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185012831

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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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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 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.
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¡£
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