{"id":58267,"date":"2014-11-08T03:00:53","date_gmt":"2014-11-07T19:00:53","guid":{"rendered":"http:\/\/highscope.ch.ntu.edu.tw\/wordpress\/?p=58267"},"modified":"2021-10-06T16:12:49","modified_gmt":"2021-10-06T08:12:49","slug":"%e9%81%b7%e7%a7%bb%e5%8f%8d%e6%87%89%ef%bc%88migration%ef%bc%89","status":"publish","type":"post","link":"http:\/\/localhost\/%e9%81%b7%e7%a7%bb%e5%8f%8d%e6%87%89%ef%bc%88migration%ef%bc%89\/","title":{"rendered":"\u9077\u79fb\u53cd\u61c9\uff08Migration\uff09"},"content":{"rendered":"

\u9077\u79fb\u53cd\u61c9\uff08Migration\uff09<\/strong><\/span>
\n\u570b\u7acb\u81fa\u7063\u5e2b\u7bc4\u5927\u5b78\u5316\u5b78\u7cfb\u78a9\u58eb\u73ed\u4e8c\u5e74\u7d1a\u9673\u57f9\u6770\u7814\u7a76\u751f<\/strong><\/span><\/p>\n

\u9077\u79fb(migration)\u901a\u5e38\u6d89\u53ca\u4e00\u500b\u53d6\u4ee3\u57fa\u7531\u4e00\u500b\u539f\u5b50\u8f49\u79fb\u5230\u540c\u4e00\u500b\u5206\u5b50\u4e2d\u7684\u53e6\u4e00\u500b\u539f\u5b50\u7684\u904e\u7a0b\uff0c\u4e5f\u7b97\u662f\u91cd\u6392\u53cd\u61c9(rearrangement)\u88e1\u9762\u7684\u5176\u4e2d\u4e00\u7a2e\u3002\u5148\u8b93\u6211\u5011\u4f86\u770b\u770b\u7c21\u55ae\u7684\u78b3\u967d\u96e2\u5b50\u91cd\u6392\u53cd\u61c9(carbocation rearrangement)\uff0c\u4ee5 3-Methyl-2-butanol \u70ba\u4f8b\uff1a<\/p>\n

Step1: \u6c27\u4e0a\u7684\u5b64\u5c0d\u96fb\u5b50\u9032\u884c\u8cea\u5b50\u5316(protonation)\u53cd\u61c9<\/p>\n

\"58267_eq1\"<\/a><\/p>\n

Step2: \u812b\u6c34\u53cd\u61c9\uff0c\u96e2\u53bb\u4e00\u5206\u5b50\u7684\u6c34\u3002<\/p>\n

\"58267_eq2\"<\/a><\/p>\n

Step3:\u6c2b\u8f49\u79fb(Hydrogen shift)<\/p>\n

\"58267_eq3\"<\/a><\/p>\n

\u539f\u7406:\u91cd\u6392\u53cd\u61c9\u901a\u5e38\u90fd\u6703\u6d89\u53ca\u5230\u78b3\u967d\u96e2\u5b50\u7684\u751f\u6210\uff0c\u70ba\u4e86\u5f62\u6210\u7a69\u5b9a\u7684\u78b3\u967d\u96e2\u5b50\u4e2d\u9593\u9ad4\uff0c\u901a\u5e38\u6703\u9032\u884c $$\\mathrm{H}$$ \u7684\u9077\u79fb\u53c8\u6216\u8005\u662f\u70f7\u57fa\u6216\u82ef\u57fa\u7684\u9077\u79fb\u3002\u7576\u4e00\u500b\u78b3\u967d\u96e2\u5b50\u65c1\u908a\u7684\u78b3\u4e0a\u6c92\u6709\u6c2b\u6642\uff0c\u53ef\u4ee5\u9032\u884c\u53e6\u5916\u4e00\u7a2e\u91cd\u6392\uff0c\u90a3\u5c31\u662f\u70f7\u57fa\u9077\u79fb(alkyl migration) \u3002\u53cd\u61c9\u901f\u7387\u53c8\u53d7\u5230 step 2 \u4e2d\u7684\u78b3\u967d\u96e2\u5b50\u7a69\u5b9a\u5ea6\u6240\u5f71\u97ff:<\/p>\n

