{"id":15837,"date":"2017-10-19T06:08:11","date_gmt":"2017-10-18T22:08:11","guid":{"rendered":"\/\/www.gsbet888.com\/?p=15837"},"modified":"2019-08-02T18:52:41","modified_gmt":"2019-08-02T10:52:41","slug":"zweifel-%e7%83%af%e5%9f%ba%e5%8c%96","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/reactions\/2017\/10\/zweifel-%e7%83%af%e5%9f%ba%e5%8c%96.html","title":{"rendered":"Zweifel \u70ef\u57fa\u5316"},"content":{"rendered":"
Zweifel \u70ef\u57fa\u5316\u662f\u5728\u78b1\u6027\u6761\u4ef6\u4e0b\uff0c\u70ef\u57fa\u787c\u9178\u916f\u6216\u70ef\u57fa\u787c\u70f7\u4e0e\u7898\u4f5c\u7528\u5f62\u6210\u70ef\u70c3\u7684\u53cd\u5e94\u3002\u8be5\u53cd\u5e94\u57281967\u5e74\u7531\u7f8e\u56fdCalifornia\u5927\u5b66(Unicersity of California)\u7684G. Zweifel\u8bfe\u9898\u7ec4\u9996\u6b21\u62a5\u9053\uff0c\u53cd\u5e94\u5177\u6709\u9ad8\u5ea6\u7684\u7acb\u4f53\u9009\u62e9\u6027\uff0c\u4e3b\u8981\u751f\u6210(Z)-\u70ef\u70c3[1]<\/sup>\u3002\uff08\u5c01\u9762\u56fe\uff09<\/p>\n <\/p>\n \u4e4b\u540e\uff0c\u8be5\u8bfe\u9898\u7ec4\u5728\u65e0\u78b1\u5b58\u5728\u7684\u6761\u4ef6\u4e0b\uff0c\u91c7\u7528\u6eb4\u5316\u6c30\u8fdb\u884c\u53cd\u5e94\uff0c\u4ee5\u9ad8\u5ea6\u7acb\u4f53\u9009\u62e9\u6027\u7684\u65b9\u5f0f\u83b7\u5f97(E)-\u70ef\u70c3[2]<\/sup>\u3002\u540c\u65f6\uff0c\u7814\u7a76\u53d1\u73b0\u91c7\u7528\u624b\u6027\u787c\u70f7\u65f6\uff0c\u8be5\u53cd\u5e94\u540c\u6837\u5177\u6709\u9ad8\u5ea6\u7684\u7acb\u4f53\u4e13\u4e00\u6027[3]<\/sup>\u3002<\/p>\n 1973\u5e74\uff0cH. C. Brown\u5c06\u8be5\u53cd\u5e94\u6761\u4ef6\u5e94\u7528\u4e8e\u7094\u70c3\u7684\u5408\u6210[4]<\/sup>\u3002<\/p>\n \u7136\u800c\uff0c\u5728\u53cd\u5e94\u7ed3\u675f\u540e\uff0c\u70ef\u57fa\u787c\u70f7\u7684\u4e24\u4e2a\u70f7\u57fa\u4e2d\uff0c\u53ea\u6709\u4e00\u4e2a\u70f7\u57fa\u80fd\u591f\u8fdb\u5165\u70ef\u70c3\u4ea7\u7269\u4e2d\uff0c\u7531\u6b64\u9020\u6210\u787c\u70f7\u7684\u6d6a\u8d39(\u5c24\u5176\u5bf9\u4e8e\u4e00\u4e9b\u96be\u4ee5\u5408\u6210\u4e14\u4ef7\u683c\u6602\u8d35\u7684\u787c\u70f7)\uff0c\u6709\u65f6\u8fd8\u5b58\u5728\u4e0d\u540c\u70f7\u57fa\u95f4\u7684\u7ade\u4e89\u6027\u8fc1\u79fb\u95ee\u9898\uff0c\u4ece