{"_buckets": {"deposit": "a9b90e44-de0f-4006-963a-74efb964fd20"}, "_deposit": {"created_by": 5, "id": "12804", "owners": [5], "pid": {"revision_id": 0, "type": "depid", "value": "12804"}, "status": "published"}, "_oai": {"id": "oai:gifu-pu.repo.nii.ac.jp:00012804", "sets": ["202"]}, "author_link": ["17844", "17843", "17845"], "item_1_biblio_info_14": {"attribute_name": "書誌情報", "attribute_value_mlt": [{"bibliographicIssueDates": {"bibliographicIssueDate": "2006-06-30", "bibliographicIssueDateType": "Issued"}, "bibliographicPageEnd": "42", "bibliographicPageStart": "31", "bibliographicVolumeNumber": "55", "bibliographic_titles": [{"bibliographic_title": "岐阜藥科大學紀要"}, {"bibliographic_title": "The annual proceedings of Gifu College of Pharmacy", "bibliographic_titleLang": "en"}]}]}, "item_1_creator_6": {"attribute_name": "著者名(日)", "attribute_type": "creator", "attribute_value_mlt": [{"creatorNames": [{"creatorName": "廣田, 耕作"}], "nameIdentifiers": [{"nameIdentifier": "17843", "nameIdentifierScheme": "WEKO"}]}]}, "item_1_creator_7": {"attribute_name": "著者名よみ", "attribute_type": "creator", "attribute_value_mlt": [{"creatorNames": [{"creatorName": "ヒロタ, コウサク"}], "nameIdentifiers": [{"nameIdentifier": "17844", "nameIdentifierScheme": "WEKO"}]}]}, "item_1_creator_8": {"attribute_name": "著者名(英)", "attribute_type": "creator", "attribute_value_mlt": [{"creatorNames": [{"creatorName": "HIROTA, Kosaku", "creatorNameLang": "en"}], "nameIdentifiers": [{"nameIdentifier": "17845", "nameIdentifierScheme": "WEKO"}]}]}, "item_1_description_1": {"attribute_name": "ページ属性", "attribute_value_mlt": [{"subitem_description": "P(論文)", "subitem_description_type": "Other"}]}, "item_1_description_11": {"attribute_name": "抄録(日)", "attribute_value_mlt": [{"subitem_description": "ウラシル誘導体は核酸の構成塩基として重要であり、その反応性に関する研究が広範囲に実施されている。筆者の研究室ではウラシル誘導体が求核試薬に対して特色ある反応性を示すことに着目し、5-ブロモウラシル誘導体と種々の求核試薬との反応性を検討した。シアンイオンとの反応ではcine(シネ)置換反応が進行して6-シアノウラシルが生成した。また、塩基存在下、活性メチレン化合物由来のカルバニオンとの反応では活性メチレン化合物の違いによりcine置換生成物、5位置換体、5,6-シクロプロパン体が生成した。一方、アミン類との反応では5-ブロモウラシル誘導体の置換様式、アミンの種類や反応条件の違いによりS_N2,型の反応、ヒダントイン環への環変換反応など、異なる反応が進行した。これらの反応機構はいずれの場合も求核種がウラシル環6位への求核攻撃で始まることを明らかにした。次いで、グアニジンや尿素など、分子内に2ヶ所の求核部位をもつ1,3-アンビデント求核試薬と1,3-ジメチルウラシルとの反応ではウラシル環のウレア部分とアンビデント求核試薬が入れ替わる新規の環変換反応を見いだした。求核試薬としてC-C-N型のアンビデント試薬であるマロンアミドを用いると、同様の反応が進行して対応するピリジン環へ変換した生成物を与えた。この反応を5-ニトロ-、5-シアノ-あるいは5-ホルミルウラシル誘導体で行うと、それぞれ環開裂、再開環を経て5-カルバモイルウランル、6-アミノウラシル、ピリジン誘導体を与えた。以上について詳細に紹介する。", "subitem_description_type": "Other"}]}, "item_1_description_12": {"attribute_name": "抄録(英)", "attribute_value_mlt": [{"subitem_description": "Uracil derivatives are a component of nucleic acid and very important hterocyclic compounds, and their synthesis and reactivity have been widely investigated. In our laboratory reaction of 5-bromouracil derivatives with nucleophiles such as NaCN and various amines was carried out. Treatment of 5-bromo-1, 3-dimmethyluracil with NaCN at room temperature cased cine-substitution to give the corresponding 6-cyanouracil derivative. Carbanions derived from active methylene compounds and base was allowed to react with 5-bromouracil derivatives to give the sole product, e.g. 6-subsutituted uracils, 5-subsitituted uracils and cyclopropnae derivatives, depending on the employed active methylene compounds. Reaction of 5-bromo-6-methyl-1-phenyluracil with aniline and methylamine gave the corresponding 6-anilinomethyluracil and a ring transformation product, hidantoin derivative, respectively. It was demonstrated that every reaction described above was initiated by an attack of a nucleophile on the 6-position of the uracil ring. Upon employment