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首页> 外文期刊>Journal of Physical Organic Chemistry >Formylation of activated arenes by phenyl formate: implications for the mechanism of the Fries rearrangement oef aryl formates
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Formylation of activated arenes by phenyl formate: implications for the mechanism of the Fries rearrangement oef aryl formates

机译：甲酸苯酯对活化的芳烃的甲酰化：对弗里斯重排芳基甲酸酯的机理的影响

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摘要

We present an NMR and DFT investigation of the reaction of phenyl formate with 3-methoxyphenol and 3,5-dimethoxyphenol with excess BCl3. The products obtained (3-methoxy- and 3,5-dimethoxy-salicylaidehyde, respectively) are the same as those resulting from the Fries rearrangement of 3-methoxy- and 3,5-dimethoxy-phenyl formate. These results represent a novel regioselective synthetic route to aromatic aldehydes, using phenyl formate as a source of formylating agent. They also unambiguously prove that the Fries rearrangement of aryl formates (that we recently investigated in J. Org. Chem. 71, 9331-9340, 2006) is intermolecular: the intermediate formyl chloride is released in situ and, in turn, it formylates the intermediate dichloroborate ester of 3-methoxy- and 3,5-dimethoxy-phenol in a second independent step. The - BCl2 moiety bound to the aryl oxygen of the substituted phenol interacts with the formyl chloride strongly favouring the ortho substitution.
机译：我们提出了NMR和DFT研究甲酸苯酯与3-甲氧基苯酚和3,5-二甲氧基苯酚与过量BCl3的反应。所得产物（分别为3-甲氧基-和3,5-二甲氧基-水杨醛）与由3-甲氧基-和3,5-二甲氧基-苯基甲酸酯的弗里斯重排得到的产物相同。这些结果代表了使用甲酸苯酯作为甲酰化剂的来源的一种新的选择性合成芳香族醛的方法。他们还明确证明芳基甲酸酯的弗里斯重排（我们最近在J. Org。Chem。71，9331-9340，2006中进行了研究）是分子间的：中间体甲酰氯在原位释放，然后将甲酰氯甲酰化。在第二独立步骤中，得到3-甲氧基-和3，5-二甲氧基-苯酚的中间体二氯硼酸酯。结合到取代苯酚的芳基氧上的-BCl2部分与甲酰氯相互作用，强烈促进邻位取代。

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