{"id":28295,"date":"2018-08-08T01:00:00","date_gmt":"2018-08-09T03:54:48","guid":{"rendered":"http:\/\/www.05921.net\/index.php\/2018\/08\/09\/%e9%a2%a0%e8%a6%86%e6%95%99%e7%a7%91%e4%b9%a6%e7%9a%84%e5%8f%91%e7%8e%b0%ef%bc%9a13c-kie%e7%a0%94%e7%a9%b6%e6%8f%ad%e7%a4%ba%e8%8a%b3%e9%a6%99%e4%ba%b2%e6%a0%b8%e5%8f%96%e4%bb%a3%e5%8f%8d%e5%ba%94\/"},"modified":"2018-08-09T11:54:51","modified_gmt":"2018-08-09T03:54:51","slug":"%e9%a2%a0%e8%a6%86%e6%95%99%e7%a7%91%e4%b9%a6%e7%9a%84%e5%8f%91%e7%8e%b0%ef%bc%9a13c-kie%e7%a0%94%e7%a9%b6%e6%8f%ad%e7%a4%ba%e8%8a%b3%e9%a6%99%e4%ba%b2%e6%a0%b8%e5%8f%96%e4%bb%a3%e5%8f%8d%e5%ba%94","status":"publish","type":"post","link":"https:\/\/www.05921.net\/index.php\/28295\/","title":{"rendered":"\u98a0\u8986\u6559\u79d1\u4e66\u7684\u53d1\u73b0\uff1a13C KIE\u7814\u7a76\u63ed\u793a\u82b3\u9999\u4eb2\u6838\u53d6\u4ee3\u53cd\u5e94\u673a\u7406 \u2014 \u89e3\u8bfb | \u4e13\u8bbf"},"content":{"rendered":"
\n

\u200d\u200d<\/span>\u200d\"\u98a0\u8986\u6559\u79d1\u4e66\u7684\u53d1\u73b0\uff1a13C<\/span><\/a><\/span><\/a><\/p>\n

<\/p>\n

\u524d\u8a00\uff1a\u54c8\u4f5b\u5927\u5b66\u7684Eric Jacobsen\u8bfe\u9898\u7ec4\u8fd1\u671f\u5728<\/span>Nature Chemistry<\/em><\/span> \u4e0a\u62a5\u9053\u4e86\u82b3\u9999\u4eb2\u6838\u53d6\u4ee3\u53cd\u5e94\u673a\u7406\u7684\u7814\u7a76\u65b0\u7a81\u7834\u3002\u6211\u4eec\u5f88\u8363\u5e78\u5730\u91c7\u8bbf\u5230\u4e86Jacobsen\u8bfe\u9898\u7ec4\u7684\u66fe\u88d5\u6587<\/strong>\u535a\u58eb\uff0c\u4e13\u8bbf\u7eaa\u8981\u9644\u4e8e\u8bba\u6587\u89e3\u8bfb\u4e4b\u540e\uff0c\u6b22\u8fce\u5404\u4f4d\u8bfb\u8005\u9605\u8bfb\u3002<\/span><\/p>\n

\"\u98a0\u8986\u6559\u79d1\u4e66\u7684\u53d1\u73b0\uff1a13C<\/p>\n

Eric Jacobsen\u6559\u6388\u3002\u56fe\u7247\u6765\u6e90\uff1aHarvard University<\/span><\/p>\n

<\/p>\n

\u5206\u6b65\u8fd8\u662f\u534f\u540c\uff1f<\/span><\/strong><\/p>\n

<\/p>\n

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<\/p>\n

\u82b3\u9999\u4eb2\u6838\u53d6\u4ee3<\/span><\/strong>\uff08Nucleophilic aromatic substitution, S<\/span>N<\/sub><\/span>Ar\uff09\u53cd\u5e94\u6700\u65e9\u53d1\u73b0\u4e8e\u5341\u4e5d\u4e16\u7eaa\u672b\u671f\uff0c\u662f\u540d\u526f\u5176\u5b9e\u7684\u767e\u5e74\u7ecf\u5178\u53cd\u5e94\uff0c\u5728\u5404\u5408\u6210\u9886\u57df\u4e2d\u5747\u6709\u5e7f\u6cdb\u7684\u5e94\u7528\u3002\u7814\u7a76\u8868\u660e\uff0cS<\/span>N<\/sub><\/span>Ar\u53cd\u5e94\u5728\u836f\u7269\u5316\u5b66\u4e2d\u7684\u4f7f\u7528\u9891\u7387\u4ec5\u6b21\u4e8e\u9170\u80fa\u952e\u5f62\u6210\u548c\u5076\u8054\u53cd\u5e94\uff0c\u4f4d\u5217\u7b2c\u4e09<\/span> [1]<\/sup><\/span>\u30021902\u5e74\uff0c\u5fb7\u56fd\u5316\u5b66\u5bb6Meisenheimer\u9996\u6b21\u63d0\u51fa\u4e86\u5171\u632f\u7a33\u5b9a\u7684\u8d1f\u79bb\u5b50\u4e2d\u95f4\u4f53\uff0c\u4ece\u6b64\u8be5\u4e2d\u95f4\u4f53\u88ab\u547d\u540d\u4e3aMeisenheimer\u7edc\u5408\u7269\u3002\u4e0a\u4e2a\u4e16\u7eaa\u4e2d\u671f\uff0c\u7269\u7406\u6709\u673a\u5316\u5b66\u5bb6\u5bf9S<\/span>N<\/sub><\/span>Ar\u53cd\u5e94\u8fdb\u884c\u4e86\u5e7f\u6cdb\u7684\u7814\u7a76\uff0c\u5927\u91cf\u7684Meisenheimer\u4e2d\u95f4\u4f53\u5f97\u4ee5\u8868\u5f81\u751a\u81f3\u5206\u79bb\u3002\u81f3\u6b64\uff0cS<\/span>N<\/sub><\/span>Ar\u53cd\u5e94\u7ecf\u5386\u52a0\u6210-\u6d88\u9664\u4e24\u4e2a\u5206\u6b65\u8fc7\u7a0b\u7684\u89c2\u5ff5\u88ab\u6709\u673a\u5316\u5b66\u754c\u5e7f\u4e3a\u63a5\u53d7\u3002\u6b64\u540e\u7684\u516d\u5341\u591a\u5e74\u65f6\u95f4\u91cc\uff0c\u5728\u6240\u6709\u7684\u6559\u79d1\u4e66\u4e2d\uff0cS<\/span>N<\/sub><\/span>Ar\u53cd\u5e94\u90fd\u662f\u4ee5\u5206\u6b65\u673a\u7406\u7684\u5f62\u5f0f\u51fa\u73b0\uff08\u56fe1\uff09\u3002<\/span><\/p>\n

\"\u98a0\u8986\u6559\u79d1\u4e66\u7684\u53d1\u73b0\uff1a13C<\/p>\n

\u56fe1. \u6559\u79d1\u4e66\u4e2d\u5bf9\u4e8eS<\/span><\/span>N<\/sub><\/span>Ar\u53cd\u5e94\u673a\u7406\u7684\u4ecb\u7ecd<\/span><\/p>\n

