{"created":"2023-07-27T06:26:47.827966+00:00","id":10664,"links":{},"metadata":{"_buckets":{"deposit":"b63a5705-e151-414f-9387-c07be1652732"},"_deposit":{"created_by":3,"id":"10664","owners":[3],"pid":{"revision_id":0,"type":"depid","value":"10664"},"status":"published"},"_oai":{"id":"oai:kanazawa-u.repo.nii.ac.jp:00010664","sets":["934:935:937"]},"author_link":["16255","16257","16254","16256"],"item_4_biblio_info_8":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"1995-08-10","bibliographicIssueDateType":"Issued"},"bibliographicIssueNumber":"8","bibliographicPageEnd":"640","bibliographicPageStart":"635","bibliographicVolumeNumber":"1995","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":"カルシウム, ストロソチウム及びバリウムアルコキシドは臭化オクチル,臭化ヘキシル及び塩化ベソジルのようなハロゲン化第一級アルキルとDMSO-アルコール(1/1)溶媒中,70-100℃ で反応し,s72-94%の収率で第一級エーテルが得られた.次に二つの反応点を有するエチレングリコール及び-2-プロピン-1-オールのアルカリ土類金属塩と塩化ベンジルとの反芯では一置換体のみが選択的に与えられた.アルカリ金属塩の反応では一置換体の他に二置換体が副生するのに比べて対照的な結果である.一方アルカリ土類金属フェノキシド及びナフチルオキシドは第一級アルキル化物とDMSO中で反応しアリールアルキルエーテルが高収率で得られた.さらにヨウ化イソプロピル,臭化イソプロピル,メタンスルポソ酸イソプロビル,ヨウ化 s-ブチル及びメタンスルホソ酸 s-ブチルとの反応により第二級アルキルアリールエーテルが56-71%の収率で得られた.従来のアルカリ金属塩と第二級アルキル化物との反応ではエーテルの収率は20-30%に過ぎなかった.したがってアルカリ土類金属塩はアルカリ金属塩に比べて明らかに反応性,選択性が大きい.特にCa塩はSr塩及びBa塩よりも反応性は小さいが,安全性と緬格の点からも有機合成に有用である. Calcium, strontium, and barium alkoxides reacted with primary alkyl halides such as hexyl bromide, octyl bromide, and benzyl chloride at 70-100° C in DMSOalcohol (1/1). The substitution reaction gave the corresponding primary alkyl ethers in 72 94% yields. The alkaline earth metal salts of ethylene glycol and 2-pr opyn-1-ol, which have two reactive points, were heated with benzyl chloride, and gave a mono-substituted product exclusively, although a similar reaction of alkali metal salts is known to give both mono and di-substituted products. On the other hand, alkaline earth metal phenoxide and naphthyl oxide reacted with primary alkyl substrates in DMSO to afford aryl alkyl ethers in high yields. Furthermore, secondary alkyl substrates also reacted with alkaline earth metal aryl oxides to give secondary alkyl aryl ethers in 5671% yields. Isopropyl iodide, isopropyl bromide, isopropyl methanesulfonate, s-butyl iodide, and s-butyl methanesulfonate were used as the secondary alkyl substrate. According to the previous study, the reaction of secondary alkyl substrates with sodium alkoxides and aryl oxides gave only 20 30% of ethers. Therefore alkaline earth metal salts are much more selective than alkali metal salts in the substitution reactions. Although calcium salts are less reactive than strontium and barium salts, calcium salts are more selective and useful for organic synthesis from the viewpoints of safety and cost.","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.1995.635","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/10001683445/","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":"今井, 康人"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"村中, 豊"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"嵯峨田, 敬"}],"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-635.pdf","filesize":[{"value":"1.8 MB"}],"format":"application/pdf","licensetype":"license_note","mimetype":"application/pdf","url":{"label":"TE-PR-MASADA-H-635.pdf","url":"https://kanazawa-u.repo.nii.ac.jp/record/10664/files/TE-PR-MASADA-H-635.pdf"},"version_id":"62e4d497-2c7d-4281-9594-72be7d67201a"}]},"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":"アルカリ土類金属塩を用いたエ-テル類の合成","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"アルカリ土類金属塩を用いたエ-テル類の合成"},{"subitem_title":"Synthesis of Ethers Using Alkaline Earth Metal Salts","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":"10664","relation_version_is_last":true,"title":["アルカリ土類金属塩を用いたエ-テル類の合成"],"weko_creator_id":"3","weko_shared_id":-1},"updated":"2023-07-28T01:38:08.050749+00:00"}