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In contrast we have found that a wide variety of allylic trichloroacetamidates, which are easily prepared in nearly quantitative yield from the corresponding alcohol and trichlorIn contrast we have found that a wide variety of allylic trichloroacetamidates,which are easily prepared in nearly quantitative yield from the corresponding alcohol and trichloroacetonitrile, readily undergo thermal rearrangement within a few hours in refluxing m-xylene to afford the corresponding trichloroacetamides in isolated yields in excess of 80 In no case has the trichloroacetamide with an unrearranged carbon skeleton been detected. This transformation is formulated as a simple electrocyclic reaction on the basis of its stereo- and regiospecificity which is similar to that observed in related [3,3]-sigmatropic processes. 2,8 For example, the trichloroacetimidate of 1-hepten-3-01 affords 2-heptenyltrichloroacetamide with a trans to cis ratio of at least 98:2.acetonitrile,~ readily undergo thermal rearrangement within a few hours in refluxing m-xylene to afford the corresponding trichloroacetamides in isolated yields in excess of 80 In no case has the trichloroacetamide with an unrearranged carbon skeleton been detected. This transformation is formulated as a simple electrocyclic reaction on the basis of its stereo- and regiospecificity which is similar to that observed in related [3,3]-sigmatropic processes. 2,8 For example, the trichloroacetimidate of 1-hepten-3-01 affords 2-heptenyltrichloroacetamide with a trans to cis ratio of at least 98:2. |
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- ×¢²á: 2011-11-02
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°®ÓëÓêÏÂ(½ð±Ò+1): 2011-12-04 09:59:53
sltmac(½ð±Ò+10): 2011-12-14 12:38:48
185012831(½ð±Ò+40, ·ÒëEPI+1): ·ÒëµÄºÜºÃ£¬²»¹ýÓÐЩ¹À¼ÆÊÇÄúûѧÓлú»¯Ñ§µÄÔÒò£¬²»ÊǺÜͨ˳°¡¡£¡£ 2011-12-03 14:48:00
°®ÓëÓêÏÂ(½ð±Ò+1): 2011-12-04 09:59:53
sltmac(½ð±Ò+10): 2011-12-14 12:38:48
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