<\/p>\n

\u5bf9\u4e4b\u524d\u4f17\u591a\u673a\u7406\u7814\u7a76\u8fdb\u884c\u603b\u7ed3\u548c\u5206\u6790\u4e4b\u540e\uff0c\u6211\u4eec\u53ef\u4ee5\u53d1\u73b0\u8fd9\u4e9b\u7814\u7a76\u4f53\u7cfb\u57fa\u672c\u90fd\u5177\u6709\u4ee5\u4e0b\u4e24\u4e2a\u7279\u5f81\uff1a\uff081\uff09\u9ad8\u5ea6\u7a33\u5b9a\u5316\u7684\u82b3\u9999\u4f53\u7cfb\uff08\u4e2d\u95f4\u4f53\u7684\u8d1f\u7535\u8377\u88ab\u591a\u4e2a\u785d\u57fa\u53d6\u4ee3\u57fa\u7a33\u5b9a\uff09\uff1b\uff082\uff09\u5f31\u79bb\u6838\u4f53\u7cfb\uff08C-Nu\u4e0eC-LG\u952e\u80fd\u5f88\u5f3a\uff0c\u96be\u4ee5\u65ad\u88c2\uff09\u3002\u8fd9\u662f\u56e0\u4e3a\u5728\u4e0a\u4e16\u7eaa\u4e94\u516d\u5341\u5e74\u4ee3\uff0c\u673a\u7406\u7814\u7a76\u7684\u65b9\u6cd5\u8fd8\u5f88\u6709\u9650\u3002\u4e3a\u4e86\u7814\u7a76\u9ad8\u80fd\u91cf\u7684\u82b3\u57fa\u8d1f\u79bb\u5b50\u4e2d\u95f4\u4f53\uff0c\u7269\u7406\u6709\u673a\u5316\u5b66\u5bb6\u4eec\u503e\u5411\u4e8e\u5f15\u5165\u5404\u79cd\u7a33\u5b9a\u56e0\u7d20\u6765\u7a33\u5b9a\u8be5\u4e2d\u95f4\u4f53\uff0c\u8fdb\u800c\u7528\u7d2b\u5916-\u53ef\u89c1\u5149\u8c31\uff08UV-Vis\uff09\u3001\u6838\u78c1\u5171\u632f\uff08NMR\uff09\u4ee5\u53caX\u5c04\u7ebf\u884d\u5c04\u7684\u65b9\u6cd5\u6765\u7814\u7a76\u548c\u8868\u5f81\u3002\u56e0\u6b64\uff0c\u5728\u9ad8\u5ea6\u7f3a\u7535\u5b50\u7684\u82b3\u9999\u4f53\u7cfb\u4e2d\u89c2\u5bdf\u5230\u7a33\u5b9a\u7684Meisenheimer\u4e2d\u95f4\u4f53\u5e76\u4e0d\u60ca\u5947\u3002\u4f46\u95ee\u9898\u7684\u5173\u952e\u662f\uff0c\u6781\u7aef\u6761\u4ef6\u4e0b\u6240\u5f97\u5230\u7684\u7814\u7a76\u7ed3\u679c\u662f\u5426\u53ef\u4ee5\u63a8\u5e7f\u5230\u6240\u6709\u7684\u53cd\u5e94\u4f53\u7cfb\uff1f\u66f4\u8fdb\u4e00\u6b65\u8bb2\uff0c\u5bf9\u4e8e\u66f4\u4e3a\u5e38\u89c1\u7684\uff0c\u4e0d\u90a3\u4e48\u7f3a\u7535\u5b50\u7684S<\/span>N<\/sub><\/span>Ar\u53cd\u5e94\u4f53\u7cfb\uff0c\u662f\u5426\u5b58\u5728\u7740\u534f\u540c\u673a\u7406\u7684\u53ef\u80fd\u6027\uff1f<\/span><\/p>\n

<\/p>\n

13<\/sup><\/span>C<\/span> KIE\u5728\u53cd\u5e94\u534f\u540c\u6027\u7814\u7a76\u4e2d\u7684\u5e94\u7528<\/span><\/strong><\/p>\n

<\/p>\n

\u54c8\u4f5b\u5927\u5b66<\/span><\/strong>\u7684Eric Jacobsen<\/strong>\u8bfe\u9898\u7ec4\u957f\u671f\u81f4\u529b\u4e8e\u53cd\u5e94\u673a\u7406\u7684\u7814\u7a76\u3002\u5bf9\u4e8e\u201c\u5206\u6b65\u8fd8\u662f\u534f\u540c\u201d\u8fd9\u4e2a\u7ecf\u5178\u95ee\u9898\uff0cJacobsen\u8bfe\u9898\u7ec4\u7684Eugene Kwan<\/strong>\u535a\u58eb\u548c\u66fe\u88d5\u6587<\/strong>\u535a\u58eb\u7b49\u7814\u7a76\u8005\u5c1d\u8bd5\u7528<\/span>12<\/sup><\/span>C\/13<\/sup><\/span>C<\/span>\u52a8\u529b\u5b66\u540c\u4f4d\u7d20\u6548\u5e94<\/strong>\uff08Kinetic isotope effect, KIE\uff09\u6765\u56de\u7b54\u3002\u7531\u4e8e13<\/sup><\/span>C<\/span> KIE\u80fd\u591f\u63d0\u4f9b\u53cd\u5e94\u8fc7\u6e21\u6001\uff08Transition state, TS\uff09\u4e2d\u78b3\u539f\u5b50\u6210\u952e\/\u65ad\u88c2\u65f6\u7684\u76f4\u63a5\u4fe1\u606f\uff0c\u5728\u53cd\u5e94\u534f\u540c\u6027\uff08concertedness\uff09\u7814\u7a76\u4e2d\u5177\u6709\u5148\u5929\u7684\u4f18\u52bf\uff08\u56fe2\uff09\u3002\u5177\u4f53\u6765\u8bb2\uff0c\u5728\u5bf9\u79f0\u7684\u534f\u540c\u53cd\u5e94\u4e2d\uff0c\u8fc7\u6e21\u6001\uff08TS\uff09\u5728\u53cd\u5e94\u5750\u6807\u7684\u4e2d\u95f4\u3002\u65b0\u952e\u5c1a\u672a\u5f62\u6210\u7684\u540c\u65f6\uff0c\u65e7\u952e\u5df2\u7ecf\u65ad\u88c2\uff0c\u6b64\u65f6\u8fc7\u6e21\u6001\u4e2d12<\/sup><\/span>C<\/span>\u548c13<\/sup><\/span>C<\/span>\u96f6\u70b9\u80fd\u5dee\u63a5\u8fd1\u4e8e\u96f6\uff0c\u6545\u4eba\u4eec\u80fd\u89c2\u5bdf\u5230\u6781\u9650\u7684KIE\u503c\uff08\u56fe2\uff0c\u5de6\uff09\u3002\u4f8b\u5982\uff0c\u5728S<\/span>N<\/sub><\/span>2\u53cd\u5e94\u4e2d\uff0c13<\/sup><\/span>C <\/span>KIE\u4e00\u822c\u57281.04-1.08\u4e4b\u95f4\uff08\u4e00\u7ea713<\/sup><\/span>C <\/span>KIE\u7684\u6781\u503c\u7ea6\u4e3a1.08\uff09\u3002\u4e0e\u6b64\u540c\u65f6\uff0c\u5728\u5206\u6b65\u673a\u7406\u4e2d\uff0c\u7531\u4e8e\u4e2d\u95f4\u4f53\u80fd\u91cf\u9ad8\uff0c\u8fc7\u6e21\u6001\u4e00\u822c\u5f88\u65e9\u6216\u5f88\u665a\uff08early\/late TS\uff09\uff0c\u6b64\u65f6\u8fc7\u6e21\u6001\u4e2d12<\/sup><\/span>C<\/span>\u548c13<\/sup><\/span>C<\/span>\u96f6\u70b9\u80fd\u5dee\u63a5\u8fd1\u4e8e\u539f\u6599\u4e2d12<\/sup><\/span>C<\/span>\u548c13<\/sup><\/span>C<\/span>\u96f6\u70b9\u80fd\u5dee\uff0c\u6545\u53ea\u80fd\u89c2\u5bdf\u5230\u76f8\u5bf9\u5c0f\u7684KIE\uff08\u56fe2\uff0c\u53f3\uff09\u3002\u4f8b\u5982\u5728S<\/span>N<\/sub><\/span>1\u53cd\u5e94\u4e2d\uff0c13<\/sup><\/span>C<\/span> KIE\u4e00\u822c\u63a5\u8fd1\u4e8e1.00\u3002<\/span><\/p>\n

