{"@context":{"@vocab":"https://cir.nii.ac.jp/schema/1.0/","rdfs":"http://www.w3.org/2000/01/rdf-schema#","dc":"http://purl.org/dc/elements/1.1/","dcterms":"http://purl.org/dc/terms/","foaf":"http://xmlns.com/foaf/0.1/","prism":"http://prismstandard.org/namespaces/basic/2.0/","cinii":"http://ci.nii.ac.jp/ns/1.0/","datacite":"https://schema.datacite.org/meta/kernel-4/","ndl":"http://ndl.go.jp/dcndl/terms/","jpcoar":"https://github.com/JPCOAR/schema/blob/master/2.0/"},"@id":"https://cir.nii.ac.jp/crid/1390282679365921152.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1246/nikkashi.1988.1691"}},{"identifier":{"@type":"URI","@value":"https://www.jstage.jst.go.jp/article/nikkashi1972/1988/10/1988_10_1691/_pdf"}},{"identifier":{"@type":"NAID","@value":"130004158850"}}],"dc:title":[{"@language":"en","@value":"Preparation of Ethylene Glycol by the Oxidation of Ethylene with Thallium (III) Chloridet"},{"@language":"ja","@value":"塩化タリウム (III) を用いたエチレンの酸化によるエチレングリコールの生成"},{"@value":"Preparation of ethylene glycol by the oxidation of ethylene with thallium(III) chloride."}],"description":[{"type":"abstract","notation":[{"@language":"en","@value":"The oxidation of ethylene by thallium (III) chloride in aqueous hydrochloric acid solution was investigated at temperatures between 120 and 170°C.<BR>Ethylene was oxidized stoichiometrically with Tl(III) to yield in situ ethylene glycol (EG). The oxidation proceeded by typical successive reaction from ethylene to EG via ethylene chlorohydrin. When the molar ratio of [Cl<SUP>-</SUP>]/[Tl<SUP>3+</SUP>] in the solution was above 7, EG was formed in 80% yield. The effects of reaction period and temperature on the yield of EG were examined, and the results obtained were plotted contour graphically. The optimum conditions for the preparation of EG were thus determined as follows. The best results will be obtained by running the reaction for 3-5 h at 140-150°C.<BR>The effects of Tl<SUP>3+</SUP>, H<SUP>+</SUP>, Cl<SUP>-</SUP> and alkali metal cations on the reaction were also studied, the results suggesting that most of EG was not formed by direct oxidation of ethylene with T1(III) but formed by hydrolysis of ethylene chlorohydrin."},{"@language":"ja","@value":"塩化タリウム (III) によるエチレン酸化反応の低温下における主生成物エチレンクロロヒドリン (ECH) そのまま加水分解をうけてエチレングリコール (EG) になるように, 加圧下, 100℃ 以上のが高温ので塩化タリウム (III) 水溶液によるエチレンの酸化反応を行なった。反応はエチレンと TI(III) との完全な 1:1 当量反応でいったん ECH を急速に生成しつぎにこれが緩やかに EG に転化する典型的逐次反応で進行した。低温下の反応の場合にほとんど選択的に ECH を生成するような反応条件下 ([Cl<SUP>-</SUP>]/[Tl<SUP>3+</SUP>]>7～10) では, 使用した Tl (III) (およびエチレン) に対して約80%弱の高収率でEGが得られた。<BR>実用上の見地から反応温度と時間についてEG収率等高線図を求め,これからEGを高奴率で得るための最適条件範囲として, 160℃, 2時間から135℃, 7時間まで, とくに150℃, 3時間から140℃, 5時間までを得た。<BR>この酸化反応における Tl<SUP>3+</SUP>, H<SUP>+</SUP>, Cl<SUP>-</SUP> 各イオンおよびアルカリ金属イオンの影響を検討した結果と, またこの反応を ECH の加水分解反応 (実験値および計算値) と比較した結果は, いずれもこの反応における EG の生成が ECH の加水分解に支配されることを強く示唆した。"}],"abstractLicenseFlag":"disallow"}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1410851398292702336","@type":"Researcher","personIdentifier":[{"@type":"NRID","@value":"9000256046984"}],"foaf:name":[{"@language":"en","@value":"HIROSE Isao"},{"@language":"ja","@value":"広瀬 功"}],"jpcoar:affiliationName":[{"@language":"ja","@value":"帝人株式会社生産技術研究所"},{"@language":"en","@value":"Products DevelopmenIt nstitute, Teijin Ltd."}]},{"@id":"https://cir.nii.ac.jp/crid/1410851398292702337","@type":"Researcher","personIdentifier":[{"@type":"NRID","@value":"9000256046985"}],"foaf:name":[{"@language":"en","@value":"FUJI Takeshi"},{"@language":"ja","@value":"藤井 健史"}],"jpcoar:affiliationName":[{"@language":"ja","@value":"帝人株式会社生産技術研究所"},{"@language":"en","@value":"Products DevelopmenIt nstitute, Teijin Ltd."}]},{"@id":"https://cir.nii.ac.jp/crid/1410851398292702338","@type":"Researcher","personIdentifier":[{"@type":"NRID","@value":"9000256046986"}],"foaf:name":[{"@language":"en","@value":"KOBAYASHI Takayuki"},{"@language":"ja","@value":"小林 隆幸"}],"jpcoar:affiliationName":[{"@language":"ja","@value":"帝人株式会社生産技術研究所"},{"@language":"en","@value":"Products DevelopmenIt nstitute, Teijin Ltd."}]}],"publication":{"publicationIdentifier":[{"@type":"PISSN","@value":"03694577"},{"@type":"EISSN","@value":"21850925"}],"prism:publicationName":[{"@language":"en","@value":"NIPPON KAGAKU KAISHI"},{"@language":"ja","@value":"日本化学会誌（化学と工業化学）"},{"@language":"en","@value":"Nippon Kagaku Kaishi"},{"@language":"ja","@value":"日化"},{"@language":"en","@value":"NIPPON KAGAKU KAISHI"},{"@language":"ja","@value":"日本化学会誌"}],"dc:publisher":[{"@language":"en","@value":"The Chemical Society of Japan"},{"@language":"ja","@value":"公益社団法人 日本化学会"}],"prism:publicationDate":"1988-10-10","prism:volume":"1988","prism:number":"10","prism:startingPage":"1691","prism:endingPage":"1697"},"reviewed":"false","url":[{"@id":"https://www.jstage.jst.go.jp/article/nikkashi1972/1988/10/1988_10_1691/_pdf"}],"availableAt":"1988-10-10","foaf:topic":[{"@id":"https://cir.nii.ac.jp/all?q=General%20Chemistry","dc:title":"General Chemistry"}],"dataSourceIdentifier":[{"@type":"JALC","@value":"oai:japanlinkcenter.org:0022311666"},{"@type":"CROSSREF","@value":"10.1246/nikkashi.1988.1691"},{"@type":"CIA","@value":"130004158850"}]}