Synthesis of Amides and Amidines by Reaction of Carboxylic Acids and Amines in the Presence of Polyphophoric Acid Trimethylsilyl Ester (PPSE)
Synthesis of Amides and Amidines by Reaction of Carboxylic Acids and Amines in the Presence of Polyphophoric Acid Trimethylsilyl Ester (PPSE)
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DOI：
10.1246/bcsj.59.2171
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发表时间：
1986-07
影响因子：
4
通讯作者：
S. Ogata;A. Mochizuki;M. Kakimoto;Y. Imai
中科院分区：
文献类型：
--
作者：
S. Ogata;A. Mochizuki;M. Kakimoto;Y. Imai
从合成酰胺和酰胺的角度出发，研究了在聚磷酸三甲基硅酯(PPSE)存在下，胺与羧酸的反应。在PPSE和吡啶存在下，苯甲酸和苯胺在100℃下选择性地合成了苯甲胺，而在没有吡啶的情况下得到了苯甲胺和N，N‘-二苯基苯甲胺的混合物。在160℃下反应几乎完全生成N，N‘-二苯基苯甲胺。通过在160℃下与四个摩尔量的PPSE简单地加热，从羧酸和芳香胺的组合中高产率地获得了各种对称的胺。在相同条件下，脂肪胺和芳香胺与N-单取代和N，N-二取代酰胺反应也得到相应的不对称酰胺。对反应机理进行了较为详细的讨论。
The reaction between amines and carboxylic aicds in the presence of polyphosphoric acid trimethylsilyl ester (PPSE) has been investigated from the view point of the synthesis of amides and amidines. Benzanilide was selectively prepared from benzoic acid and aniline in the presence of PPSE and pyridine at 100 °C, whereas a mixture of benzanilide and N,N′-diphenylbenzamidine was obtained without the use of pyridine. The reaction at 160 °C almost exclusively gave N,N′-diphenylbenzamidine. Various symmetrical amidines were obtained from combinations of carboxylic acids and aromatic amines in high yields by simply heating at 160 °C with four molar amounts of PPSE. The reactions of aliphatic and aromatic amines with N-monosubstituted and N,N-disubstituted amides also afforded corresponding unsymmetrical amidines under the same conditions. The reaction mechanism is discussed in some detail.