\"\u98a0\u8986\u6559\u79d1\u4e66\u7684\u53d1\u73b0\uff1a13C<\/p>\n

\u56fe2. \u534f\u540c\u8def\u5f84\u4e0e\u5206\u6b65\u8def\u5f84\u5bf9<\/span>13<\/sup><\/span>C KIE\u7684\u5f71\u54cd<\/span><\/p>\n

<\/p>\n

\u4e3a\u4e86\u66f4\u597d\u5730\u7814\u7a76S<\/span>N<\/sub><\/span>Ar\u53cd\u5e94\u7684\u534f\u540c\u6027\uff0c\u4ed6\u4eec\u9009\u53d6\u4e86\u4e09\u4e2a\u5177\u6709\u4ee3\u8868\u6027\u7684\u53cd\u5e94\uff08\u56fe3\uff09\uff1a\uff08A\uff09\u6781\u5ea6\u7f3a\u7535\u5b50\u7684\u82b3\u9999\u4f53\u7cfb\u4e2d\u62e5\u6709\u5f31\u7684\u79bb\u53bb\u57fa\u56e2\uff08F\uff09\uff1b\uff08B\uff09\u4e2d\u7b49\u7f3a\u7535\u5b50\u7684\u6742\u73af\u4f53\u7cfb\u4e2d\u62e5\u6709\u597d\u7684\u79bb\u53bb\u57fa\u56e2\uff08Br\uff09\uff1b\uff08C\uff09\u6781\u5ea6\u7f3a\u7535\u5b50\u7684\u82b3\u9999\u4f53\u7cfb\u4e2d\u62e5\u6709\u597d\u7684\u79bb\u53bb\u57fa\u56e2\uff08Cl\uff09\u3002<\/span><\/p>\n

\"\u98a0\u8986\u6559\u79d1\u4e66\u7684\u53d1\u73b0\uff1a13C<\/p>\n

\u56fe3. \u4e09\u79cd\u4e0d\u540c\u7684\u53cd\u5e94\u4f53\u7cfb\u3002\u56fe\u7247\u6765\u6e90\uff1aNat. Chem.<\/em><\/span><\/p>\n

<\/p>\n

\u9996\u5148\uff0c\u8026\u5408\u7c07\uff08coupled cluster\uff09\u7406\u8bba\u8ba1\u7b97\uff08\u7cbe\u5ea6\u9ad8\uff0c\u88ab\u89c6\u4e3a\u8ba1\u7b97\u4e2d\u7684\u91d1\u6807\u51c6\uff09\u5f97\u5230\u4e86\u4e09\u4e2a\u53cd\u5e94\u7684\u52bf\u80fd\u9762\uff08\u56fe4a\u30014c\u30014f\uff09\u3002\u4ece\u56fe4a\u53ef\u4ee5\u770b\u51fa\uff0c\u53cd\u5e94A\u7ecf\u5386\u4e86\u4e00\u4e2a\u7a33\u5b9a\u7684Meisenheimer\u4e2d\u95f4\u4f53\uff08\u5de6\u4e0b\u89d2\uff09\u3002\u4e3a\u4e86\u8fdb\u4e00\u6b65\u9a8c\u8bc1\u8ba1\u7b97\u7684\u51c6\u786e\u6027\uff0c\u7814\u7a76\u8005\u8fd8\u8ba1\u7b97\u4e86\u8be5\u53cd\u5e94\u7684\u201cKIE\u56fe\u201d\uff08\u56fe4b\uff09\u3002\u7531\u56fe4b\u53ef\u77e5\uff0c\u8be5\u53cd\u5e94KIE\u7684\u6781\u503c\u4e3a1.070\uff0c\u5176\u5bf9\u6620\u7684\u53cd\u5e94\u8fc7\u6e21\u6001\u5728\u4e2d\u95f4\u7684\u7ea2\u8272\u533a\u57df\u5904\uff0c\u53ea\u6709\u7ecf\u5386\u534f\u540c\u8fc7\u7a0b\u624d\u80fd\u8fbe\u5230\u3002\u4e8b\u5b9e\u4e0a\uff0c\u53cd\u5e94A\u7ecf\u5386\u7684\u662f\u5206\u6b65\u8fc7\u7a0b\uff0c\u5206\u522b\u5bf9\u5e94\u56fe4b\u4e2d\u7684\u4e24\u6761\u767d\u7ebf\uff0c\u4ece\u800c\u89c4\u907f\u4e86\u9ad8KIE\u533a\u57df\u3002\u5bf9\u4e8e\u8be5\u53cd\u5e94\uff0c\u8ba1\u7b97\u9884\u6d4b\u768413<\/sup><\/span>C<\/span> KIE\u7ed3\u679c\u4e3a1.033\uff0c\u4e0e\u5b9e\u9645\u6d4b\u91cf\u7ed3\u679c\uff081.035\uff09\u4e00\u81f4\uff0c\u8fdb\u4e00\u6b65\u9a8c\u8bc1\u4e86\u8ba1\u7b97\u7684\u51c6\u786e\u6027\u3002\u540c\u65f6\uff0c\u5b9e\u9645KIE\u4e3a\u7406\u8bba\u6781\u503c\u768447 %\uff0c\u4e5f\u663e\u793a\u4e86\u53cd\u5e94\u7ecf\u5386\u5206\u6b65\u673a\u7406\u3002\u5bf9\u4e8e\u53cd\u5e94B\uff0c\u8ba1\u7b97\u5219\u8868\u660e\u53cd\u5e94\u662f\u534f\u540c\u8fc7\u7a0b\uff0c\u4f53\u7cfb\u4e2d\u6ca1\u6709\u89c2\u5bdf\u5230\u7a33\u5b9a\u7684\u4e2d\u95f4\u4f53\uff08\u56fe4c\uff09\u3002\u540c\u6837\uff0c\u8be5\u53cd\u5e94\u7684\u6781\u9650KIE\u4e3a1.045\uff0c\u800c\u89c2\u6d4b\u7ed3\u679c\u4e3a1.035\uff0c\u4e3a\u7406\u8bba\u6781\u503c\u768487 %\uff0c\u8fd9\u4e5f\u8bf4\u660e\u53cd\u5e94\u7ecf\u5386\u4e86\u534f\u540c\u8fc7\u7a0b\uff08\u56fe4d\uff09\u3002<\/span><\/p>\n

