{"@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/1390282679394428416.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1246/nikkashi.1979.239"}},{"identifier":{"@type":"COI","@value":"1:CAS:528:DyaE1MXitVegtbs%3D"}},{"identifier":{"@type":"URI","@value":"https://www.jstage.jst.go.jp/article/nikkashi1972/1979/2/1979_2_239/_pdf"}},{"identifier":{"@type":"NAID","@value":"130004156366"}}],"dc:title":[{"@language":"en","@value":"Syntheses of 9-Substituted 1-methylfluorene Derivatives and Restricted Rotation around the C(9)-C Single Bonds in these Compounds"},{"@language":"ja","@value":"9-置換1-メチルフルオレン誘導体の合成とそれらのC(9)-C単結合の束縛回転"},{"@value":"フルオレン誘導体の回転異性　ＩＶ　　９‐置換１‐メチルフルオレン誘導体の合成とそれらのＣ（９）‐Ｃ単結合の束縛回転"}],"description":[{"type":"abstract","notation":[{"@language":"en","@value":"Reaction of 1-methyl-9-fluorenone [ 1 ] with a variety of Grignard reagents or organolithium compounds gave 9-substituted 1-methyl-9-fluorenols [ 4].9-Alkoxy-9-ary1-1-methylfluorenes [6 ] were obtained by refluxing the solution of 9-bromo-1-methylfluorenes [ 5 ] in alcohol which in turn were prepared from C 4 J with HBr in acetic acid. Reduction of [ 4 ] with HI in acetic acid gave 9-substituted 1-methylfluorenes [ 7 ] (e. g., 9- (2-methylpheny1)- [7 e], 9- (3- methylpheny1)- [7 f], 9- (4-methylphenyl) - [7 g], 9- (1-naphthyl) [7 h], and 9- (2-methyl-1-naphthyl)-1-methylfluorene [7 i]).<BR>The restricted rotation around the C<SUB>sp3</SUB>-C<SUB>sp2</SUB> single bond in [ 7 ] has been investigated by means of the DNMR method. Rotational barriers around the C<SUB>sp3</SUB>-C<SUB>sp2</SUB> bond in [7 e] (Δ G<SUB>115c</SUB>=19.6 kcal/mol) and [7 h] (Δ G<SUB>160o</SUB>=21.4 kcal/mol) were found to be 2-3 kcal/mol higher than those of 9- (2-methylphenyl)fluorene and 9- (1-naphthyl) fluorene, respectively."},{"@language":"ja","@value":"1-メチル-9-フルオレノン〔1〕に種々のGrignard試薬や有機リチウム化合物を作用させて種々の9-置換1-メチル-9-フルオレノール誘導体〔4〕を合成した。つぎにこれを9-プロモ体〔5〕としたのちアルコールと加熱して9-アルコキシ誘導体〔6〕とした。また〔4〕を還元して9-置換1-メチルフルオレン〔7〕を合成した。ついでこれらの化合物のC(9)-C単結合の束縛回転をDNMRスペクトルから検討した。この場合,とくに1-メチル-9-(2-メチルフェニル)フルオレン〔7e〕および1-メチル-9-(1-ナフチル)フルオレン〔7h〕においてはC<SUB>sp3</SUB>が-C<SUB>sp2</SUB>単結合の回転のエネルギー障壁が,9-(2-メチルフェニル)フルオレンや9-(1-ナフチル)フルオレンにくらべて2～3kcal/mol高いことが判明した。"}],"abstractLicenseFlag":"disallow"}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1030566608929299585","@type":"Researcher","personIdentifier":[{"@type":"KAKEN_RESEARCHERS","@value":"90035030"},{"@type":"NRID","@value":"1000090035030"},{"@type":"NRID","@value":"9000002267318"},{"@type":"NRID","@value":"9000006162235"},{"@type":"NRID","@value":"9000253104159"},{"@type":"NRID","@value":"9000021047380"},{"@type":"NRID","@value":"9000253100054"},{"@type":"NRID","@value":"9000003424020"},{"@type":"NRID","@value":"9000252794252"},{"@type":"NRID","@value":"9000256035422"},{"@type":"NRID","@value":"9000256039021"},{"@type":"NRID","@value":"9000018197348"},{"@type":"NRID","@value":"9000020294859"},{"@type":"NRID","@value":"9000252794284"},{"@type":"NRID","@value":"9000256048256"},{"@type":"NRID","@value":"9000256035509"},{"@type":"NRID","@value":"9000256048949"},{"@type":"NRID","@value":"9000256045853"},{"@type":"NRID","@value":"9000253100820"},{"@type":"NRID","@value":"9000255706928"},{"@type":"NRID","@value":"9000256044900"},{"@type":"NRID","@value":"9000254694126"},{"@type":"NRID","@value":"9000253100190"},{"@type":"NRID","@value":"9000255708423"},{"@type":"NRID","@value":"9000256034045"},{"@type":"NRID","@value":"9000256045849"},{"@type":"NRID","@value":"9000253101399"},{"@type":"NRID","@value":"9000255705021"},{"@type":"NRID","@value":"9000256036539"},{"@type":"NRID","@value":"9000020946109"},{"@type":"NRID","@value":"9000020296244"},{"@type":"NRID","@value":"9000255708415"},{"@type":"NRID","@value":"9000256042919"},{"@type":"NRID","@value":"9000256047490"},{"@type":"NRID","@value":"9000256049004"},{"@type":"NRID","@value":"9000020962340"},{"@type":"NRID","@value":"9000255705016"},{"@type":"NRID","@value":"9000255705038"},{"@type":"NRID","@value":"9000256042817"},{"@type":"NRID","@value":"9000256043554"},{"@type":"NRID","@value":"9000254690708"},{"@type":"NRID","@value":"9000256047473"},{"@type":"NRID","@value":"9000256036681"},{"@type":"NRID","@value":"9000256039186"},{"@type":"NRID","@value":"9000256048760"}],"foaf:name":[{"@language":"en","@value":"KAJIGAESHI