$$\\mathrm{{CH_3}^+<{CH_3CH_2}^+<(CH_3)_2CH^+\\cong CH_2}\\text{=}\\mathrm{CH}\\text{-}\\mathrm{{CH_2}^+<{C_6H_5CH_2}^+\\cong (CH_3)_3C^+}$$<\/p>\n

\u4ee5 3,3-Dimethyl-2-butanol \u70ba\u4f8b\u5b50\uff1a<\/p>\n

\"58267_p1\"<\/a><\/p>\n

\u4e00\u6a23\u5148\u8cea\u5b50\u5316\u5f8c\u96e2\u53bb\u4e00\u5206\u5b50\u7684\u6c34\uff0c\u5f97\u5230\u4e00\u8f03\u4e0d\u7a69\u5b9a\u7684\u78b3\u967d\u96e2\u5b50\uff0c\u56e0\u5176\u65c1\u908a\u7684\u78b3\u4e0a\u7121\u591a\u9918\u7684\u6c2b\u53ef\u4ee5\u9077\u79fb\uff0c\u6539\u7531\u7532\u70f7\u57fa\u9032\u884c\u9077\u79fb\uff0c\u9077\u79fb\u7684\u7532\u70f7\u57fa\u5f9e\u539f\u672c\u4f4d\u7f6e\u7684\u78b3\u4e0a\u7372\u5f97\u5230\u5169\u500b\u96fb\u5b50\uff0c\u7136\u5f8c\u518d\u9077\u79fb\u5230\u9694\u58c1\u8f03\u7f3a\u96fb\u5b50\u7684\u78b3\u967d\u96e2\u5b50\u4e0a\uff0c\u8b8a\u6210\u8f03\u70ba\u7a69\u5b9a\u7684\u4e09\u7d1a\u78b3\u967d\u96e2\u5b50<\/p>\n

\u9084\u6709\u53e6\u4e00\u7a2e\u9023\u7e8c(concerted)\u7684\u65b9\u6cd5<\/p>\n

\"58267_p2\"<\/a><\/p>\n

\u4e5f\u662f\u5148\u9032\u884c\u8cea\u5b50\u5316\uff0c\u63a5\u8457\u7532\u70f7\u57fa\u9077\u79fb\uff0c\u628a\u6c34\u7576\u4f5c\u96e2\u53bb\u57fa\u9806\u4fbf\u812b\u53bb\u4e00\u5206\u5b50\u7684\u6c34\u3002\u9019\u7a2e\u9023\u7e8c\u7684\u65b9\u6cd5\u9084\u53ef\u4ee5\u907f\u514d\u5f62\u6210\u4e0d\u7a69\u5b9a\u7684\u4e8c\u7d1a\u78b3\u967d\u96e2\u5b50\u3002<\/p>\n

\u8457\u540d\u7684\u983b\u90a3\u9187\u91cd\u6392 (Pinacol rearrangement)\u4fbf\u662f\u5229\u7528\u9019\u7a2e\u9077\u79fb\u7684\u65b9\u6cd5<\/p>\n

