{"created":"2023-07-27T06:52:44.959193+00:00","id":46853,"links":{},"metadata":{"_buckets":{"deposit":"3b79fadb-10bf-461d-8dcb-6fbbc7b302fa"},"_deposit":{"created_by":18,"id":"46853","owners":[18],"pid":{"revision_id":0,"type":"depid","value":"46853"},"status":"published"},"_oai":{"id":"oai:kanazawa-u.repo.nii.ac.jp:00046853","sets":["2812:2813:2843"]},"author_link":["81641","81640"],"item_9_biblio_info_8":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"1991-03","bibliographicIssueDateType":"Issued"},"bibliographicPageStart":"5p.","bibliographicVolumeNumber":"1989-1990","bibliographic_titles":[{"bibliographic_title":"平成2(1990)年度 科学研究費補助金 一般研究(C) 研究成果報告書"},{"bibliographic_title":"1990 Fiscal Year Final Research Report","bibliographic_titleLang":"en"}]}]},"item_9_creator_33":{"attribute_name":"著者別表示","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{}],"nameIdentifiers":[{},{}]}]},"item_9_description_21":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"海綿の構成成分6ーiminoー1,9ーdimethylー8ーoxopurine (I)やイソギンチャクの構成成分caissarone(塩酸塩をIIで示す)は,天然プリン類としては珍しい8ーoxo構造を有しているので,これらの生物活性には興味が持たれる.これらの8ーオキソプリン類の化学合成は未検討であったので,本研究ではI及びIIを次のようにして合成し,それらの化学的性質を調べることができた.\n1.9ーMethyladenine(III)を臭素化し,得られた8ーBr体(IV)をMeIでメチル化すると8ーlromoー1,9ーdimethyladesine(V)が得られた.Vを沸騰酢酸中NaOAcで処理すると,標的化合物IがIIIからの通算収率25%で得られた.別法では,IVを1NNaOH水溶液中で煮沸し,生成した9ーmethylー8ーoxoadenineをMelでメチル化したところ,IIIからの通算収率63%でIを合成することができた.\n2.このようにして得たIは,1NNaOH水溶液中で煮沸すると,Dimroth転位を起してN___ー^6,9ーdimethylー8ーoxoadenine(VI)を与えた.Vも同様のDimroth転位を起すことが判明した.これらの転位の容易さを,1,9ーdimethyladenine(VII)を基準化合物に用いて反応速度論的に比較したところ,pH7.00ー11.42,40℃,イオン強度1.0ではV>VII>Iの順で転位が遅くなることが判明した.\n3.VIをMel/AcNMe_2でメチル化したところ,3ーMe体・HI塩(VIII)(収率50%)及び1ーMe体・HI塩(13%)が得られた.次に,VIIIの水溶液をAmberlite IRAー402(Cl^-)カラムに通すことによって,他の標的化合物IIを98%の収率で得た.ここに得られたIIは,天然caissarone塩酸塩と同定することができた.この結果,IIIから6工程,通算収率28%によるIIの合成経路を確立することができた.","subitem_description_type":"Abstract"},{"subitem_description":"1. The first total synthesis of 6-imino-1, 9-dimethy1-8-oxopurine (I), a constituent of the marine sponge Hymeniacidon sanguinea Grant, has been achieved via two alternative routes starting from 8-bromo-9-methyladenine (II), which is obtainable from 9-methyladenine (III) by bromination. The first route includes methylation of II with MeI to give 8-bromo-1, 9-di-methyladenine (IV) and treatment of IV with NaOAc in boiling AcOH to produce I in 25% overall yield (from III). The second route includes treatment of II with boiling 1 N aqueous NaOH and methylation of the resulting 8-oxo derivative with MeI, affording I in 63% overall yield (from III).\n2.The reaction rates in the Dimroth rearrangements of the marine sponge base 6-imino-1, 9-dimethyl-8-oxopurine (I) and related compounds such as 1, 9-dimethyladenine (V) and 8-bromo-1, 9-dimethyladenine (IV) were measured in H_2O at various pH's and ionic strength 1.0 at 40^ﾟC. In all cases, attack of hydroxide ion on the protonated species of the substrate at the 2-position was faster than that on the neutral species by a factor of 100-1400. In the reaction of the protonated species, the relative ease of undergoing Dimroth rearrangement was in the order of IV > V > I. The same order of reactivity was found to hold for the neutral species.\n3.The first chemical synthesis of caissarone hydrochloride, a constituent of the sea anemone Bunodosoma caissarum Correa 1964, has been accomplished via a two-step route including methylation of N6, 9-dimethyl-8-oxoadenine. This synthesis was based on a methylation study of N^6 -benzy1-9-methy1-8-oxoadenine.","subitem_description_type":"Abstract"}]},"item_9_description_22":{"attribute_name":"内容記述","attribute_value_mlt":[{"subitem_description":"研究課題/領域番号:01571148, 研究期間(年度):1989-1990","subitem_description_type":"Other"},{"subitem_description":"出典：「海洋動物由来の新規8ーオキソプリン類の合成」研究成果報告書　課題番号01571148\n(KAKEN：科学研究費助成事業データベース（国立情報学研究所）)\n　　　本文データは著者版報告書より作成","subitem_description_type":"Other"}]},"item_9_identifier_registration":{"attribute_name":"ID登録","attribute_value_mlt":[{"subitem_identifier_reg_text":"10.24517/00053180","subitem_identifier_reg_type":"JaLC"}]},"item_9_publisher_17":{"attribute_name":"公開者","attribute_value_mlt":[{"subitem_publisher":"金沢大学薬学部"}]},"item_9_relation_28":{"attribute_name":"関連URI","attribute_value_mlt":[{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/search/?qm=20019649"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/search/?qm=20019649","subitem_relation_type_select":"URI"}},{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-01571148/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-01571148/","subitem_relation_type_select":"URI"}},{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/report/KAKENHI-PROJECT-01571148/015711481990kenkyu_seika_hokoku_gaiyo/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/report/KAKENHI-PROJECT-01571148/015711481990kenkyu_seika_hokoku_gaiyo/","subitem_relation_type_select":"URI"}}]},"item_9_version_type_25":{"attribute_name":"著者版フラグ","attribute_value_mlt":[{"subitem_version_resource":"http://purl.org/coar/version/c_ab4af688f83e57aa","subitem_version_type":"AM"}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2019-02-14"}],"displaytype":"detail","filename":"PH-PR-FUJII-T-kaken 1991-5p.pdf","filesize":[{"value":"81.8 kB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"PH-PR-FUJII-T-kaken 1991-5p.pdf","url":"https://kanazawa-u.repo.nii.ac.jp/record/46853/files/PH-PR-FUJII-T-kaken 1991-5p.pdf"},"version_id":"e66563c8-e9d9-49e3-97e2-041542a2f7e4"}]},"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":"research report","resourceuri":"http://purl.org/coar/resource_type/c_18ws"}]},"item_title":"海洋動物由来の新規8ーオキソプリン類の合成","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"海洋動物由来の新規8ーオキソプリン類の合成"},{"subitem_title":"Syntheses of Novel 8-Oxopurines Derived from Sea Animals","subitem_title_language":"en"}]},"item_type_id":"9","owner":"18","path":["2843"],"pubdate":{"attribute_name":"公開日","attribute_value":"2019-02-14"},"publish_date":"2019-02-14","publish_status":"0","recid":"46853","relation_version_is_last":true,"title":["海洋動物由来の新規8ーオキソプリン類の合成"],"weko_creator_id":"18","weko_shared_id":-1},"updated":"2023-07-27T14:51:38.646973+00:00"}