\"\u98a0\u8986\u6559\u79d1\u4e66\u7684\u53d1\u73b0\uff1a13C<\/p>\n

\u56fe4. \u7406\u8bba\u8ba1\u7b97\u5206\u6790\u4ece\u5206\u6b65\u5230\u534f\u540c\u673a\u7406\u7684\u8fc7\u6e21\u60c5\u51b5\u3002\u56fe\u7247\u6765\u6e90\uff1aNat. Chem.<\/em><\/span><\/p>\n

<\/p>\n

\u53cd\u5e94C\u5219\u5c5e\u4e8e\u4e34\u754c\u60c5\u51b5\uff08\u56fe4f\uff09\u3002\u517613<\/sup><\/span>C<\/span> KIE\u9884\u6d4b\u503c\uff081.040\uff09\u4e3a\u7406\u8bba\u6700\u5927\u503c\uff081.055\uff09\u768473%\uff0c\u4ecb\u4e8e\u524d\u9762\u4e24\u79cd\u6781\u7aef\u60c5\u51b5\u4e4b\u95f4\u3002\u4ece\u53cd\u5e94\u52bf\u80fd\u56fe\u6765\u770b\uff0c\u6574\u4e2a\u8fc7\u7a0b\u4e2d\u6ca1\u6709\u4e2d\u95f4\u4f53\uff1b\u4f46\u4ece\u53cd\u5e94\u52a8\u529b\u5b66\u89d2\u5ea6\u6765\u770b\uff0c\u5206\u5b50\u5728Meisenheimer\u533a\u57df\u505c\u7559\u65f6\u95f4\u8f83\u957f\uff08\u5e73\u5747\u65f6\u95f4\u4e3a233 fs\uff0c\u56fe4f\u4e2d\u865a\u7ebf\u6240\u793a\uff09\u3002\u6545\u8be5\u53cd\u5e94\u65e2\u53ef\u89c6\u4e3a\u534f\u540c\u8fc7\u7a0b\uff0c\u4f46\u5176\u8fc7\u6e21\u6001\u5bff\u547d\u663e\u8457\u957f\u4e8e\u666e\u901a\u8fc7\u6e21\u6001\uff1b\u53c8\u53ef\u89c6\u4e3a\u5206\u6b65\u8fc7\u7a0b\uff0c\u4f46\u5176\u4e2d\u95f4\u4f53\u5bff\u547d\u8fdc\u4f4e\u4e8e\u666e\u901a\u4e2d\u95f4\u4f53\u3002<\/span><\/p>\n

<\/p>\n

\u5982\u4f55\u7406\u89e3\u7814\u7a76\u7ed3\u679c<\/span><\/strong><\/p>\n

<\/p>\n

\u4ee5\u4e0a\u7684\u7814\u7a76\u663e\u793aS<\/span>N<\/sub><\/span>Ar\u53cd\u5e94\u53ef\u4ee5\u5177\u6709\u4e09\u79cd\u4e0d\u540c\u7684\u53cd\u5e94\u8def\u5f84\uff0c\u8fd9\u4e0d\u4ec5\u5f02\u4e8e\u4eba\u4eec\u5728\u6559\u79d1\u4e66\u4e0a\u6240\u63a5\u89e6\u5230\u7684\u7b80\u5355\u56fe\u793a\uff0c\u540c\u65f6\u4e5f\u6709\u4e9b\u98a0\u8986\u5e38\u89c4\u7406\u8bba\u3002\u90a3\u4e48\uff0c\u5982\u4f55\u624d\u80fd\u66f4\u597d\u5730\u7406\u89e3\u8fd9\u4e9b\u7814\u7a76\u7ed3\u679c\u5462\uff1f<\/span><\/p>\n

\"\u98a0\u8986\u6559\u79d1\u4e66\u7684\u53d1\u73b0\uff1a13C<\/p>\n

\u56fe5. \u5206\u6b65 vs. \u534f\u540cS<\/span><\/span>N<\/sub><\/span>Ar\u53cd\u5e94\u7684\u7b80\u5316Marcus\u5206\u6790\u3002\u56fe\u7247\u6765\u6e90\uff1aNat. Chem.<\/em><\/span><\/p>\n

<\/p>\n

\u4ece\u80fd\u91cf\u89d2\u5ea6\u6765\u770b\uff0c\u6839\u636eMarcus\u7406\u8bba\uff0c\u53cd\u5e94\u7684\u8def\u5f84\u7531\u8d77\u59cb\u539f\u6599\u3001\u4ea7\u7269\u548c\u4e2d\u95f4\u4f53\u8fd9\u4e09\u8005\u7684\u76f8\u5bf9\u80fd\u91cf\u6240\u51b3\u5b9a\uff08\u9075\u5faa\u80fd\u91cf\u6700\u4f4e\u539f\u5219\uff09\u3002\u5f53Meisenheimer\u4e2d\u95f4\u4f53\u88ab\u4e24\u4e2a\u5f3a\u5438\u7535\u5b50\u7684\u785d\u57fa\u7a33\u5b9a\u4e4b\u540e\uff08\u53cd\u5e94A\uff09\uff0c\u5176\u80fd\u91cf\u663e\u8457\u964d\u4f4e\uff0c\u5f00\u59cb\u4e0e\u539f\u6599\u548c\u4ea7\u7269\u7684\u52bf\u80fd\u9762\u76f8\u4ea4\uff0c\u6b64\u65f6\u7684\u53cd\u5e94\u4e3a\u5206\u6b65\u8fc7\u7a0b\uff08\u56fe5a\uff09\u3002\u4e0e\u6b64\u540c\u65f6\uff0c\u5982\u679c\u82b3\u9999\u73af\u4e0a\u7684\u5438\u7535\u5b50\u57fa\u4e0d\u80fd\u63d0\u4f9b\u8db3\u591f\u7684\u7a33\u5b9a\u4f5c\u7528\uff08\u53cd\u5e94B\uff09\uff0c\u5219Meisenheimer\u4e2d\u95f4\u4f53\u7684\u80fd\u91cf\u8f83\u9ad8\uff0c\u53cd\u5e94\u7ecf\u534f\u540c\u65b9\u5f0f\u8fdb\u884c\uff08\u56fe5b\uff09\u3002\u7136\u800c\uff0c\u5bf9\u4e8e\u4e2d\u95f4\u72b6\u6001\u7684\u53cd\u5e94C\uff0c\u60c5\u51b5\u5219\u66f4\u52a0\u590d\u6742\u3002\u9996\u5148\uff0c\u785d\u57fa\u7684\u5f3a\u5438\u7535\u5b50\u4f5c\u7528\u4f7f\u5f97\u53cd\u5e94\u5b58\u5728\u7ecf\u5386\u5206\u6b65\u8def\u5f84\u7684\u53ef\u80fd\u6027\u3002\u4f46\u662f\uff0c\u7531\u4e8e\u7ed3\u6784\u4e2d\u542b\u6709\u4e00\u4e2a\u975e\u5e38\u597d\u7684\u79bb\u53bb\u57fa\u56e2\uff0c\u7b2c\u4e8c\u6b65\u6d88\u9664\u53cd\u5e94\u7684\u80fd\u5792\u5927\u5927\u964d\u4f4e\uff0c\u4ee5\u81f3\u4e8e\u4e2d\u95f4\u4f53\u7684\u5bff\u547d\u6781\u77ed\u3002\u6b64\u65f6\u4e2d\u95f4\u4f53\u53ef\u80fd\u9000\u5316\u4e3a\u4e00\u4e2a\u6d45\u52bf\u9631\u6216\u4ec5\u4ec5\u5728\u52bf\u80fd\u9762\u4e0a\u7559\u4e0b\u4e00\u4e2a\u5c0f\u80a9\u5cf0\uff08\u56fe5c\uff09\u3002<\/span><\/p>\n

