{"created":"2023-05-15T12:20:46.506348+00:00","id":11459,"links":{},"metadata":{"_buckets":{"deposit":"3731ba60-5490-4745-a2df-f235423e619e"},"_deposit":{"created_by":1,"id":"11459","owners":[1],"pid":{"revision_id":0,"type":"depid","value":"11459"},"status":"published"},"_oai":{"id":"oai:kansai-u.repo.nii.ac.jp:00011459","sets":["528:1588:1595:1597"]},"author_link":["26428","26426","26431","26422","26427","26429","26425","26430","26424","26423"],"item_9_biblio_info_7":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2001","bibliographicIssueDateType":"Issued"},"bibliographicIssueNumber":"2","bibliographicPageEnd":"370","bibliographicPageStart":"363","bibliographicVolumeNumber":"74","bibliographic_titles":[{"bibliographic_title":"Bulletin of the Chemical Society of Japan"}]}]},"item_9_description_4":{"attribute_name":"概要","attribute_value_mlt":[{"subitem_description":"The rates of solvolysis in various solvents were determined for 1,1,3,3-tetramethyl-2-oxobutyl tosylate (1OTs) and 1,3,3-trimethyl-2-oxocyclopentyl mesylate (4\nOMs). The rate data for 1OTs reinforced that the linear Grunwald−Winstein (GW) relationship of 1OMs previously reported by Creary for non-aqueous solvents must also hold for aqueous organic solvents.4OMs showed a markedly dispersed GW relationship that is, on the other hand, well correlated\nwith an extended GW equation involving a nucleophilicity parameter. Such solvent dependence, such marked effects of added sodium azide on rates, and the 100% inversion of configuration of the solvolysis product showed that the solvolysis of 4OMs would be categorized to SN2(intermediate), whereas 1OMs and1OTs solvolyze via limiting S\nN1.The negligible susceptibility of 1OTs toward nucleophilicity of solvent and azide probe indicates that the nucleofuge leaves along the C=O axis in such a manner that the back-strain (B-strain) in the ground state is efficiently relieved in the transition state. Comparison of solvolysis rates of \n1OMs and 4OMs with those of the corresponding parent substrates suggests that the transition states of these substrates would not be stabilized by carbonylπ conjugation. The origin of the \nunexpectedly fast rates of solvolysis of 1\nOMs has been discussed.","subitem_description_type":"Other"}]},"item_9_full_name_3":{"attribute_name":"著者別名","attribute_value_mlt":[{"nameIdentifiers":[{"nameIdentifier":"26430","nameIdentifierScheme":"WEKO"}],"names":[{"name":"田中, 耕一"}]},{"nameIdentifiers":[{"nameIdentifier":"26431","nameIdentifierScheme":"WEKO"}],"names":[{"name":"戸田, 芙三夫"}]}]},"item_9_publisher_34":{"attribute_name":"出版者","attribute_value_mlt":[{"subitem_publisher":"Chemical Society of Japan"}]},"item_9_relation_12":{"attribute_name":"DOI","attribute_value_mlt":[{"subitem_relation_type":"isIdenticalTo","subitem_relation_type_id":{"subitem_relation_type_id_text":"10.1246/bcsj.74.363","subitem_relation_type_select":"DOI"}}]},"item_9_source_id_10":{"attribute_name":"書誌レコードID","attribute_value_mlt":[{"subitem_source_identifier":"AA00580132","subitem_source_identifier_type":"NCID"}]},"item_9_source_id_8":{"attribute_name":"ISSN","attribute_value_mlt":[{"subitem_source_identifier":"00092673","subitem_source_identifier_type":"ISSN"}]},"item_9_text_35":{"attribute_name":"出版者（他言語）","attribute_value_mlt":[{"subitem_text_value":"日本化学会"}]},"item_9_version_type_17":{"attribute_name":"著者版フラグ","attribute_value_mlt":[{"subitem_version_resource":"http://purl.org/coar/version/c_970fb48d4fbd8a85","subitem_version_type":"VoR"}]},"item_creator":{"attribute_name":"著者","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"Takeuchi, Ken'ichi"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Ushino, Takuhiro"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Okazaki, Takao"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Kitagawa, Toshikazu"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Kinoshita, Tomomi"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Ohga, Yasushi"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Tanaka, Koichi"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Toda, Fumio"}],"nameIdentifiers":[{}]}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2019-05-23"}],"displaytype":"detail","filename":"KU-1100-20011207-21.pdf","filesize":[{"value":"240.3 kB"}],"format":"application/pdf","licensetype":"license_note","mimetype":"application/pdf","url":{"label":"KU-1100-20011207-21.pdf","url":"https://kansai-u.repo.nii.ac.jp/record/11459/files/KU-1100-20011207-21.pdf"},"version_id":"5cf92599-d16c-4e9f-87ff-0c906f12c67e"}]},"item_language":{"attribute_name":"言語","attribute_value_mlt":[{"subitem_language":"eng"}]},"item_resource_type":{"attribute_name":"資源タイプ","attribute_value_mlt":[{"resourcetype":"journal article","resourceuri":"http://purl.org/coar/resource_type/c_6501"}]},"item_title":"Solvent Effects and Steric Course in the Solvolysis of 1,3,3-Trimethyl-2- oxocyclopentyl Mesylate in Comparison with 1,1,3,3-Tetramethyl-2- oxobutyl System","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"Solvent Effects and Steric Course in the Solvolysis of 1,3,3-Trimethyl-2- oxocyclopentyl Mesylate in Comparison with 1,1,3,3-Tetramethyl-2- oxobutyl System"}]},"item_type_id":"9","owner":"1","path":["1597"],"pubdate":{"attribute_name":"公開日","attribute_value":"2011-11-21"},"publish_date":"2011-11-21","publish_status":"0","recid":"11459","relation_version_is_last":true,"title":["Solvent Effects and Steric Course in the Solvolysis of 1,3,3-Trimethyl-2- oxocyclopentyl Mesylate in Comparison with 1,1,3,3-Tetramethyl-2- oxobutyl System"],"weko_creator_id":"1","weko_shared_id":1},"updated":"2023-05-15T18:31:00.847019+00:00"}