{"id":58198,"date":"2014-11-02T02:47:16","date_gmt":"2014-11-01T18:47:16","guid":{"rendered":"http:\/\/highscope.ch.ntu.edu.tw\/wordpress\/?p=58198"},"modified":"2021-10-06T16:13:21","modified_gmt":"2021-10-06T08:13:21","slug":"%e5%85%8b%e8%90%8a%e6%a3%ae%e7%b8%ae%e5%90%88%e5%8f%8d%e6%87%89claisen-condensation-reaction","status":"publish","type":"post","link":"http:\/\/localhost\/%e5%85%8b%e8%90%8a%e6%a3%ae%e7%b8%ae%e5%90%88%e5%8f%8d%e6%87%89claisen-condensation-reaction\/","title":{"rendered":"\u514b\u840a\u68ee\u7e2e\u5408\u53cd\u61c9Claisen Condensation Reaction"},"content":{"rendered":"

\u514b\u840a\u68ee\u7e2e\u5408\u53cd\u61c9Claisen Condensation Reaction<\/strong><\/span>
\n\u570b\u7acb\u81fa\u7063\u5e2b\u7bc4\u5927\u5b78\u5316\u5b78\u7cfb\u535a\u58eb\u751f\u6797\u6b23\u6167<\/strong><\/span><\/p>\n

\"58198_p1\"<\/a>

\u5716\u4e00<\/p><\/div>\n

\u514b\u840a\u68ee\u7e2e\u5408\u53cd\u61c9\u53c8\u7a31\u70ba\u514b\u840a\u68ee\u916f\u985e\u7e2e\u5408\u53cd\u61c9\uff0c\u662f\u7531\u5fb7\u570b\u79d1\u5b78\u5bb6 Rainer Ludwig Claisen (\u5716\u4e00)1<\/sup>\u5728 1887 \u5e74\u6240\u767c\u8868\u3002<\/p>\n

\u6709\u5225\u65bc\u50b3\u7d71\u4e14\u5ee3\u70ba\u4eba\u77e5\u7684\u6709\u6a5f\u9178\u52a0\u9187\u985e\u5728\u9e7c\u6027\u689d\u4ef6\u4e0b\u9032\u884c\u53cd\u61c9\u53ef\u5f97\u5230\u916f\u985e\u5316\u5408\u7269\uff1b\u514b\u840a\u68ee\u7e2e\u5408\u53cd\u61c9\u662f\u5c07\u5177\u6709 $$\\alpha$$(alfa)\u6c2b\u7684\u916f\u985e\u5316\u5408\u7269\u5728\u9e7c\u6027\u689d\u4ef6\u4e0b\u9032\u884c\u5169\u500b\u76f8\u540c\u916f\u985e\u5206\u5b50\u7684\u7e2e\u5408\u53cd\u61c9\u9032\u800c\u7372\u5f97\u916e\u9178\u916f(keto ester)\u5316\u5408\u7269\u3002<\/p>\n

\u4ee5\u4e01\u9178\u7532\u916f(I<\/b>)\u70ba\u4f8b\uff0c\u5728\u7fb0\u57fa\u65c1\u908a\u7684\u7b2c\u4e00\u500b\u78b3\u6211\u5011\u5c07\u5b83\u7de8\u865f\u70ba $$\\alpha$$(alfa)\uff0c\u6b64\u78b3\u4e0a\u82e5\u6709\u63a5\u4e0a\u6c2b\u6211\u5011\u4fbf\u7a31\u70ba $$\\alpha$$ \u6c2b\uff1b\u7de8\u865f\u4f9d\u5e8f\u70ba $$\\alpha$$\u3001$$\\beta$$\u3001$$\\gamma$$\u3001$$\\delta$$ \u7b49\u7b49\u4ee5\u6b64\u985e\u63a8\uff08\u5716\u4e8c\uff09\u3002<\/p>\n

\"58198_p2\"<\/a>

\u5716\u4e8c<\/p><\/div>\n

\u800c $$\\alpha$$ \u4f4d\u4e0a\u7684\u6c2b\u56e0\u70ba\u53d7\u5230\u7fb0\u57fa\u5f71\u97ff\u7684\u95dc\u4fc2 $$pKa$$ \u8f03\u5c0f\uff0c\u5f88\u5bb9\u6613\u88ab\u9e7c\u62d4\u6389\uff0c\u5f62\u6210\u5177\u6709\u70ef\u9187\u9e7d(enolate)\u5171\u632f\u5f0f\u7684\u96e2\u5b50(II<\/b>)\uff08\u5716\u4e09\uff09\u3002<\/p>\n