<\/p>\n

\u4ece\u7a7a\u95f4\u548c\u8f68\u9053\u7684\u89d2\u5ea6\u6765\u770b\uff0c\u534f\u540c\u7684S<\/span>N<\/sub><\/span>Ar\u53cd\u5e94\u4f3c\u4e4e\u8fd8\u662f\u96be\u4ee5\u7406\u89e3\u3002\u56e0\u4e3a\u4e0d\u50cf\u534f\u540c\u7684S<\/span>N<\/sub><\/span>2\u53cd\u5e94\uff0c\u5728S<\/span>N<\/sub><\/span>Ar\u53cd\u5e94\u4e2d\uff0c\u4eb2\u6838\u8bd5\u5242\u4eceC-X\u7684\u03c3*\u8f68\u9053\u8fdb\u653b\u662f\u7a7a\u95f4\u7981\u963b\u7684\u3002\u4e8b\u5b9e\u4e0a\uff0c\u7531\u4e8e\u80fd\u91cf\u4e0a\u76f8\u8fd1\uff0c\u8fc7\u6e21\u6001\u7684\u7ed3\u6784\u5c06\u66f4\u63a5\u8fd1\u4e8e\u4e2d\u95f4\u4f53\u800c\u4e0d\u662f\u8d77\u59cb\u539f\u6599\uff08\u56fe5b\uff09\u3002\u56e0\u6b64\uff0c\u5728\u8fc7\u6e21\u6001\u4e2d\uff0cF\u79bb\u5b50\u4ece\u03c0\u5e73\u9762\u7684\u4e0a\u65b9\u8fdb\u653b\uff0c\u7535\u5b50\u586b\u5145\u5230C=N\u7684\u03c0*\u8f68\u9053\uff1b\u4e0e\u6b64\u540c\u65f6\uff0cN\u4e0a\u7684\u5b64\u5bf9\u7535\u5b50\u5f00\u59cb\u586b\u5145C-Br\u7684\u03c3*\u8f68\u9053\uff0c\u81f4\u4f7fBr\u79bb\u5b50\u79bb\u53bb\uff08\u56fe5d\uff09\u3002\u7b80\u5355\u6765\u8bf4\uff0c\u5bf9\u4e8e\u534f\u540c\u7684S<\/span>N<\/sub><\/span>Ar\u53cd\u5e94\uff0c\u52a0\u6210\u548c\u6d88\u9664\u4e24\u4e2a\u57fa\u5143\u8fc7\u7a0b\u4ecd\u7136\u5b58\u5728\uff0c\u4e0d\u540c\u7684\u662f\u8fd9\u4e24\u6b65\u5e76\u6ca1\u6709\u660e\u663e\u7684\u5148\u540e\u987a\u5e8f\uff0c\u800c\u662f\u51e0\u4e4e\u540c\u65f6\u53d1\u751f\u3002\u8fd9\u4e00\u7ed3\u8bba\u4e5f\u5f97\u5230\u4e86\u7535\u8377\u5206\u6790\uff08Charge analysis\uff09\u3001\u6838\u72ec\u7acb\u5316\u5b66\u4f4d\u79fb\uff08Nucleus-independent chemical shift, NICS\uff09\u5206\u6790\u4e0e\u81ea\u7136\u952e\u8f68\u9053\uff08Natural bond orbital, NBO\uff09\u5206\u6790\u7684\u8bc1\u5b9e\uff08\u56fe4e\uff09\u3002<\/span><\/p>\n

<\/p>\n

S<\/span>N<\/sub><\/span>Ar\u53cd\u5e94\u4e2d\u534f\u540c\u673a\u7406\u7684\u666e\u904d\u6027<\/span><\/strong><\/p>\n

<\/p>\n

\u8fd1\u5e74\u6765\u7684\u5c11\u91cf\u7814\u7a76\u8868\u660e <\/sup><\/span>[2-3]<\/sup><\/span>\uff0c\u5bf9\u4e8e\u67d0\u4e9b\u7279\u5b9a\u7684\u5e95\u7269\uff0cS<\/span>N<\/sub><\/span>Ar\u53cd\u5e94\u4e5f\u53ef\u4ee5\u534f\u540c\u7684\u65b9\u5f0f\u8fdb\u884c\u3002\u4f46\u66f4\u4ee4\u4eba\u597d\u5947\u7684\u662f\u5728S<\/span>N<\/sub><\/span>Ar\u53cd\u5e94\u4e2d\uff0c\u534f\u540c\u8fc7\u7a0b\u7a76\u7adf\u662f\u7279\u4f8b\uff0c\u8fd8\u662f\u666e\u904d\u73b0\u8c61\u3002\u6b64\u5916\uff0c\u5bf9\u4e8e\u4eba\u4eec\u5e38\u89c1\u7684S<\/span>N<\/sub><\/span>Ar\u53cd\u5e94\u4f53\u7cfb\uff0c\u53c8\u6709\u591a\u5927\u7684\u6982\u7387\u4ee5\u534f\u540c\u673a\u7406\u8fdb\u884c\u3002<\/span><\/p>\n

<\/p>\n

\u4e3a\u4e86\u56de\u7b54\u8fd9\u4e9b\u95ee\u9898\uff0c\u7814\u7a76\u8005\u9009\u53d6\u4e86120\u4e2a\u5e38\u89c1\u7684S<\/span>N<\/sub><\/span>Ar\u53cd\u5e94\uff0c\u8fd9\u4e9b\u53cd\u5e94\u6db5\u76d6\u4e86\u4e0d\u540c\u7684\u82b3\u9999\u4f53\u7cfb\u3001\u4eb2\u6838\u8bd5\u5242\u548c\u79bb\u53bb\u8bd5\u5242\uff0c\u5177\u6709\u666e\u904d\u7684\u4ee3\u8868\u6027\u3002\u8ba1\u7b97\u7ed3\u679c\u663e\u793a\uff0c\u5728\u8fd9120\u4e2a\u53cd\u5e94\u4e2d\uff0c\u4ec5\u670921\u4e2a\u53cd\u5e94\u5b58\u5728\u7a33\u5b9a\u7684Meisenheimer\u4e2d\u95f4\u4f53\u3002\u8be5\u7ed3\u679c\u4e0d\u4ec5\u5411\u4eba\u4eec\u5c55\u793a\u4e86\u534f\u540cS<\/span>N<\/sub><\/span>Ar\u53cd\u5e94\u7684\u666e\u904d\u6027\uff0c\u4e5f\u8fdb\u4e00\u6b65\u9a8c\u8bc1\u4e86\u4e4b\u524d\u7684\u7ed3\u8bba\uff1a\u53ea\u6709\u5728\u975e\u5e38\u7f3a\u7535\u5b50\u7684\u82b3\u9999\u4f53\u7cfb\u3001\u540c\u65f6\u7f3a\u4e4f\u597d\u7684\u79bb\u53bb\u57fa\u56e2\u7684\u60c5\u51b5\u4e0b\uff0c\u4e2d\u95f4\u4f53\u624d\u6709\u53ef\u80fd\u7a33\u5b9a\u5b58\u5728\uff0c\u9664\u6b64\u4e4b\u5916\uff0cS<\/span>N<\/sub><\/span>Ar\u53cd\u5e94\u57fa\u672c\u90fd\u4ee5\u534f\u540c\u65b9\u5f0f\u8fdb\u884c\u3002<\/span><\/p>\n