\"58267_p3\"<\/a><\/p>\n

\u5728\u983b\u90a3\u9187\u91cd\u6392\u4e2d\uff0c\u983b\u90a3\u9187\u5176\u4e2d\u7684 $$\\mathrm{OH}$$ \u5b98\u80fd\u57fa\u5148\u8cea\u5b50\u5316\uff0c\u812b\u6c34\u4e4b\u5f8c\u5f97\u5230\u4e00\u500b\u4e09\u7d1a\u78b3\u967d\u96e2\u5b50\uff0c\u63a5\u8457\u7532\u57fa\u9077\u79fb\u5230\u539f\u672c\u7684\u78b3\u967d\u96e2\u5b50\u7684\u4f4d\u7f6e\uff0c\u6b64\u9077\u79fb\u7684\u9a45\u52d5\u529b\u88ab\u8a8d\u70ba\u662f\u6240\u5f97\u5230\u7684 oxonium ion \u6709\u8f03\u7a69\u5b9a\u7684\u516b\u9685\u9ad4\u4e2d\u5fc3\uff0c\u4e4b\u5f8c\u6c27\u4e0a\u7684\u5b64\u5c0d\u96fb\u5b50\u518d\u5171\u632f\u5230\u78b3\u4e0a\u5f62\u6210\u6700\u5f8c\u7684 pinacolone\u3002<\/p>\n

\u70f7\u57fa\u9077\u79fb\u9084\u8981\u5fc5\u9808\u8003\u616e\u5e7e\u500b\u8981\u7d20\uff1a<\/p>\n

    \n
  1. \u7522\u7269\u5728\u7af6\u722d\u91cd\u6392\u4e2d\u7684\u7a69\u5b9a\u5ea6
    \n    \"58267_p4\"<\/a>
    \n\u7531\u5716\u53ef\u4ee5\u77e5\u9053\uff0c\u74b0\u5167\u7684\u4e9e\u7532\u57fa\u548c\u7532\u57fa\u90fd\u53ef\u4ee5\u9077\u79fb\uff0c\u4f46\u662f\u8f03\u504f\u597d\u4e9e\u7532\u57fa\u53bb\u9077\u79fb\uff0c\u96d6\u7136\u5177\u6709equatorial\u7532\u57fa\u7684\u6905\u578b\u7d50\u69cb\u61c9\u8a72\u662f\u8f03\u7a69\u5b9a\u7684\uff0c\u4f46\u662f\u4e0d\u9069\u7528\u65bc\u7532\u57fa\u9077\u79fb<\/li>\n
  2. \u74b0\u5f35\u529b\u5c0d\u9077\u79fb\u7684\u5f71\u97ff
    \n    \"58267_p5\"<\/a>
    \n\u6b64\u9077\u79fb\u70ba\u4e00\u500b\u8f03\u4e0d\u5c0b\u5e38\u7684\u9077\u79fb\uff0c\u96d6\u7136\u82ef\u57fa\u6709\u4e0d\u932f\u7684\u9077\u79fb\u80fd\u529b\u4f46\u662f\u4e26\u672a\u5f97\u5230 2,2-diphenylcyclobutanone \u7684\u7522\u7269\uff0c\u7531\u4e00\u500b\u5c0f\u74b0\u5f62\u6210\u53e6\u4e00\u500b\u66f4\u5c0f\u7684\u74b0\uff0c\u56e0\u70ba\u5982\u679c\u662f\u7531\u82ef\u57fa\u9077\u79fb\uff0c\u6240\u5f97\u5230\u7684\u7522\u7269\u6703\u56e0\u70ba\u74b0\u5f35\u529b\u7684\u539f\u56e0\u800c\u8f03\u4e0d\u7a69\u5b9a<\/li>\n<\/ol>\n

    \u53e6\u5916\u9084\u6709\u4e00\u4e9b\u5229\u7528\u904e\u6e21\u91d1\u5c6c\u4f86\u9032\u884c\u70f7\u57fa\u9077\u79fb<\/p>\n

