PREPARATION OF ALPHA-NITROKETONES - C-ACYLATION OF PRIMARY NITROPARAFFINS
PREPARATION OF ALPHA-NITROKETONES - C-ACYLATION OF PRIMARY NITROPARAFFINS
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DOI：
10.1021/ja01527a031
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发表时间：
1959-01-01
影响因子：
15
通讯作者：
HOKAMA, T
中科院分区：
文献类型：
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作者：
BACHMAN, GB;HOKAMA, T
自从最初发现硝化烷烃以来，它们引起了相当大的理论兴趣，因为它们对应的阴离子具有两面性，这使得取代反应可以发生在硝基的氧上或硝基上的碳上。许多工作人员研究了在不同条件下，硝化烷烃在不同条件下用酸盐、3酸酐、4酮、3E-5酰基吡啶6和酸酯7进行的酰化反应。在所有的例子中，除了一例外，最初的O-酰化完全发生，随后从初级硝基烷烃生成酰化异羟肟酸的硝酸酐发生后排反应。最近提出了这些烷烃和二次硝基重排生成亚硝基酰氧基化合物的合理反应顺序。8唯一的酸衍生物C-酰化反应是Gabriel4a在1903年报道的，当时他在乙醚中由邻苯二甲酸酐和亚硝酸钠反应得到的2-(硝基乙酰基)-苯甲酸的产率很低且不一致。另一种例外情况是从羰基化合物中获得了-硝基酮-
The nitroparaffins have attracted considerable, theoretical interest since their initial discovery because of the ambivalency of their corresponding anions whichpermits substitution reactions to occur either at the oxygen of thenitro group or at the carbon attached to the nitro group. Numerous workers have investigated the acylation of nitroparaffins using acidhalides, 3 acid anhydrides, 4 ketene, 3e-5 acylpyridinium chlorides6 and acid es-ters7 under a variety of conditions. In all but one case, initial O-acylation was observed to occur exclusively with subsequent rear-rangement of the nitronic anhydrides formed to acylated hydroxamic acids from primary nitro-paraffins. A logical sequence of reactionsfor these paraffins and to nitroso acyloxy compounds from secondary nitro rearrangements has recently been proposed. 8 The only case of C-acylation by an acid derivative was that reported by Gabriel4a in 1903 when he obtained poor and inconsistent yields of 2-(nitroacetyl)-benzoic acid from the reaction of phthalic anhydride withsodium methanenitronate in ether. Another exceptional case in which an-nitroketone was obtained from a carbonyl com-