\u800c\u964d\u4f4e\u70ef\u70c3\u7684\u4ea7\u7387\u4e0e\u53cd\u5e94\u7684\u533a\u57df\u9009\u62e9\u6027\u3002\u4e3a\u89e3\u51b3\u8fd9\u4e00\u95ee\u9898\uff0cZweifel\u91c7\u7528\u4e09\u7532\u80fa\u6c27\u5316\u7269\u5c06\u800c\u4e59\u70ef\u57fa\u787c\u70f7\u6c27\u5316\u4e3a\u787c\u9178\u916f(\u5728\u7a7a\u6c14\u4e2d\u8f83\u4e3a\u7a33\u5b9a)\uff0c\u968f\u540e\u8fdb\u884c\u4e0b\u4e00\u6b65\u7684\u70ef\u57fa\u5316\u53cd\u5e94\uff0c\u6210\u529f\u5730\u89e3\u51b3\u4e86\u4e4b\u524d\u91c7\u7528\u5177\u6709\u4f4e\u8fc1\u79fb\u6027\u80fd\u7684\u70f7\u57fa\u53d6\u4ee3\u7684\u70ef\u57fa\u787c\u70f7\u65f6\u51fa\u73b0\u7684\u7ade\u4e89\u6027\u8fc1\u79fb(\u70f7\u6c27\u57fa\u7684\u8fc1\u79fb\u80fd\u529b\u8f83\u4f4e)\u53ca\u787c\u70f7\u5229\u7528\u7387\u4f4e\u7684\u95ee\u9898[5]<\/sup>\u3002<\/p>\n 1976\u5e74\uff0cEvans\u4e0eMattesson \u91c7\u7528\u6709\u673a\u9502\u8bd5\u5242\u4e0e\u787c\u9178\u916f\u5f62\u6210\u7684\u9178\u6839\u914d\u5408\u7269\uff0c\u5c06\u787c\u9178\u916f\u7684\u5e95\u7269\u8303\u56f4\u6269\u5c55\u81f3\u70ef\u57fa\u787c\u9178\u916f\u4e0e\u4e8c\u7ea7\u70f7\u57fa\u787c\u9178\u916f[6]-[8]<\/sup>\u3002<\/p>\n <\/p>\n 2016\u5e74\uff0cAggarwal\u7814\u7a76\u7ec4\u91c7\u7528\u7c7b\u4f3c\u6761\u4ef6\uff0c\u5c06\u787c\u9178\u916f\u7684\u5e94\u7528\u8303\u56f4\u8fdb\u4e00\u6b65\u6269\u5c55\u81f3\u5177\u6709\u6742\u539f\u5b50\u7684\u70ef\u57fa\u787c\u9178\u916f\uff0c\u540c\u65f6\uff0c\u4f7f\u8be5\u53cd\u5e94\u5177\u6709\u9ad8\u5ea6\u7684\u5bf9\u6620\u4e13\u4e00\u6027[9]<\/sup>\u3002<\/p>\n 2017\u5e74\uff0cAggarwal\u91c7\u7528\u787c\u9178\u916f\u4e0eGrignard\u8bd5\u5242\u5f62\u6210\u7684\u9178\u6839\u914d\u5408\u7269\uff0c\u5c06\u787c\u9178\u916f\u7684\u5e94\u7528\u8303\u56f4\u6709\u6548\u5730\u6269\u5c55\u81f3\u4e00\u7ea7\u3001\u4e8c\u7ea7\u3001\u4e09\u7ea7\u70f7\u57fa\u787c\u9178\u916f\u53ca\u82b3\u57fa\u787c\u9178\u916f\uff0c\u540c\u65f6\uff0c\u5c06\u8be5\u53cd\u5e94\u6210\u529f\u5e94\u7528\u4e8e\u5927\u4f4d\u963b\u70ef\u70c3\u7684\u5408\u6210[10]- [13]<\/sup>\u3002<\/p>\n Zweifel \u70ef\u57fa\u5316\u53cd\u5e94\u4e3aSuzuki-Miyaura\u53cd\u5e94\u7684\u5f3a\u6709\u529b\u7684\u8865\u5145[14]<\/sup>\uff0c\u53cd\u5e94\u65e0\u9700\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u5242\u53c2\u4e0e\uff0c\u80fd\u591f\u4ee5\u9ad8\u5ea6\u5bf9\u6620\u4e13\u4e00\u6027\u7684\u65b9\u5f0f\u5b9e\u73b0\u5149\u5b66\u7eaf\u5ea6\u7684\u4e8c\u7ea7\u3001\u4e09\u7ea7\u70f7\u57fa\u787c\u9178\u916f\u4e0e\u70ef\u57fa\u91d1\u5c5e\u5316\u5408\u7269\u4e4b\u95f4\u7684\u5076\u8054\u53cd\u5e94\u3002<\/p>\n (+)-faranal\u7684\u5168\u5408\u6210[1]\n (-)-stemaphylline\u7684\u5168\u5408\u6210[2]\n (Z<\/em>)-<\/strong>\u70ef\u70c3\u7684\u5408\u6210<\/strong>:<\/strong> \u5728-10o<\/sup>C\u4e0b\uff0c\u5411\u539f\u4f4d\u5236\u5907\u7684\u70ef\u57fa\u787c\u70f7(1 eq.)\u4e2d\u52a0\u51656 M NaOH(3.6 eq.)\u6eb6\u6db2\uff0c\u968f\u540e\u7528\u6052\u538b\u6ef4\u6db2\u6f0f\u6597\u5411\u4e0a\u8ff0\u53cd\u5e94\u6df7\u5408\u7269\u4e2d\u7f13\u6162\u6ef4\u52a0\u7898(1.3 eq.)\u7684\u56db\u6c22\u544b\u5583\u6eb6\u6db2(2.5 M, \u8d85\u8fc715 min\u6ef4\u52a0\u5b8c\u6bd5)\u3002\u518d\u5c06\u4e0a\u8ff0\u53cd\u5e94\u6db2\u5347\u81f3\u5ba4\u6e29\uff0c\u76f4\u81f3\u53cd\u5e94\u5b8c\u6210\u3002\u53cd\u5e94\u7ed3\u675f\u540e\uff0c\u7528\u786b\u4ee3\u786b\u9178\u94a0\u6eb6\u6db2\u9664\u53bb\u8fc7\u91cf\u7684\u7898\uff0c\u518d\u5c06\u4e0a\u8ff0\u53cd\u5e94\u6df7\u5408\u7269\u7528\u620a\u70f7\u8fdb\u884c\u8403\u53d6\uff0c\u5408\u5e76\u7684\u6709\u673a\u76f8\u91c7\u7528\u65e0\u6c34\u786b\u9178\u94a0\u8fdb\u884c\u5e72\u71e5\u3002\u84b8\u998f\u7eaf\u5316\u540e\uff0c\u83b7\u5f97\u76f8\u5e94\u76ee\u6807\u4ea7\u7269\u3002<\/p>\n (E<\/em>)-<\/strong>\u70ef\u70c3\u7684\u5408\u6210<\/strong>: <\/strong>\u2460 \u70ef\u57fa\u787c\u70f7\u7684\u539f\u4f4d\u5408\u6210:<\/strong>\u5728THF\u4e2d\u52a0\u5165\u70ef\u70c3(2 eq.)\u4e0eBH3<\/sub> (1.1 eq.)\uff0c\u518d\u5c06\u4e0a\u8ff0\u6eb6\u6db2\u4e2d\u52a0\u5165\u7094\u70c3(1 eq.)\u7684THF\u6eb6\u6db2(2.5 M), \u5e76\u7ef4\u6301\u53cd\u5e94\u6db2\u6e29\u5ea6\u57280-5o<\/sup>C\u4e4b\u95f4\u3002\u4e4b\u540e\u5c06\u4e0a\u8ff0\u53cd\u5e94\u6df7\u5408\u7269\u5347\u81f3\u5ba4\u6e29\uff0c\u5e76\u5728\u5ba4\u6e29\u4e0b\u6405\u62cc30min\u3002\u2461\u70ef\u57fa\u5316:<\/strong>\u57280o<\/sup>C\u4e0b\u51cf\u538b\u9664\u53bb\u70ef\u57fa\u787c\u70f7\u4e2d\u7684THF\u6eb6\u5242\uff0c\u5e76\u7ef4\u63010o<\/sup>C\uff0c\u540c\u65f6\u52a0\u5165\u4e8c\u6c2f\u7532\u70f7\u53ca\u6eb4\u5316\u6c30(1.3 eq.)