    \"58267_p6\"<\/a><\/p>\n

    \u5229\u7528\u91d1\u5c6c\u4f86\u50ac\u5316\u5e36\u6709 $$R^1$$\u00a0\u53d6\u4ee3\u57fa\u7684\u5206\u5b50 $$b$$ \u4ee5\u53ca\u5e36\u6709 $$R^2$$\u00a0\u53d6\u4ee3\u57fa\u7684\u5206\u5b50 $$e$$\uff0c\u7d93\u7531\u4e00\u9023\u4e32\u7684 $$[2+2]$$ \u4ee5\u53ca\u53cd $$[2+2]$$ \u53cd\u61c9\uff0c\u4f7f\u539f\u672c\u53ea\u5e36\u6709\u4e00\u500b\u53d6\u4ee3\u57fa\u7684\u5206\u5b50 $$b$$ \u8ddf $$c$$ \u53cd\u61c9\u70ba\u5e36\u6709\u5169\u500b\u53d6\u4ee3\u57fa\u7684\u5206\u5b50 $$f$$\uff0c\u5176\u53cd\u61c9\u8def\u5f91\u7c21\u7565\u5982\u4e0b<\/p>\n

    \"58267_p7\"<\/a><\/p>\n

    \u5206\u5b50 $$a$$\u00a0\u5148\u8207\u5206\u5b50 $$b$$\u00a0\u9032\u884c $$[2+2]$$ \u53cd\u61c9\u5f97\u5230\u5206\u5b50 $$i$$\uff0c\u63a5\u8457\u9032\u884c\u53cd $$[2+2]$$ \u53cd\u61c9\u5f97\u5230\u5206\u5b50 $$c$$\u00a0\u8207 $$d$$\uff0c\u5206\u5b50 $$d$$\u00a0\u6703\u8207\u5206\u5b50 $$e$$\u00a0\u9032\u884c $$[2+2]$$ \u7f6e\u63db\u53cd\u61c9\uff08metathesis\uff09\u5f97\u5230\u5206\u5b50 $$g$$\u3002\u6700\u5f8c\u5206\u5b50 $$g$$\u00a0\u9032\u884c\u53cd $$[2+2]$$ \u53cd\u61c9\u5f97\u5230\u5206\u5b50 $$a$$\u00a0\u8207 $$f$$\u3002<\/p>\n

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

      \n
    1. https:\/\/www2.chemistry.msu.edu\/faculty\/reusch\/virttxtjml\/rearrang.htm<\/a><\/li>\n
    2. http:\/\/en.wikipedia.org\/wiki\/Rearrangement_reaction<\/a><\/li>\n<\/ol>\n<\/div>","protected":false},"excerpt":{"rendered":"

      \u9077\u79fb\u53cd\u61c9\uff08Migration\uff09 \u570b\u7acb\u81fa\u7063\u5e2b\u7bc4\u5927\u5b78\u5316\u5b78\u7cfb\u78a9\u58eb\u73ed\u4e8c\u5e74\u7d1a\u9673\u57f9\u6770\u7814\u7a76\u751f \u9077\u79fb(migration)\u901a\u5e38…<\/p>\n","protected":false},"author":50,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"footnotes":""},"categories":[108,68,67],"tags":[7326,7327,7325],"class_list":["post-58267","post","type-post","status-publish","format-standard","hentry","category-chemistry00","category-chemistry05-01","category-chemistry05","tag-7326","tag-7327","tag-7325","loop-entry","cat-108","cat-68","cat-67","no-thumbnail"],"views":8986,"_links":{"self":[{"href":"http:\/\/localhost\/wp-json\/wp\/v2\/posts\/58267","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=58267"}],"version-history":[{"count":1,"href":"http:\/\/localhost\/wp-json\/wp\/v2\/posts\/58267\/revisions"}],"predecessor-version":[{"id":86759,"href":"http:\/\/localhost\/wp-json\/wp\/v2\/posts\/58267\/revisions\/86759"}],"wp:attachment":[{"href":"http:\/\/localhost\/wp-json\/wp\/v2\/media?parent=58267"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"http:\/\/localhost\/wp-json\/wp\/v2\/categories?post=58267"},{"taxonomy":"post_tag","embeddable":true,"href":"http:\/\/localhost\/wp-json\/wp\/v2\/tags?post=58267"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}