<\/p>\n

\u66fe\u88d5\u6587\u535a\u58eb\u4e13\u8bbf\u7eaa\u8981<\/span><\/strong><\/span><\/p>\n

<\/p>\n

X-MOL\uff1a<\/span><\/strong><\/p>\n

\u66fe\u88d5\u6587\u535a\u58eb\u60a8\u597d\uff0c\u975e\u5e38\u8363\u5e78\u60a8\u613f\u610f\u63a5\u53d7\u6211\u4eec\u7684\u4e13\u8bbf\u3002<\/span><\/p>\n


<\/span><\/p>\n

\u8fd9\u7bc7\u6587\u7ae0\u4e2d\uff0c\u6211\u4eec\u6ce8\u610f\u5230\u8d35\u56e2\u961f\u65b0\u5f00\u53d1\u768413<\/sup><\/span>C<\/span> KIE\u6d4b\u91cf\u65b9\u6cd5\uff0c\u7075\u654f\u5ea6\u5927\u5927\u63d0\u9ad8\uff0c\u80fd\u5426\u5148\u4ecb\u7ecd\u4e00\u4e0b\u8fd9\u79cd\u65b0\u65b9\u6cd5\uff1f<\/span><\/p>\n

<\/p>\n

\u66fe\u88d5\u6587\u535a\u58eb\uff1a<\/span><\/strong><\/p>\n

\u73b0\u6709\u768413<\/sup><\/span>C<\/span> KIE\u6d4b\u91cf\u65b9\u6cd5\uff08Singleton method\uff09\u4e3b\u8981\u662f\u57fa\u4e8e\u5b9a\u91cf\u78b3\u8c31\u6765\u76f4\u63a5\u83b7\u53d613<\/sup><\/span>C<\/span>\u4fe1\u606f\uff0c\u5c5e\u4e8e\u76f4\u63a5\u6d4b\u91cf\u3002\u7531\u4e8e13<\/sup><\/span>C<\/span>\u7684\u78c1\u65cb\u6bd4\u4e3a\u6c22\u7684\u56db\u5206\u4e4b\u4e00\uff0c\u4e14\u5929\u7136\u4e30\u5ea6\u4ec5\u4e3a1.1%\uff0c\u5bfc\u81f4\u8be5\u65b9\u6cd5\u7075\u654f\u5ea6\u6781\u4f4e\u3002\u4e3a\u4e86\u83b7\u5f97\u53ef\u63a5\u53d7\u7684\u7cbe\u786e\u5ea6\uff0c\u6d4b\u91cf\u5f80\u5f80\u9700\u8981\u51e0\u767e\u6beb\u514b\u6837\u54c1\uff0c\u5e76\u4e14\u6d4b\u91cf\u6570\u5929\uff0c\u8fd9\u5bf9\u4e8e\u9700\u8981\u8d35\u91cd\u539f\u6599\/\u50ac\u5316\u5242\u7684\u53cd\u5e94\u662f\u4e0d\u53ef\u63a5\u53d7\u7684\u3002\u4e0e\u6b64\u540c\u65f6\uff0c\u7531\u4e8e\u6d4b\u91cf\u65f6\u95f4\u592a\u957f\uff0c\u6838\u78c1\u8fd8\u5e38\u5e38\u4f1a\u51fa\u73b0\u4e0d\u7a33\u5b9a\u7684\u60c5\u51b5\uff0c\u5bfc\u81f4\u6211\u4eec\u8981\u91cd\u590d\u6d4b\u91cf\u591a\u6b21\uff0c\u6781\u4e3a\u8d39\u65f6\u3002<\/span><\/p>\n


<\/span><\/p>\n

\u6211\u4eec\u7684\u65b0\u65b9\u6cd5\u5219\u5c5e\u4e8e\u95f4\u63a5\u6d4b\u91cf\u3002\u7b80\u5355\u6765\u8bf4\uff0c\u6211\u4eec\u4e0d\u662f\u6d4b\u91cf13<\/sup><\/span>C<\/span>\uff0c\u800c\u662f\u6d4b\u91cf\u4e0e13<\/sup><\/span>C<\/span>\u76f8\u8fde\u7684F\u7684\u6838\u78c1\u4fe1\u53f7\uff0c\u5e76\u901a\u8fc7\u6bd4\u8f8313<\/sup><\/span>C<\/span>-F\u4fe1\u53f7\u5f3a\u5ea6\u4e0e12<\/sup><\/span>C<\/span>-F\u4fe1\u53f7\u5f3a\u5ea6\u6765\u83b7\u5f9713<\/sup><\/span>C<\/span>\/12<\/sup><\/span>C<\/span>\u6bd4\u4f8b\u3002\u4ec5\u8fd9\u4e00\u70b9\uff0c\u6211\u4eec\u5c31\u53ef\u5c06\u6d4b\u91cf\u7075\u654f\u5ea6\uff08S\/N\uff09\u63d0\u9ad8\uff08\u7406\u8bba\u4e0a\uff0913.6*n\u500d\uff08n\u4e3aF\u539f\u5b50\u4e2a\u6570\uff0c\u4f8b\u5982CF3\u4e2dn\u4e3a3\uff09\u3002\u4e5f\u5c31\u662f\u8bf4\uff0c\u6211\u4eec\u53ef\u4ee5\u5c06\u6837\u54c1\u7528\u91cf\u964d\u4f4e\u5230\u4e4b\u524d\u7684\u201c(13.6*n)\u5206\u4e4b\u4e00\u201d\uff0c\u6216\u628a\u6d4b\u91cf\u65f6\u95f4\u7f29\u77ed\u5230\u4e4b\u524d\u7684\u201c(13.6*n)<\/span>2<\/sup><\/span>\u5206\u4e4b\u4e00\u201d\uff08\u8003\u8651\u5230C\u548cF\u5f1b\u8c6b\u65f6\u95f4\u7684\u4e0d\u540c\uff0c\u6d4b\u91cf\u65f6\u95f4\u8fd8\u53ef\u4ee5\u518d\u51cf\u5c11\u4e09\u5206\u4e4b\u4e8c\uff09\u3002<\/span><\/p>\n


<\/span><\/p>\n

\u4f46\u95ee\u9898\u662f\uff0c13<\/sup><\/span>C<\/span>-F\uff08\u536b\u661f\u5cf0\uff09\u4fe1\u53f7\u592a\u5f31\uff0c\u5f80\u5f80\u88ab\u6df9\u6ca1\u572812<\/sup><\/span>C<\/span>-F\uff08\u4e3b\u5cf0\uff09\u4fe1\u53f7\u4e2d\uff0c\u4ee5\u81f3\u4e8e\u6211\u4eec\u4e0d\u80fd\u83b7\u5f97\u51c6\u786e\u768413<\/sup><\/span>C<\/span>-F\u5cf0\u79ef\u5206\u4fe1\u606f\u3002\u6240\u4ee5\u6211\u4eec\u5f00\u53d1\u4e86\u4e00\u79cd\u591a\u91cf\u5b50\u8fc7\u6ee4\u6280\u672f\uff08Multiple quantum filtered\uff0cMQF\uff09\u6765\u201c\u8fc7\u6ee4\u201d\u638912<\/sup><\/span>C<\/span>-F\u4fe1\u53f7\uff08\u4e3b\u5cf0\uff09\u800c\u4ec5\u5269\u4e0b13<\/sup><\/span>C<\/span>-F\u4fe1\u53f7\uff08\u536b\u661f\u5cf0\uff09\uff0c\u4ee5\u6b64\u5c0613<\/sup><\/span>C<\/span> KIE\u7684\u6d4b\u91cf\u5b9e\u7528\u5316\u3002<\/span><\/p>\n