\"58198_p3\"<\/a>

\u5716\u4e09<\/p><\/div>\n

\u7576\u5f62\u6210\u70ef\u9187\u9e7d\u96e2\u5b50(II<\/b>)\u5f8c\uff0c$$\\alpha$$ \u4f4d\u7684\u78b3\u56e0\u70ba\u5177\u6709\u8ca0\u96fb\u8377\uff0c\u6b64\u6642\u4fbf\u53ef\u4ee5\u9032\u884c\u89aa\u6838\u653b\u64ca\uff0c\u53bb\u653b\u6253\u53e6\u5916\u4e00\u500b\u916f\u5206\u5b50\u4e2d\u7fb0\u57fa\u4e0a\u7684\u78b3\uff0c\u5f97\u5230\u6c27\u4e0a\u5e36\u8ca0\u96fb\u7684\u4e2d\u9593\u9ad4(III<\/b>)\uff1b\u4e4b\u5f8c\uff0c\u5e36\u6709\u8ca0\u96fb\u7684\u6c27\u4e0a\u96fb\u5b50\u56de\u63a8\uff0c\u800c\u53ef\u626e\u6f14\u96e2\u53bb\u57fa\u89d2\u8272\u7684\u7532\u6c27\u57fa $$(\\mathrm{-OCH_3})$$\u00a0\u6b64\u6642\u5c31\u812b\u53bb\u800c\u5f97\u5230\u5169\u500b\u916f\u5206\u5b50\u7e2e\u5408\u5f8c\u7684 $$\\beta$$(beta)-\u916e\u9178\u916f(IV<\/b>)\uff08\u5716\u56db\uff09\u3002<\/p>\n

\"58198_p4\"<\/a>

\u5716\u56db<\/p><\/div>\n

\u8207\u514b\u840a\u68ee\u7e2e\u5408\u53cd\u61c9\u76f8\u8fd1\u3001\u4e5f\u5f88\u5e38\u88ab\u63d0\u8d77\u4e00\u540c\u9032\u884c\u6bd4\u8f03\u7684\u9084\u6709\u72c4\u514b\u66fc\u7e2e\u5408\u53cd\u61c9 (Dieckmann condensation)\u3002\u7576\u4e00\u500b\u5206\u5b50\u5177\u6709\u5169\u500b\u916f\u57fa\u3001\u4e14\u916f\u57fa\u4e2d\u9593\u9593\u9694\u56db\u500b\u4ee5\u4e0a\u7684\u78b3\uff0c\u5728\u9e7c\u6027\u689d\u4ef6\u4e0b\u4fbf\u53ef\u4ee5\u9032\u884c\u5206\u5b50\u5167\u7684\u7e2e\u5408\u53cd\u61c9\uff0c\u7a31\u70ba\u72c4\u514b\u66fc\u7e2e\u5408\u3002\u5b83\u7684\u53cd\u61c9\u6a5f\u5236\u8207\u514b\u840a\u68ee\u7e2e\u5408\u53cd\u61c9\u4e00\u6a23\uff0c\u90fd\u662f\u5229\u7528\u9e7c\u5c07 $$\\alpha$$ \u4f4d\u4e0a\u7684\u6c2b\u62d4\u9664\u5f8c\uff0c\u9032\u884c\u89aa\u6838\u653b\u64ca\u3001\u518d\u7d93\u7531\u812b\u53bb\u53cd\u61c9\u5f97\u5230\u74b0-$$\\beta$$-\u916e\u9178\u916f(VI<\/b>)\uff08\u5716\u4e94\uff09\u3002<\/p>\n