of 1, 3-ambident nucleophiles such as guangine and thiourea (N-C-N type), novel type of ring transformation occurred by displacement of 1, 3-dimethylurea moiety of the uracil ring with the nucleophile that was used. When malonamide was used as a C-C-N type of 1, 3-ambident nucleophile, uracil to pyridine ring transformation occurred. Reaction of 5-nitro-, 5-cyano-, and 5-formyluracil derivatives with malonamide induced a different type of ring transformation to afford 5-carbamoyluracil, 6-aminouracil, and pyridine derivatives, respectively.", "subitem_description_type": "Other"}]}, "item_1_source_id_13": {"attribute_name": "雑誌書誌ID", "attribute_value_mlt": [{"subitem_source_identifier": "AN00053514", "subitem_source_identifier_type": "NCID"}]}, "item_1_text_10": {"attribute_name": "著者所属(英)", "attribute_value_mlt": [{"subitem_text_language": "en", "subitem_text_value": "Laboratory of Medicinal Chemistry, Gifu Pharmaceutical University"}]}, "item_1_text_2": {"attribute_name": "記事種別(日)", "attribute_value_mlt": [{"subitem_text_value": "総説"}]}, "item_1_text_3": {"attribute_name": "記事種別(英)", "attribute_value_mlt": [{"subitem_text_language": "en", "subitem_text_value": "Review"}]}, "item_1_text_9": {"attribute_name": "著者所属(日)", "attribute_value_mlt": [{"subitem_text_value": "岐阜薬科大学薬品化学教室"}]}, "item_files": {"attribute_name": "ファイル情報", "attribute_type": "file", "attribute_value_mlt": [{"accessrole": "open_date", "date": [{"dateType": "Available", "dateValue": "2006-06-30"}], "displaytype": "detail", "download_preview_message": "", "file_order": 0, "filename": "KJ00004509212.pdf", "filesize": [{"value": "1.1 MB"}], "format": "application/pdf", "future_date_message": "", "is_thumbnail": false, "licensetype": "license_free", "mimetype": "application/pdf", "size": 1100000.0, "url": {"url": "https://gifu-pu.repo.nii.ac.jp/record/12804/files/KJ00004509212.pdf"}, "version_id": "e23c348d-de9d-43bb-9065-a99d2b838380"}]}, "item_keyword": {"attribute_name": "キーワード", "attribute_value_mlt": [{"subitem_subject": "5-ブロモウラシル", "subitem_subject_scheme": "Other"}, {"subitem_subject": "求核試薬", "subitem_subject_scheme": "Other"}, {"subitem_subject": "cine置換反応 アンビデント求核試薬", "subitem_subject_scheme": "Other"}, {"subitem_subject": "環変換反応", "subitem_subject_scheme": "Other"}, {"subitem_subject": "reaction of 5-bromouracil with nucleophiles", "subitem_subject_language": "en", "subitem_subject_scheme": "Other"}, {"subitem_subject": "cine-substitution", "subitem_subject_language": "en", "subitem_subject_scheme": "Other"}, {"subitem_subject": "ambident nucleophiles", "subitem_subject_language": "en", "subitem_subject_scheme": "Other"}, {"subitem_subject": "ring-transformation", "subitem_subject_language": "en", "subitem_subject_scheme": "Other"}]}, "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": "departmental bulletin paper", "resourceuri": "http://purl.org/coar/resource_type/c_6501"}]}, "item_title": "ウラシル誘導体の求核試薬に対する反応性と環変換反応への展開", "item_titles": {"attribute_name": "タイトル", "attribute_value_mlt": [{"subitem_title": "ウラシル誘導体の求核試薬に対する反応性と環変換反応への展開"}, {"subitem_title": "Reactivity of Uracil Derivatives Toward Nucleophiles and its Development into Ring Transformation Reaction", "subitem_title_language": "en"}]}, "item_type_id": "1", "owner": "5", "path": ["202"], "permalink_uri": "https://gifu-pu.repo.nii.ac.jp/records/12804", "pubdate": {"attribute_name": "公開日", "attribute_value": "2006-06-30"}, "publish_date": "2006-06-30", "publish_status": "0", "recid": "12804", "relation": {}, "relation_version_is_last": true, "title": ["ウラシル誘導体の求核試薬に対する反応性と環変換反応への展開"], "weko_shared_id": -1}