\u7684\u4e8c\u6c2f\u7532\u70f7(0.83 M)\u6eb6\u6db2\uff0c\u4e4b\u540e\u7ee7\u7eed\u7ef4\u63010o<\/sup>C\uff0c\u5c06\u4e0a\u8ff0\u53cd\u5e94\u6db2\u6405\u62cc2 h\uff0c2 h\u540e\uff0c\u52a0\u51656M NaOH\u6eb6\u6db2\uff0c\u5c06\u53cd\u5e94\u6df7\u5408\u7269\u8fdb\u884c\u7a00\u91ca\u3002\u70ef\u70c3\u4ea7\u7269\u91c7\u7528\u620a\u70f7\u8fdb\u884c\u8403\u53d6\uff0c\u7c97\u4ea7\u7269\u901a\u8fc7\u77edVigreux\u5206\u998f\u67f1\u8fdb\u884c\u5206\u998f\u7eaf\u5316\uff0c\u83b7\u5f97\u76f8\u5e94\u76ee\u6807\u4ea7\u7269\u3002<\/p>\n \u5b9e\u9a8c\u5b9e\u9a8c\u5b89\u5168\u987b\u77e5<\/strong><\/span><\/p>\n \u5c0f\u7f16\u90d1\u91cd\u63d0\u793a\uff1a\u6eb4\u5316\u6c30\u6709\u5267\u6bd2\uff0c\u53cd\u5e94\u7ed3\u675f\u540e\uff0c\u52a0\u78b1\u7a00\u91ca\u83b7\u5f97<\/strong>(E)-<\/strong>\u70ef\u70c3\u7684\u8fc7\u7a0b\u4e2d\uff0c\u4f1a\u4ea7\u751f\u5267\u6bd2\u7684\u6c30\u5316\u7269\u3002\u53cd\u5e94\u9700\u8981\u5728\u901a\u98ce\u6548\u679c\u6781\u4e3a\u4f18\u826f\u7684\u901a\u98ce\u6a71\u5185\u5c0f\u5fc3\u64cd\u4f5c\u3002\u53cd\u5e94\u540e\u5904\u7406\u8fc7\u7a0b\u4ea7\u751f\u7684\u5e9f\u6db2\u53ca\u4f7f\u7528\u8fc7\u7684\u73bb\u7483\u5668\u76bf\u5747\u9700\u8981\u91c7\u7528\u9971\u548c\u6b21\u6c2f\u9178\u94a0\u6eb6\u6db2\u8fdb\u884c\u65e0\u5bb3\u5316\u5904\u7406<\/strong>(<\/strong>\u52a0\u5165\u78b1\u5c06<\/strong>pH<\/strong>\u8c03\u81f3<\/strong>11<\/strong>\uff0c\u52a0\u5165\u6b21\u6c2f\u9178\u94a0\u9971\u548c\u5f7b\u5e95\u6405\u62cc\u540e\uff0c\u9759\u7f6e\u8fc7\u591c\u3002<\/strong>1mol<\/strong>\u7684\u6c30\u5316\u7269\u9700\u8981\u52a0\u5165<\/strong>500mL NaOCl<\/strong>\u9971\u548c\u6eb6\u6db2<\/strong>)<\/strong>\uff0c\u5e76\u7528\u6c30\u6839\u8bd5\u7eb8\u68c0\u6d4b\u81f3\u6c30\u79bb\u5b50\u542b\u91cf<\/strong>(<\/strong>\u5c0f\u4e8e<\/strong>10-4<\/sup> M)<\/strong>\u5408\u683c\u540e\uff0c\u624d\u53ef\u5012\u5165\u6307\u5b9a\u5e9f\u6db2\u7f38\u3002\u6c30\u5316\u7269\u7684\u5904\u7406\u8fc7\u7a0b\u540c\u6837\u9700\u8981\u5728\u901a\u98ce\u6548\u679c\u6781\u4e3a\u4f18\u826f\u7684\u901a\u98ce\u6a71\u5185\u4ed4\u7ec6\u64cd\u4f5c\u3002<\/strong><\/p>\n <\/p>\n <\/p>\n \u672c\u6587\u7248\u6743\u5c5e\u4e8e Chem-Station\u5316\u5b66\u7a7a\u95f4\uff0c \u6b22\u8fce\u70b9\u51fb\u6309\u94ae\u5206\u4eab\uff0c\u672a\u7ecf\u8bb8\u53ef\uff0c\u8c22\u7edd\u8f6c\u8f7d\uff01 <\/p>\n","protected":false},"excerpt":{"rendered":"\u6982\u8981 Zweifel \u70ef\u57fa\u5316\u662f\u5728\u78b1\u6027\u6761\u4ef6\u4e0b\uff0c\u70ef\u57fa\u787c\u9178\u916f\u6216\u70ef\u57fa\u787c\u70f7\u4e0e\u7898\u4f5c\u7528\u5f62\u6210\u70ef\u70c3\u7684\u53cd\u5e94\u3002\u8be5\u53cd\u5e94\u57281967\u5e74\u7531\u7f8e\u56fdCalifornia\u5927\u5b66(Unicersity of California)\u7684G. Zweifel\u8bfe\u9898\u7ec4\u9996\u6b21\u62a5\u9053\uff0c\u53cd\u5e94\u5177\u6709\u9ad8\u5ea6\u7684\u7acb\u4f53\u9009\u62e9\u6027\uff0c\u4e3b\u8981\u751f\u6210(Z)-\u70ef\u70c3[1]\u3002\uff08\u5c01\u9762\u56fe\uff09 \u4e4b\u540e\uff0c\u8be5\u8bfe\u9898\u7ec4\u5728\u65e0\u78b1\u5b58\u5728\u7684\u6761\u4ef6\u4e0b\uff0c\u91c7\u7528\u6eb4\u5316\u6c30\u8fdb\u884c\u53cd\u5e94\uff0c\u4ee5\u9ad8\u5ea6\u7acb\u4f53\u9009\u62e9\u6027\u7684\u65b9\u5f0f\u83b7\u5f97(E)-\u70ef\u70c3[2]\u3002\u540c\u65f6\uff0c\u7814\u7a76\u53d1\u73b0\u91c7\u7528\u624b\u6027\u787c\u70f7\u65f6\uff0c\u8be5\u53cd\u5e94\u540c\u6837\u5177\u6709\u9ad8\u5ea6\u7684\u7acb\u4f53\u4e13\u4e00\u6027[3]\u3002 1973\u5e74\uff0cH. C. 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Zweifel, H. Arzoumanian, C. C. Whitney, J. Am. Chem. Soc.1967, 89, 3652. doi: 10.1021\/ja00990a061. [2] G. Zweifel, R. P. Fisher, J. T. Snow, C. C.Whitney, J. Am. Chem.\u00a0Soc. 1971, 93, 6309. doi: 10.1021\/ja00752a075. [3] G. Zweifel, R. P. Fisher, J. T. Snow, C. C. Whitney, J. Am. Chem.\u00a0Soc. 1972, 94, 6560. doi: 10.1021\/ja00773a059. [4] A. Suzuki, N. Miyaura, S. Abiko, M. Itoh, H. C. Brown, J. A. Sinclair,\u00a0M.M. Midland, J. Am. Chem. Soc. 1973, 95, 3080. doi: 10.1021\/ja00790a092. [5] G. Zweifel, N. L. Polston, C. C. 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