\"58198_p5\"<\/a>

\u5716\u4e94<\/p><\/div>\n

\u5728\u514b\u840a\u68ee\u7e2e\u5408\u53cd\u61c9\u88ab\u767c\u8868\u5f8c\uff0c\u8d8a\u4f86\u8d8a\u591a\u76f8\u95dc\u7684\u7814\u7a76\u8207\u5408\u6210\u5617\u8a66\u767c\u73fe\u6b64\u53cd\u61c9\u6a5f\u5236\u53ef\u4ee5\u5229\u7528\u65bc\u4e0d\u540c\u7684\u916f\u985e\u5206\u5b50\u9593\u7684\u9032\u884c\u7e2e\u5408\uff0c\u7a31\u70ba\u201c\u4ea4\u514b\u4f86\u68ee\u7e2e\u5408\u53cd\u61c9\u201d(corss Cliasen condensation)\uff1b\u4f46\u662f\u56e0\u70ba\u53cd\u61c9\u904e\u7a0b\u4e2d\uff0c\u53ef\u80fd\u6703\u7522\u751f\u5f88\u591a\u8907\u96dc\u7684\u526f\u7522\u7269\uff0c\u4ee5\u4e59\u9178\u4e59\u916f\u8207\u4e19\u9178\u4e59\u916f\u9032\u884c\u53cd\u61c9\u70ba\u4f8b\uff0c\u53ef\u4ee5\u5f97\u5230\u4e09\u7a2e\u4e0d\u540c\u7684\u7522\u7269\uff08\u5716\u516d\uff09\u3002\u7531\u6b64\u53ef\u898b\u50b3\u7d71\u7684\u514b\u840a\u68ee\u7e2e\u5408\u53cd\u61c9\u5728\u5408\u6210\u61c9\u7528\u4e0a\u662f\u6709\u6240\u9650\u5236\u7684\u3002<\/p>\n

\"58198_p6\"<\/a>

\u5716\u516d<\/p><\/div>\n

\u4f46\u96a8\u8457\u6642\u9593\u7684\u63a8\u79fb\uff0c\u7d93\u7531\u79d1\u5b78\u5bb6\u5011\u7684\u52aa\u529b\u7814\u7a76\u4e0b\uff0c\u767c\u73fe\u82e5\u5229\u7528\u5177\u6709 $$\\alpha$$ \u6c2b\u7684\u916f\u985e\u5316\u5408\u7269\u8207\u53e6\u4e00\u7a2e\u4e0d\u5177\u6709 $$\\alpha$$ \u6c2b\u7684\u916f\u985e\u5316\u5408\u7269\u9032\u884c\u53cd\u61c9\u4fbf\u53ef\u4ee5\u5f97\u5230\u55ae\u4e00\u7522\u7269\uff0c\u4f8b\u5982\u4e59\u9178\u4e59\u916f\u8207\u82ef\u7532\u9178\u7532\u916f\u53cd\u61c9\uff0c\u6703\u751f\u6210\u82ef\u7532\u91af\u4e59\u9178\u4e59\u916f\uff08\u5716\u4e03\uff09\u3002<\/p>\n

\"58198_p7\"<\/a>

\u5716\u4e03<\/p><\/div>\n

\u53e6\u5916\uff0c\u82e5\u5c07\u53cd\u61c9\u7576\u4e2d\u626e\u6f14\u96e2\u53bb\u57fa\u89d2\u8272\u7684\u70f7\u6c27\u57fa\u4ee5\u6c2f\u4ee3\u66ff\uff0c\u5229\u7528\u91af\u6c2f\u5316\u5408\u7269\u9032\u884c\u514b\u840a\u68ee\u7e2e\u5408\u53cd\u61c9\uff0c\u53ef\u4f7f\u6b64\u53cd\u61c9\u7684\u61c9\u7528\u6027\u66f4\u52a0\u5ee3\u6cdb\uff0c\u5c24\u5176\u662f\u5728\u5929\u7136\u7269\u7684\u5408\u6210\u4e2d\u4e5f\u76f8\u7576\u5e38\u898b\u3002<\/p>\n

\u4f8b\u5982\u7531 C.H. Heathcock \u5728 1992 \u5e74\u6240\u767c\u8868\u7684\u5929\u7136\u7269(-)-Secodaphniphylline \u5408\u62102<\/sup>\uff0c\u904e\u7a0b\u4e2d\u5229\u7528\u514b\u840a\u68ee\u7e2e\u5408\u53cd\u61c9\u5c07\u5169\u500b\u5206\u5b50\u63a5\u8d77\u4f86\uff0c\u518d\u7d93\u7531\u591a\u6b65\u5408\u6210\u5f8c\u53ef\u4ee5\u5f97\u5230\u76ee\u6a19\u7522\u7269\uff08\u5716\u516b\uff09\u3002<\/p>\n