Shoji"},{"@language":"ja","@value":"梶返 昭二"}],"jpcoar:affiliationName":[{"@language":"en","@value":"Department of Industrial Chemistry, Faculty of Engineering Yamaguchi University"},{"@language":"ja","@value":"山口大学工学部工業化学科"}]},{"@id":"https://cir.nii.ac.jp/crid/1030285133318733441","@type":"Researcher","personIdentifier":[{"@type":"KAKEN_RESEARCHERS","@value":"60035045"},{"@type":"NRID","@value":"1000060035045"},{"@type":"NRID","@value":"9000002267396"},{"@type":"NRID","@value":"9000002267334"},{"@type":"NRID","@value":"9000008359110"},{"@type":"NRID","@value":"9000002389331"},{"@type":"NRID","@value":"9000253104161"},{"@type":"NRID","@value":"9000006162315"},{"@type":"NRID","@value":"9000256035420"},{"@type":"NRID","@value":"9000256039022"},{"@type":"NRID","@value":"9000256035508"},{"@type":"NRID","@value":"9000256048948"},{"@type":"NRID","@value":"9000256045852"},{"@type":"NRID","@value":"9000255706927"},{"@type":"NRID","@value":"9000256044897"},{"@type":"NRID","@value":"9000255708426"},{"@type":"NRID","@value":"9000256034048"},{"@type":"NRID","@value":"9000256045848"},{"@type":"NRID","@value":"9000255705039"},{"@type":"NRID","@value":"9000255705017"},{"@type":"NRID","@value":"9000256036536"},{"@type":"NRID","@value":"9000256042917"},{"@type":"NRID","@value":"9000256047495"},{"@type":"NRID","@value":"9000255705012"},{"@type":"NRID","@value":"9000255705034"},{"@type":"NRID","@value":"9000256042814"},{"@type":"NRID","@value":"9000256043553"},{"@type":"NRID","@value":"9000256036678"},{"@type":"NRID","@value":"9000256039182"}],"foaf:name":[{"@language":"en","@value":"FUJISAKI Shizuo"},{"@language":"ja","@value":"藤崎 静男"}],"jpcoar:affiliationName":[{"@language":"ja","@value":"山口大学工学部工業化学科"},{"@language":"en","@value":"Department of Industrial Chemistry, Faculty of Engineering Yamaguchi University"}]},{"@id":"https://cir.nii.ac.jp/crid/1410569845480432768","@type":"Researcher","personIdentifier":[{"@type":"NRID","@value":"9000256039023"}],"foaf:name":[{"@language":"en","@value":"KADOYA Naoyuki"},{"@language":"ja","@value":"角屋 直行"}],"jpcoar:affiliationName":[{"@language":"en","@value":"Department of Industrial Chemistry, Faculty of Engineering Yamaguchi University"},{"@language":"ja","@value":"山口大学工学部工業化学科"}]},{"@id":"https://cir.nii.ac.jp/crid/1410569845480432769","@type":"Researcher","personIdentifier":[{"@type":"NRID","@value":"9000256039024"}],"foaf:name":[{"@language":"en","@value":"KONDO Masahiko"},{"@language":"ja","@value":"近藤 正彦"}],"jpcoar:affiliationName":[{"@language":"en","@value":"Department of Industrial Chemistry, Faculty of Engineering Yamaguchi University"},{"@language":"ja","@value":"山口大学工学部工業化学科"}]},{"@id":"https://cir.nii.ac.jp/crid/1410569845480432771","@type":"Researcher","personIdentifier":[{"@type":"NRID","@value":"9000256039025"}],"foaf:name":[{"@language":"en","@value":"UEDA Koji"},{"@language":"ja","@value":"上田 幸次"}],"jpcoar:affiliationName":[{"@language":"ja","@value":"山口大学工学部工業化学科"},{"@language":"en","@value":"Department of Industrial Chemistry, Faculty of Engineering Yamaguchi University"}]}],"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":"1979-02-10","prism:volume":"1979","prism:number":"2","prism:startingPage":"239","prism:endingPage":"242"},"reviewed":"false","url":[{"@id":"https://www.jstage.jst.go.jp/article/nikkashi1972/1979/2/1979_2_239/_pdf"}],"availableAt":"1979-02-10","foaf:topic":[{"@id":"https://cir.nii.ac.jp/all?q=General%20Chemistry","dc:title":"General Chemistry"}],"dataSourceIdentifier":[{"@type":"JALC","@value":"oai:japanlinkcenter.org:0030915898"},{"@type":"CROSSREF","@value":"10.1246/nikkashi.1979.239"},{"@type":"CIA","@value":"130004156366"}]}