopted to highly disperse the active component copper or the oxide thereof, so the reaction conversion rate and the methyl glycolate selectivity are improved; adoption of a precious metal assistant is avoided, so the catalyst cost is reduced; and a high oxalate conversion rate and a high methyl glycolate selectivity are simultaneously realized.
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Paragraph 0020; 0021; 0026; 0027
(2017/03/14)
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- Reactions of diols with dimethyl carbonate in the presence of W(CO) 6 and Co2(CO)8
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Dimethoxyalkanes and dimethyl alkanediyl biscarbonates were synthesized by reactions of diols with dimethyl carbonate in the presence of tungsten and cobalt carbonyls. Optimal reactant and catalyst ratios and reaction conditions were found to ensure selective formation of dimethoxyalkanes or dimethyl alkanediyl biscarbonates.
- Khusnutdinov,Shchadneva,Mayakova
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p. 948 - 952
(2014/10/16)
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- PROCESS FOR PREPARING FLUORINE-CONTAINING ALKOXYALKANE
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A process for preparing a fluorine-containing alkoxyalkane represented by the general formula (1) R1—O—R2—O—R3 where at least one of R1, R2 and R3 contains one or more fluorine atoms. An alcohol with the highest acidity selected from the group consisting of the compounds represented by the general formula (2) R1—OH, the general formula (3) R3—O—R2—OH, the general formula (4) R1—O—R2—OH, and the general formula (5) R3—OH is reacted with at least one selected from the group consisting of the compounds represented by the general formula (6) Lg-R2—O—R3, the general formula (7) Lg-R1, the general formula (8) Lg-R3, and the general formula (9) Lg-R2—O—R1 where Lg represents an anionic leaving group in the presence of a basic compound.
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Page/Page column 7-8
(2009/01/20)
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- METHOD FOR THE PRODUCTION OF POLYOXYMETHYLENE DIALKYL ETHERS FROM TRIOXAN AND DIALKYLETHERS
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The invention relates to a method for production of polyoxymethylene dialkyl ethers of formula H2m+1CmO(CH2O)nCmH2m+1, where n = 2 - 10, m independently = 1 or 2, in which a dialkyl ether selected from dimethyl ether, methyl ethyl ether or diethyl ether and trioxan are fed into a reactor and reacted in the presence of an acid catalyst, whereby the amount of water introduced into the reaction mixture with the dialkyl ether, trioxan and/or the catalyst is 1 wt. %, with relation to the reaction mixture.
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Page/Page column 6
(2008/06/13)
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- METHOD FOR PRODUCING ALKYLENE GLYCOL DIETHERS
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The invention concerns a method for producing alkylene glycol diethers by reacting a linear or cyclic ether with an alkylene oxide in the presence of a Lewis acid. The invention is characterized in that the reaction is continuously carried out in a microreactor.
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Page/Page column 7-9
(2008/06/13)
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- METHOD OF PRODUCING GLYCOL ETHERS
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The present invention provides a method of producing glycol ethers, which are also commonly known as glymes. The method according to the invention includes contacting a glycol with a monohydric alcohol in the presence of a polyperfluorosulfonic acid resin catalyst under conditions effective to produce the glyme. The method of the invention can be used to produce, for example, monoglyme, ethyl glyme, diglyme, ethyl diglyme, triglyme, butyl diglyme, tetraglyme, and their respective corresponding monoalkyl ethers. The present invention also provides a method of producing 1,4-dioxane from mono- or diethylene glycol and tetrahydrofuran from 1,4-butanediol.
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- SYNTHESIS OF DIALKYL ETHERS OF POLYETHYLENE GLYCOLS
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Methods were developed for synthesis of dimethyl and diethyl ethers of polyethylene glycols in one step (without isolation of intermediates) with the general formula R(OC2H4)mOR, where R=CH3, C2H5 and m=2-6 (degree of polyglycolicity).As starting materials monomethyl and monoethyl ethers of polyethylene glycols of the formula R(OC2H4)nOH were used, where n=1-3.As reagents toluenesulfonyl chloride and methanesulfonyl chloride were used.
- Barnakov, Ch. N.,Volgin, A. A.
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p. 152 - 155
(2007/10/02)
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- Unconventional Ionic Hydrogen Bonds. 1. Complexes of Quaternary Ions with n- and ?-Donors
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interaction energies are obtained from the clustering of quaternary onium ions with n-donor solvent molecules.The dissociation energies (ΔHoD) of Me4N(1+) clustered with the n-donor H2O, MeOH, MeNH2, and Me3N and with the ?-donors benzene and toluene range between 8 and 10 kcal mol-1.With the weak, bulky n-donor MeCl the interaction is weaker (6.5 kcal mol-1) while the more polar ligands Me2CO and MeCONMe2 attach strongly (14.6 and 18.0 kcal mol-1, respectively) to Me4N(1+).Strong interactions, 20-23 kcal mol-1, are also observed with polyethers and CH3CO-gly-OCH3, indicating polydentate complexing.The attachment energies of ligands to Et4N(1+) are smaller by 2 kcal mol-1 than those to Me4N(1+).Ab initio calculations show that in the Me4N(1+)*H2O, MeOH, MeNH2, and MeCl complexes the ligands attach electrostatically to a cavity created by protons of three CH3 gropus rather than hydrogen bonding to one proton or to one CH3 group.Both experiment and theory indicate that a second solvent molecule (H2O or CH3OH) attaches preferentially to the first solvent molecule rather than to Me4N(1+).