<\/p>\n

X-MOL\uff1a<\/span><\/strong><\/p>\n

\u5177\u4f53\u5230\u6700\u8fd1\u8fd9\u7bc7\u8bba\u6587\uff0c\u5173\u952eidea\u662f\u5982\u4f55\u4ea7\u751f\u7684\u5462\uff1f<\/span><\/p>\n

<\/p>\n

\u66fe\u88d5\u6587\u535a\u58eb\uff1a<\/span><\/strong><\/p>\n

\u6211\u4eec\u5c0f\u7ec4\u5bf9\u53cd\u5e94\u673a\u7406\u4e00\u76f4\u5f88\u611f\u5174\u8da3\uff0c\u56e0\u4e3a\u673a\u7406\u7814\u7a76\u53ef\u4ee5\u5e2e\u52a9\u6211\u4eec\u66f4\u6df1\u5165\u5730\u7406\u89e3\u548c\u6539\u8fdb\u53cd\u5e94\u3002\u4e4b\u524d\u6211\u4eec\u7528\u7684\u6700\u591a\u7684\u662f\u53cd\u5e94\u8fc7\u7a0b\u52a8\u529b\u5b66\uff08Reaction progress kinetic analysis, RPKA\uff09\u3002\u5f53\u7136\uff0c\u52a8\u529b\u5b66\u662f\u4e00\u79cd\u5f3a\u5927\u7684\u673a\u7406\u7814\u7a76\u5de5\u5177\uff0c\u4f46\u5176\u6700\u5927\u7684\u95ee\u9898\u5728\u4e8e\u4e0d\u80fd\u63d0\u4f9b\u53cd\u5e94\u51b3\u901f\u6b65\uff08Rate determining step, RDS\uff09\u4e4b\u540e\u7684\u4fe1\u606f\u3002\u540c\u4f4d\u7d20\u6548\u5e94\u5219\u53ef\u65e0\u89c6\u51b3\u901f\u6b65\u7684\u5b58\u5728\uff0c\u76f4\u63a5\u7814\u7a76\u6211\u4eec\u611f\u5174\u8da3\u7684\u6210\u952e\u8fc7\u7a0b\u3002\u76f8\u5bf9\u6765\u8bf4\uff0c13<\/sup><\/span>C<\/span> KIE\u9664\u4e86\u66f4\u96be\u6d4b\u91cf\uff0c\u5728\u5176\u5b83\u65b9\u9762\u5bf9H\/D KIE\u90fd\u6709\u7edd\u5bf9\u4f18\u52bf\uff0c\u6240\u4ee5\u6211\u4eec\u51b3\u5b9a\u5148\u5f00\u53d1\u76f8\u5e94\u7684\u6d4b\u91cf\u65b9\u6cd5\u89e3\u51b3\u8fd9\u4e2a\u7814\u7a76\u74f6\u9888\u3002<\/span><\/p>\n

<\/p>\n

X-MOL\uff1a<\/span><\/strong><\/p>\n

\u5728\u5177\u4f53\u5de5\u4f5c\u4e2d\uff0c\u8d35\u56e2\u961f\u4e3a\u4ec0\u4e48\u4f1a\u9009\u62e9\u82b3\u9999\u4eb2\u6838\u53d6\u4ee3\uff08S<\/span>N<\/sub><\/span>Ar\uff09\u53cd\u5e94\u4f5c\u4e3a\u7814\u7a76\u5bf9\u8c61\u5462\uff1f<\/span><\/p>\n

<\/p>\n

\u66fe\u88d5\u6587\u535a\u58eb\uff1a<\/span><\/strong><\/p>\n

\u5176\u5b9e\uff0c\u6211\u4eec\u9047\u5230\u7684\u6700\u5927\u6311\u6218\u5c31\u662f\u5bfb\u627e\u5408\u9002\u7684\u7814\u7a76\u4f53\u7cfb\u3002\u597d\u7684\u7814\u7a76\u5de5\u5177\u5e76\u4e0d\u7b49\u4ef7\u4e8e\u597d\u7684\u7814\u7a76\u7ed3\u679c\uff0c\u9009\u62e9\u8bfe\u9898\u65f6\u6211\u4eec\u5173\u6ce8\u7684\u662f\uff1a\u8bfe\u9898\u672c\u8eab\u662f\u4e0d\u662f\u6709\u610f\u4e49\uff1f\u662f\u4e0d\u662f\u6709\u8da3\uff1f\u80fd\u5426\u5f97\u5230\u7b80\u5355\u6e05\u6670\u7684\u7ed3\u8bba\uff1f\u5728\u8fd9\u91cc\uff0c\u6211\u4eec\u9009\u62e9S<\/span>N<\/sub><\/span>Ar\u53cd\u5e94\u4f5c\u4e3a\u7814\u7a76\u5bf9\u8c61\u5c31\u662f\u8003\u8651\u5230\u5176\u5e94\u7528\u7684\u5e7f\u6cdb\u6027\uff0c\u673a\u7406\u7684\u6709\u8da3\u6027\u3002\u63a5\u4e0b\u6765\uff0c\u4f53\u7cfb\u7684\u9009\u62e9\u4e5f\u975e\u5e38\u5173\u952e\uff0c\u597d\u7684\u7814\u7a76\u4f53\u7cfb\u53ef\u4ee5\u8ba9\u4eba\u4e8b\u534a\u529f\u500d\uff1b\u4e0d\u597d\u7684\u4f53\u7cfb\u4e0d\u4ec5\u8d39\u65f6\u8d39\u529b\uff0c\u8fd8\u5f97\u4e0d\u51fa\u6e05\u6670\u7684\u7ed3\u8bba\u3002\u4f8b\u5982\uff0c\u5728\u8fd9\u4e2a\u7814\u7a76\u4e2d\uff0c\u6211\u4eec\u4ec5\u9009\u53d6\u4e86\u4e09\u4e2a\u4ee3\u8868\u6027\u53cd\u5e94\uff0c\u5374\u5206\u522b\u5bf9\u5e94\u4e86\u4e09\u79cd\u4e0d\u540c\u7684\u673a\u7406\u8def\u5f84\uff0c\u6db5\u76d6\u4e86\u5404\u79cd\u673a\u7406\u53ef\u80fd\u6027\u3002\u6240\u4ee5\uff0c\u6574\u4e2a\u9009\u62e9\u8fc7\u7a0b\u90fd\u9700\u8981\u6211\u4eec\u6765\u56de\u8ba8\u8bba\uff0c\u4ed4\u7ec6\u5730\u63a8\u6572\u3002<\/span><\/p>\n

