{"created":"2023-07-27T06:26:47.701927+00:00","id":10661,"links":{},"metadata":{"_buckets":{"deposit":"ff514ad1-aed5-440a-8ab0-4381af93c34a"},"_deposit":{"created_by":3,"id":"10661","owners":[3],"pid":{"revision_id":0,"type":"depid","value":"10661"},"status":"published"},"_oai":{"id":"oai:kanazawa-u.repo.nii.ac.jp:00010661","sets":["934:935:937"]},"author_link":["16247","16249","16248","16246"],"item_4_biblio_info_8":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"1996-03-10","bibliographicIssueDateType":"Issued"},"bibliographicIssueNumber":"3","bibliographicPageEnd":"282","bibliographicPageStart":"275","bibliographicVolumeNumber":"1996","bibliographic_titles":[{"bibliographic_title":"日本化学会誌 : 化学と工業化学 = Journal of the Chemical Society of Japan : chemistry and industrial chemistry"}]}]},"item_4_description_21":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"一般にハロゲン化第三級アルキルとアルカリ金属アルコキシド及びフェノキシドとを極性溶媒中で反応させると,ほとんどオレフィン(E)のみが得られる。しかし本研究では無極性溶媒中で第三級アルキル基質と金属アルコキシド及びアリールオキシドとの SN 反応により第三級アルキルエーテルを合成する方法を見いだした。アルカリ金属フェノキシドは臭化及びヨウ化かブチルとヘキサン中, 60℃ で数時間反応させると t-ブチルフェニルエーテル(SN)が 41-59% の収率で得られた。同様にアルカリ土類金属フェノキシドも 54-60% の収率でこのエーテルを与えた。次にハロゲソ化 t-ブチルに比べて脱離しにくいが立体障害の極めて大きなメタソスルホソ酸 1-アダマンチルは金属アルコキシドとオクタン中, 100-110℃ で反応し対応する 1-アダマンチルアルキルエーテルを高収率で与えた。これに対してヨウ化 1-アダマンチルの反応性は著しく小さかった。一方アルカリ金属アルコキシドはハロゲン化 t-ブチルとヘプタン中で反応してほとんど 2-メチルプロペン(E)のみを与えたがストロンチウム及びバリウムアルコキシドは 80-95℃ で同様に反応させると, 15-50% のアルキルかブチルエーテル(SN)が得られた。従って SN/E の選択性は溶媒,金属カチオン,求核試薬及び基質によって主に支配されていることを明らかにした.無極性溶媒の方が極性溶媒に比べてはるかにこのSN反応に有利に作用した。この系にクラウソエーテルを添加するとSN/Eの割合は著しく減少した。しかしラジカル捕捉剤を添加しても反応に変化は見られなかった。","subitem_description_type":"Abstract"}]},"item_4_publisher_17":{"attribute_name":"出版者","attribute_value_mlt":[{"subitem_publisher":"日本化学会 = The Chemical Society of Japan"}]},"item_4_relation_12":{"attribute_name":"DOI","attribute_value_mlt":[{"subitem_relation_type":"isIdenticalTo","subitem_relation_type_id":{"subitem_relation_type_id_text":"10.1246/nikkashi.1996.275","subitem_relation_type_select":"DOI"}}]},"item_4_relation_28":{"attribute_name":"関連URI","attribute_value_mlt":[{"subitem_relation_type_id":{"subitem_relation_type_id_text":"http://www.chemistry.or.jp/","subitem_relation_type_select":"URI"}},{"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://www.jstage.jst.go.jp/browse/nikkashi/-char/ja/","subitem_relation_type_select":"URI"}},{"subitem_relation_type_id":{"subitem_relation_type_id_text":"http://ci.nii.ac.jp/naid/10001975318/","subitem_relation_type_select":"URI"}}]},"item_4_rights_23":{"attribute_name":"権利","attribute_value_mlt":[{"subitem_rights":"Copyright © 日本化学会 The Chemical Society of Japan"}]},"item_4_source_id_11":{"attribute_name":"NCID","attribute_value_mlt":[{"subitem_source_identifier":"AN00186595","subitem_source_identifier_type":"NCID"}]},"item_4_source_id_9":{"attribute_name":"ISSN","attribute_value_mlt":[{"subitem_source_identifier":"0369-4577","subitem_source_identifier_type":"ISSN"}]},"item_4_version_type_25":{"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":"政田, 浩光"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"土井, 靖夫"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"三口, 史雄"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"木越, 敬子"}],"nameIdentifiers":[{}]}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2017-10-03"}],"displaytype":"detail","filename":"TE-PR-MASADA-H-275.pdf","filesize":[{"value":"2.2 MB"}],"format":"application/pdf","licensetype":"license_note","mimetype":"application/pdf","url":{"label":"TE-PR-MASADA-H-275.pdf","url":"https://kanazawa-u.repo.nii.ac.jp/record/10661/files/TE-PR-MASADA-H-275.pdf"},"version_id":"9d90a8ec-9892-4d54-95d0-32d313e83972"}]},"item_language":{"attribute_name":"言語","attribute_value_mlt":[{"subitem_language":"jpn"}]},"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":"第三級アルキル基質を用いたエーテル類の不均一系新規Williamson合成法","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"第三級アルキル基質を用いたエーテル類の不均一系新規Williamson合成法"},{"subitem_title":"Heterogeneous Williamson Synthesis of Ethers Using t-Alkyl Substrates","subitem_title_language":"en"}]},"item_type_id":"4","owner":"3","path":["937"],"pubdate":{"attribute_name":"公開日","attribute_value":"2017-10-03"},"publish_date":"2017-10-03","publish_status":"0","recid":"10661","relation_version_is_last":true,"title":["第三級アルキル基質を用いたエーテル類の不均一系新規Williamson合成法"],"weko_creator_id":"3","weko_shared_id":-1},"updated":"2023-07-28T01:38:11.209250+00:00"}