- Meot-Ner (Mautner), Michael,Deakyne, Carol A.
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p. 469 - 474
(2007/10/02)
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- AFFINITIES OF CROWN ETHERS, GLYMES, AND POLYAMINES FOR ALKALI PICRATES IN TOLUENE. APPLICATION OF POLYMER-SUPPORTED LINEAR POLYETHERS.
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This work reports the measurements of K values for polyamines, glymes, a few glycols (including that of a long-chain polyethylene glycol, carbowax 6000), and some frequently used cation-binding ligands as complexers of lithium or sodium picrate in toluene as solvent. K values for different resins obtained with the same soluble ligand provide a comparison of the effectiveness of these resins in binding ionic solutes.
- Xu,Smid
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p. 3790 - 3796
(2007/10/02)
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- The Ionic Hydrogen Bond. 2. Multiple NH+...O and CH?+...O Bonds. Complexes of Ammonium Ions with Polyethers and Crown Ethers
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Complexes of ammonium ions RNH3+ (R = CH3, c-C6H11), (CH3)3NH+, and pyridineH+ with polyethers and crown ethers are observed in the gas phase in the abscence of the solvent effects.The dissociation energies, ΔH0D, of the RNH3+ polyether complexes range from 29.4 kcal mol-1 (for RNH3+*CH3OCH2CH2OCH3) to 46 kcal mol-1 (RNH3+*18-crown-6).The large ΔH0D values for complexes of polydentate ligands indicate multiple -NH+...O-hydrogen bonding.Such mutiple bonding can contribute up to 18 kcal mol-1 to the bonding in RNH3+*CH3(OCH2CH2)3OCH3 and 21 kcal mol-1 in RNH3+*18-crown-6.Multiple interactions are also evident in the (CH3)3NH+*polyether complexes where -CH?+...O-hydrogen bonding seems to occur; and consecutive -CH?+...O-bonds contribute approximately 6, 4, and 2 kcal/mol-1 respectively for up to three such bonds.Total ΔH0D values in the (CH3)3NH+*polyether complexes thus range from 26.7 kcal mol-1 in (CH3)3NH+*CH3O(CH2)2OCH3 to 41 kcal mol-1 in (CH3)3NH+*18-crown-6.Multiple interaction effects, possibly including van der Waals dispersion forces, are observed also in pyridineH+*polyether complexes.Large negative entropies in RNH3+*acyclic polyether complexes vs.RNH3+*cyclic crown ethers make the acyclic polyethers less efficient ligands.
- Meot-Ner (Mautner), Michael
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p. 4912 - 4915
(2007/10/02)
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- Hair dye compositions and new compounds useful therein
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Novel compounds of the general formula STR1 wherein Z represents a substituted lower alkyl radical; each of R1 and R2 is hydrogen atom, a lower alkyl or a substituted lower alkyl identical with or different from Z and the functional groups NO2 and NR1 R2 can occupy all ring positions in relation to OZ, with the exception that if Z is β-hydroxyethyl, --NO2 is in the 4 position and --N(R1)(R2) is in the 2 position then either R1 or R2 is other than hydrogen. The novel compounds are for dyeing human hair in a variety of yellow shades. The compounds of formula (I) may be used as aqueous or water-alcohol solutions to form dye compositions for dyeing human hair.
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- SYNTHESIS OF BISPEROXYDICARBONATES AND THEIR REACTIVITY
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A series of symmetrical peroxydicarbonates were obtained from the chloroformates of diethylene or dipropylene glycol monoethers.Their homolysis in benzene and in the presence of styrene and α-naphthol was investigated.The effect of the structure of the organic fragment of the peroxide on the effective, induced, and monomolecular dissociation constants is discussed.A scheme is proposed for the transformation of the free radicals which form on the basis of kinetic data and analysis of the final thermal dissociation products.
- Fomin, V. A.,Etlis, V. S.,Nozrina, F. D.
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- FLUORIDE SALTS ON ALUMINA AS REAGENTS FOR ALKYLATION OF PHENOLS AND ALCOHOLS.
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THE EFFECTIVENESS OF ALKALI METAL FLUORIDES IMPREGNATED ON ALUMINA AS A REAGENT FOR PROMOTING ALKYLATION WAS OPTIMIZED WITH RESPECT TO THE METAL CATION, THE AMOUNT OF IMPREGNATION, AND THE REACTION SOLVENT. POTASSIUM OR CAESIUM FLUORIDE ONALUMINA IN ACETONITRILE OR 1,2-DIMETHOXYETHANE WAS CONCLUDED TO BE THE BEST REACTION SYSTEM FOR GENERAL USE. O-ALKYLATION OF SUBSTITUTED PHENOLS, PRIMARY AND SECONDARY ALCOHOLS, AND A GLYCOL WAS CARRIED OUT MOSTLY IN GOOD YIELDS UNDER MILDCONDITIONS WITH SIMPLE EXPERIMENTAL PROCEDURES.
- ANDO,YAMAWAKI,KAWATE,SUMI,HANAFUSA
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p. 2504 - 2507
(2007/10/02)
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