{"created":"2023-07-27T07:01:15.620733+00:00","id":61482,"links":{},"metadata":{"_buckets":{"deposit":"3e06d7bf-1899-4b72-b994-62f56f118b60"},"_deposit":{"created_by":18,"id":"61482","owners":[18],"pid":{"revision_id":0,"type":"depid","value":"61482"},"status":"published"},"_oai":{"id":"oai:kanazawa-u.repo.nii.ac.jp:00061482","sets":["2812:2813:2845"]},"author_link":["9747","10174"],"item_9_biblio_info_8":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"1990-03-19","bibliographicIssueDateType":"Issued"},"bibliographicPageStart":"2p.","bibliographicVolumeNumber":"1987 – 1988","bibliographic_titles":[{"bibliographic_title":"昭和63(1988)年度 科学研究費補助金 一般研究(C) 研究成果報告書概要"},{"bibliographic_title":"1988 Fiscal Year Final Research Report Summary","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":"各種の1ーシリルシクロプロピルリチウム誘導体(1)とジクロロメチルメチルエーテル(DCME)の反応により、対応するシクロプロピルシリルケトン(2)を比較的良好な収率で得た。本反応では、DCMEから生じたメトキシクロロカルベンが1と反応した後、シリル基が分子内的に1,2ー転位して2が生じたと考えた。本法は、その収率の面で改善の余地はあるが、潜在的に重要である。\n2の炭素三員環がシリルカルボニル基によって強く活性化されていることを、各種酸との反応によって確かめた。ハロゲン酸との反応では三員環の開環が優先し、硫酸および関連酸との反応では環拡大が起こりジヒドロフラン誘導体が生じた。なお、2ーフェニルシクロプロピルシリルケトンと硫酸との反応では対応するシクロブタノンが高収率で得られた。\n2とアルキリデンホスホランとのWittig反応は高立体選択的に進み、対応するZ+1ーシリルー1ーシクロプロピルアルケン(3)を95%以上の純度で生じた。この結果は2におけるシリル基のかさ高さによって説明される。3のプロトン酸による脱シリル化では炭素三員環の開裂が起こりやすく、対応する二置換アルケンへの変換は困難であった。しかし、Bu_4NFを用いると3は容易に脱シリルプロトン化され、対応するEーアルケンが定量的に得られた。\n2とオキソスルホニウムメチリドとの反応では、対応するシロキシアルケンとβーケトシランが生じた。これら生成物の割合は、反応温度、溶媒の極性、硫黄イリドの調製によって異なる。特に、無塩型イリドでは前者が、有塩型イリドでは後者が選択的に生じた。これら両化合物の生成は、反応中間体でのシリル基の分子内1,2ー転位によって説明されるが、イリド溶液中に可溶性無機塩を共存させることによって、シリル基がアニオノトロピー(βーケトシランの生成)しうる状況を創出した点は合成化学的に大きな意義を持つと考えられる。","subitem_description_type":"Abstract"},{"subitem_description":"A series of new cyclopropyl trimethylsilyl ketones has been prepared in moderate yield from the novel reaction of 1-trimethylsilylcyclopropyllithium derivartives with dichloromethyl methyl ether. This reaction involves the intramolecular 1,2-silicon shift from carbon to carbon. The spectroscopic properties of these silyl ketones have been measured.\nThe ketones obtained here react with various halogen acids under milder conditions compared to that of their carbon analogs to give the ring opening products, 3-chloropropyl silyl ketones, or the ring enlargement products, 2-silyl-4,5-dihydrofuran derivatives in some cases. The reaction with sulfuric acid or trifluoromethane sulfonic acid affords only the corrensponding silyldihydrofurans in good yield. Especially, it is noteworty that the reaction of 2-phenylcyclopropyl silyl ketone with sulfuric acid yields 2-phenylcyclobutanone. The formation of these comounds is interpreted on the basis of the effect that silicon stabilizes a cation to it.\nWittig reactions of cyclopropyl silyl ketones with alkylidene-triphenylphosphoranes proceed stereoselectively to give the corresponding Z-1-silyl-1-cyclopropyl alkenes. The protiodesilylation of silyl cyclopropyl alkenes with tetrabutylammonium fluoride proceeds with retention of configuration to give E-cyclopropyl alkenes, although the reaction with hydrogen halides was unsuccessful due to the cleavage of the three membered ring.\nThe reaction of sulfur ylides in THF with cyclopropyl silyl ketones resulted in the formation of the corresponding siloxyalkenes or -ketosilanes. The relative ratio of these compounds varies with the reaction temperature, the porality of solvents used, and the preparation method of ylide. It is noteworthy that the reaction with salt free ylide affords siloxyalkenes and that of the ylide containing inorganic salt -ketosilanes, selectively. These two type of products would be formed by the anionotropic and cationotropic rearrangement of silyl group in the betaine intermediate.","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:62550627, 研究期間(年度):1987 – 1988","subitem_description_type":"Other"},{"subitem_description":"出典：研究課題「シクロプロピルトリメチルシリルケトン類の新合成法とその有機合成への応用」課題番号62550627\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（https://kaken.nii.ac.jp/ja/report/KAKENHI-PROJECT-62550627/625506271988kenkyu_seika_hokoku_gaiyo/）を加工して作成","subitem_description_type":"Other"}]},"item_9_description_5":{"attribute_name":"提供者所属","attribute_value_mlt":[{"subitem_description":"金沢大学工学部","subitem_description_type":"Other"}]},"item_9_identifier_registration":{"attribute_name":"ID登録","attribute_value_mlt":[{"subitem_identifier_reg_text":"10.24517/00067725","subitem_identifier_reg_type":"JaLC"}]},"item_9_relation_28":{"attribute_name":"関連URI","attribute_value_mlt":[{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/ja/search/?kw=70019735"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/ja/search/?kw=70019735","subitem_relation_type_select":"URI"}},{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/ja/grant/KAKENHI-PROJECT-62550627/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/ja/grant/KAKENHI-PROJECT-62550627/","subitem_relation_type_select":"URI"}},{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/ja/report/KAKENHI-PROJECT-62550627/625506271988kenkyu_seika_hokoku_gaiyo/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/ja/report/KAKENHI-PROJECT-62550627/625506271988kenkyu_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":"2022-10-31"}],"displaytype":"detail","filename":"TE-PR-NAKAJIMA-T-kaken 1990-2p.pdf","filesize":[{"value":"90.8 kB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"E-PR-NAKAJIMA-T-kaken 1990-2p.pdf","url":"https://kanazawa-u.repo.nii.ac.jp/record/61482/files/TE-PR-NAKAJIMA-T-kaken 1990-2p.pdf"},"version_id":"49fa3fce-8ef3-4af0-9c21-ded0aff25db2"}]},"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":"シクロプロピルトリメチルシリルケトン類の新合成法とその有機合成への応用","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"シクロプロピルトリメチルシリルケトン類の新合成法とその有機合成への応用"},{"subitem_title":"Novel preparation method and synthetic applications of cyclopropyl trimethylsilyl ketones","subitem_title_language":"en"}]},"item_type_id":"9","owner":"18","path":["2845"],"pubdate":{"attribute_name":"公開日","attribute_value":"2022-10-31"},"publish_date":"2022-10-31","publish_status":"0","recid":"61482","relation_version_is_last":true,"title":["シクロプロピルトリメチルシリルケトン類の新合成法とその有機合成への応用"],"weko_creator_id":"18","weko_shared_id":-1},"updated":"2023-07-27T11:53:09.956273+00:00"}