\u7531\u6b64\u53ef\u77e5\uff0c\u514b\u840a\u68ee\u7e2e\u5408\u53cd\u61c9\u662f\u76f8\u7576\u7c21\u55ae\u4e14\u5e38\u898b\u7684\u916f\u985e\u5408\u6210\u65b9\u6cd5\uff0c\u53ea\u8981\u5229\u7528\u4e0d\u5177\u6709 $$\\alpha$$ \u6c2b\u7684\u916f\u985e\u6216\u91af\u6c2f\u985e\u5316\u5408\u7269\u5728\u9069\u7576\u7684\u53cd\u61c9\u689d\u4ef6\u4e0b\uff0c\u4fbf\u53ef\u4ee5\u5408\u6210\u51fa\u6240\u8a2d\u8a08\u7684\u76ee\u6a19\u7522\u7269\uff0c\u662f\u76f8\u7576\u91cd\u8981\u4e14\u5177\u6709\u5ee3\u6cdb\u7684\u5229\u7528\u6027\u7684\u5408\u6210\u7b56\u7565\u3002<\/p>\n

\"58198_p8\"<\/a>

\u5716\u516b<\/p><\/div>\n

\u53c3\u8003\u8cc7\u6599\uff1a<\/p>\n

    \n
  1. \u5716\u7247\u4f86\u6e90\uff1ahttp:\/\/academictree.org\/chemistry\/peopleinfo.php?pid=72055<\/a><\/li>\n
  2. Heathcock, C. H., Stafford, J. A. Daphniphyllum alkaloids. 13. Asymmetric total synthesis of (-)-secodaphniphylline. J. Org. Chem.<\/i> 1992<\/b>, 57<\/i>, 2566-2574.<\/li>\n
  3. Organic Chemistry<\/i>, 6th ed.; Wade, L. G., Jr. Pearson Prentice Hall; 2006.<\/li>\n
  4. Strategic Applications of Named Reactions in Organic Synthesis<\/i>, 1st ed.; K\u00fcrti, L. and Czak\u00f3, B.; Academic Press; 2005.<\/li>\n<\/ol>\n<\/div>","protected":false},"excerpt":{"rendered":"

    \u514b\u840a\u68ee\u7e2e\u5408\u53cd\u61c9Claisen Condensation Reaction \u570b\u7acb\u81fa\u7063\u5e2b\u7bc4\u5927\u5b78\u5316\u5b78\u7cfb\u535a\u58eb\u751f\u6797\u6b23\u6167 …<\/p>\n","protected":false},"author":50,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"footnotes":""},"categories":[108,4798,4800],"tags":[7315,7314],"class_list":["post-58198","post","type-post","status-publish","format-standard","hentry","category-chemistry00","category-chemistry07","category-chemistry07-02","tag-7315","tag-7314","loop-entry","cat-108","cat-4798","cat-4800","no-thumbnail"],"views":5690,"_links":{"self":[{"href":"http:\/\/localhost\/wp-json\/wp\/v2\/posts\/58198","targetHints":{"allow":["GET"]}}],"collection":[{"href":"http:\/\/localhost\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"http:\/\/localhost\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"http:\/\/localhost\/wp-json\/wp\/v2\/users\/50"}],"replies":[{"embeddable":true,"href":"http:\/\/localhost\/wp-json\/wp\/v2\/comments?post=58198"}],"version-history":[{"count":1,"href":"http:\/\/localhost\/wp-json\/wp\/v2\/posts\/58198\/revisions"}],"predecessor-version":[{"id":86770,"href":"http:\/\/localhost\/wp-json\/wp\/v2\/posts\/58198\/revisions\/86770"}],"wp:attachment":[{"href":"http:\/\/localhost\/wp-json\/wp\/v2\/media?parent=58198"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"http:\/\/localhost\/wp-json\/wp\/v2\/categories?post=58198"},{"taxonomy":"post_tag","embeddable":true,"href":"http:\/\/localhost\/wp-json\/wp\/v2\/tags?post=58198"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}