{"created":"2021-03-01T06:43:41.706957+00:00","id":8313,"links":{},"metadata":{"_buckets":{"deposit":"bc558bb6-8eee-468a-9788-eeeae31c753e"},"_deposit":{"id":"8313","owners":[],"pid":{"revision_id":0,"type":"depid","value":"8313"},"status":"published"},"_oai":{"id":"oai:tsukuba.repo.nii.ac.jp:00008313","sets":["3:233:254"]},"author_link":["34646"],"item_12_biblio_info_6":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"1987","bibliographicIssueDateType":"Issued"}}]},"item_12_date_granted_46":{"attribute_name":"学位授与年月日","attribute_value_mlt":[{"subitem_dategranted":"1987-01-31"}]},"item_12_degree_grantor_44":{"attribute_name":"学位授与大学","attribute_value_mlt":[{"subitem_degreegrantor":[{"subitem_degreegrantor_language":"ja","subitem_degreegrantor_name":"筑波大学"},{"subitem_degreegrantor_language":"en","subitem_degreegrantor_name":"University of Tsukuba"}],"subitem_degreegrantor_identifier":[{"subitem_degreegrantor_identifier_name":"12102","subitem_degreegrantor_identifier_scheme":"kakenhi"}]}]},"item_12_degree_name_43":{"attribute_name":"取得学位","attribute_value_mlt":[{"subitem_degreename":"博士（理学）"},{"subitem_degreename":"Doctor of Philosophy in Science"}]},"item_12_description_4":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"本論文は，窒素原子を含むカルボニル化合物(α―ケトアミド及びα―ケトイミド等)及びチオカルボニル化合物(チオイミド等)の光化学反応について述べたものである。　(1)アジリジン―2，3―ジオンの生成，三員環アミドであるα―ラクタムは既知であるが，これにカルボニル基を導入したアジリジン―2，3―ジオンは合成困難で未知であった。著者はマレインイミドのオゾン化物を固相，-196℃の条件で光照射することにより初めてアジリジン―2，3―ジオンの生成と赤外吸収スペクトルによる確認に成功した。　(2)α―ケトアミドの光化学反応，α―ケトアミドは光照射によりβ―ラクタム(四員環)とオキサゾリジノン(五員環)を生成する。β―ラクタムがペニシリンの部分構造であるところからこの反応はとくに興味を持たれるが，詳細な反応機構は不明であった。著者は，置換基効果，溶媒効果，強酸性溶液中の光照射生成物の低温核磁気共鳴，紫外吸収スペクトル等により，この反応が単なるラジカル経由ではなく，双極イオン経由で進むことを明かにした。　(3)α―ケトイミドの光化学反応，近年，環状イミドの光化学反応の研究例が見かけられるが，鎖状イミドの例は殆どない。著者は種々の鎖状α―ケトイミドの光化学反応を検討した結果，N―アルキル―α―ケトイミドの光照射により，薬理学上でも活性なアゼチジン―2，4―ジオン(含窒素四員環)を好収率で得た。そしてこの反応が光によるアシル基の分子内1，5―転位を伴う環化反応であることを明らかにした。また，類似の機構により，N―ホルミル―α―ケトアミドからは3位に水酸基を持つアゼチジン―2，4―ジオンを，さらに，N―フェニルチオカルボニル―α―ケトアミドからは5位に硫黄原子を持つオキサゾリジン―2，4―ジオンを得た。　(4)チオイミドの光化学反応，チオケトンはケトンと類似の反応性を示すが，窒素を含むチオカルボニル化合物の光化学反応の例は殆どない。著者はチオイミドのβ，γ，δ位からの水素引抜反応，(2＋2)付加反応を検討し，種々の複素環化合物を合成する方法を見出した。鎖状モノチオイミドからはメルカプト―β―ラクタムを，チオカルボニル基側をジチオカルバメイトにしたものからは常温でセファム誘導体を，高温で含硫黄二環性ラクタムを，N―チオアシル尿素及びN―チオァシルチオ尿素からはメルカプトイミダゾリジノンを，N―α，β―不飽和カルボニルチオアミドからはチエタン環が縮合した形の新型β―ラクタムを得た。 The photochemical reactions of several types of nitrogen-containing carbonyl and thiocarbonyl compounds were investigated. These photoreactions provided not only new types of reactions but also useful methods for synthesizing nitrogen-containing hetero-cycles, such as, aziridine-2, 3-diones, azetidin-2-ones (β-lactams), ...","subitem_description_language":"ja","subitem_description_type":"Abstract"}]},"item_12_description_45":{"attribute_name":"学位授与年度","attribute_value_mlt":[{"subitem_description":"1986","subitem_description_type":"Other"}]},"item_12_dissertation_number_47":{"attribute_name":"報告番号","attribute_value_mlt":[{"subitem_dissertationnumber":"乙第351号"}]},"item_access_right":{"attribute_name":"アクセス権","attribute_value_mlt":[{"subitem_access_right":"open access","subitem_access_right_uri":"http://purl.org/coar/access_right/c_abf2"}]},"item_creator":{"attribute_name":"著者","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"坂本, 昌巳","creatorNameLang":"ja"},{"creatorName":"Sakamoto, Masami","creatorNameLang":"en"}],"nameIdentifiers":[{"nameIdentifier":"34646","nameIdentifierScheme":"WEKO"}]}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_access","date":[{"dateType":"Available","dateValue":"2013-12-18"}],"displaytype":"detail","filename":"B0351.pdf","filesize":[{"value":"132.1 kB"}],"format":"application/pdf","mimetype":"application/pdf","url":{"objectType":"abstract","url":"https://tsukuba.repo.nii.ac.jp/record/8313/files/B0351.pdf"},"version_id":"633a55ab-d64d-457c-a1b0-72c17922fd23"},{"accessrole":"open_access","date":[{"dateType":"Available","dateValue":"2013-12-18"}],"displaytype":"detail","filename":"1.pdf","filesize":[{"value":"5.1 MB"}],"format":"application/pdf","mimetype":"application/pdf","url":{"objectType":"fulltext","url":"https://tsukuba.repo.nii.ac.jp/record/8313/files/1.pdf"},"version_id":"b842a89b-1eea-4436-851a-65a94387a698"}]},"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":"doctoral thesis","resourceuri":"http://purl.org/coar/resource_type/c_db06"}]},"item_title":"Photochemistry of nitrogen-containing carbonyl and thiocarbonyl compounds","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"Photochemistry of nitrogen-containing carbonyl and thiocarbonyl compounds","subitem_title_language":"en"}]},"item_type_id":"12","owner":"1","path":["254"],"pubdate":{"attribute_name":"PubDate","attribute_value":"2007-07-25"},"publish_date":"2007-07-25","publish_status":"0","recid":"8313","relation_version_is_last":true,"title":["Photochemistry of nitrogen-containing carbonyl and thiocarbonyl compounds"],"weko_creator_id":"1","weko_shared_id":-1},"updated":"2023-05-02T01:11:31.660790+00:00"}