<\/p>\n

X-MOL\uff1a<\/span><\/strong><\/p>\n

\u8fd9\u4e2a\u5de5\u4f5c\u5bf9\u4e8e\u6574\u4e2a\u9886\u57df\u6709\u53ef\u80fd\u4ea7\u751f\u54ea\u4e9b\u5f71\u54cd\uff1f<\/span><\/p>\n

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\u66fe\u88d5\u6587\u535a\u58eb\uff1a<\/span><\/strong><\/p>\n

\u672c\u5de5\u4f5c\u4e3b\u8981\u6709\u4e24\u90e8\u5206\u3002\u7b2c\u4e00\u90e8\u5206\u662f\u5f00\u53d1\u4e86\u4e00\u79cd\u5728C-F\u8026\u5408\u4f53\u7cfb\u4e2d\u5feb\u901f\u6d4b\u91cf13<\/sup><\/span>C<\/span> KIE\u7684\u65b9\u6cd5\u3002\u7b80\u5355\u5730\u8bf4\uff0c\u53ea\u8981\u539f\u6599\u6216\u4ea7\u7269\u4e2d\u542b\u6709\u6c1f\u539f\u5b50\uff0c\u5c31\u53ef\u4ee5\u7814\u7a76\u4e0e\u4e4b\u76f8\u8fde\u768413<\/sup><\/span>C<\/span> KIE\uff0c\u65e0\u9700\u50cfH\/D KIE\u4e00\u6837\u9884\u5148\u7528\u91cd\u540c\u4f4d\u7d20\u6807\u8bb0\u539f\u6599\u3002\u800c\u4e14\uff0c\u8be5\u65b9\u6cd5\u6837\u54c1\u7528\u91cf\u4f4e\uff08\u53ef\u964d\u81f310 mg\uff09\uff0c\u6570\u636e\u91c7\u96c6\u65f6\u95f4\u77ed\uff0810\u4e2a\u5c0f\u65f6\uff09\uff0c\u751a\u81f3\u53ef\u4ee5\u4f7f\u7528\u672a\u7ecf\u7eaf\u5316\u7684\u53cd\u5e94\u6df7\u5408\u7269\u8fdb\u884c\u6d4b\u91cf\u3002\u53ef\u4ee5\u9884\u89c1\uff0c\u8be5\u65b9\u6cd5\u5c06\u5728\u672a\u6765\u7684\u6c1f\u5316\u5b66\u673a\u7406\u7814\u7a76\u4e2d\u8d77\u91cd\u8981\u4f5c\u7528\u3002\u7b2c\u4e8c\u90e8\u5206\u5219\u662fS<\/span>N<\/sub><\/span>Ar\u53cd\u5e94\u7684\u7814\u7a76\u3002\u901a\u8fc713<\/sup><\/span>C<\/span> KIE\u7814\u7a76\u7ed3\u5408\u9ad8\u7cbe\u5ea6\u7406\u8bba\u8ba1\u7b97\uff0c\u6211\u4eec\u5f97\u4ee5\u63cf\u7ed8\u51fa\u66f4\u4e3a\u5168\u9762\u548c\u6df1\u5165\u7684\u673a\u7406\u753b\u9762\uff0c\u52a0\u6df1\u4e86\u5bf9\u4e8e\u8fd9\u4e2a\u7ecf\u5178\u53cd\u5e94\u7684\u7406\u89e3\u3002\u6211\u4e2a\u4eba\u89c9\u5f97\uff0c\u5982\u679c\u672c\u7814\u7a76\u80fd\u5f15\u53d1\u5927\u5bb6\u5bf9\u5316\u5b66\u754c\u4e00\u4e9b\u66fe\u7ecf\u5949\u4e3a\u572d\u81ec\u7684\u89c2\u70b9\u7684\u91cd\u65b0\u601d\u8003\uff0c\u90a3\u4e5f\u662f\u975e\u5e38\u6709\u610f\u4e49\u7684\u3002<\/span><\/p>\n

<\/p>\n

\u539f\u6587\uff08\u626b\u63cf\u6216\u957f\u6309\u4e8c\u7ef4\u7801\uff0c\u8bc6\u522b\u540e\u76f4\u8fbe\u539f\u6587\u9875\u9762\uff09\uff1a<\/span><\/p>\n

\"\u98a0\u8986\u6559\u79d1\u4e66\u7684\u53d1\u73b0\uff1a13C<\/p>\n

Concerted nucleophilic aromatic substitutions<\/span><\/p>\n

Nat. Chem<\/span><\/em>., 2018<\/strong>, DOI: 10.1038\/s41557-018-0079-7<\/span><\/p>\n


<\/span><\/p>\n

\u5bfc\u5e08\u4ecb\u7ecd<\/span><\/p>\n

Eric Jacobsen<\/span><\/p>\n

http:\/\/www.x-mol.com\/university\/faculty\/26725<\/span><\/p>\n

<\/p>\n

\u53c2\u8003\u8d44\u6599\uff1a<\/span><\/p>\n

1. Analysis of past and present synthetic methodologies on medicinal chemistry: where have all the new reactions gone? J. Med. Chem<\/em>., 2016<\/strong>, 59<\/em>, 4443-4458.<\/span><\/p>\n

2. A single transition state in nucleophilic aromatic substitution: reaction of phenolate ions with 2-(49nitrophenoxy)-4,6-dimethoxy-1,3,5-triazine in aqueous solution. J. Chem. Soc. Perkin Trans<\/em>., 1993<\/strong>, 2<\/em>, 1703-1704.<\/span><\/p>\n

3. Concerted nucleophilic aromatic substitution with <\/span>19<\/sup><\/span>F<\/span>–<\/sup><\/span> and 18<\/sup><\/span>F<\/span>–<\/sup><\/span> <\/span>. Nature, <\/em>2016<\/strong>, 534<\/strong>, 369-373.<\/span><\/p>\n

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\"\u98a0\u8986\u6559\u79d1\u4e66\u7684\u53d1\u73b0\uff1a13C<\/p>\n<\/section>\n<\/section>\n<\/section>\n<\/section>\n

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\"\u98a0\u8986\u6559\u79d1\u4e66\u7684\u53d1\u73b0\uff1a13C<\/p>\n

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\u672c\u6587\u7248\u6743\u5c5e\u4e8eX-MOL<\/strong><\/span>\uff08x-mol.com\uff09\uff0c\u672a\u7ecf\u8bb8\u53ef\u8c22\u7edd\u8f6c\u8f7d\uff01\u6b22\u8fce\u8bfb\u8005\u670b\u53cb\u4eec\u5206\u4eab\u5230\u670b\u53cb\u5708or\u5fae\u535a\uff01<\/span><\/p>\n


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\u957f\u6309<\/strong><\/span>\u4e0b\u56fe\u8bc6\u522b\u56fe\u4e2d\u4e8c\u7ef4\u7801<\/strong>\uff0c\u8f7b\u677e\u5173\u6ce8\u6211\u4eec\uff01<\/span><\/p>\n<\/section>\n<\/section>\n<\/section>\n

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<\/span>\"\u98a0\u8986\u6559\u79d1\u4e66\u7684\u53d1\u73b0\uff1a13C<\/p>\n

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\u59cb\u53d1\u4e8e\u5fae\u4fe1\u516c\u4f17\u53f7\uff1a X\u4e00MOL\u8d44\u8baf <\/p>\n<\/blockquote>\n<\/div>\n","protected":false},"excerpt":{"rendered":"

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