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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. |
金蟲 (正式寫手)
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樓主也整理下再求助呀 有很多重復(fù)內(nèi)容呀 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。 對比我們發(fā)現(xiàn)的多種烯丙基trichloroacetamidate(三氯乙酰胺),他能從相應(yīng)的酒精和三氯乙氰中容易制備得到,在回流的間二甲苯中幾個小時內(nèi)容易受到熱重組影響,從而使得三氯乙酰胺的產(chǎn)量超過80%。 經(jīng)過檢測三氯乙酰胺的碳骨架無論如何都不會產(chǎn)生重排。這種轉(zhuǎn)變是一種基于其實體和區(qū)域特異性的簡單的電環(huán)化反應(yīng),這與已觀察到的單鍵轉(zhuǎn)移現(xiàn)象相似。 例如,1-hepten-3-1的三氯乙酰胺為2-heptenyltrichloroacetamide (庚烯基三氯乙酰胺)提供反順比至少98:2的乙腈,使其在回流的間二甲苯中幾個小時內(nèi)容易受到熱重組影響,從而使得三氯乙酰胺的產(chǎn)量超過80% |
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