有机化学 ›› 2008, Vol. 28 ›› Issue (03): 449-453. 上一篇    下一篇

研究论文

2-酰胺-6-乙酰基吡啶类化合物的微波合成及其晶体结构

苏碧云,赵建社*, 赵鹏   

  1. (西北大学化学系 陕西省物理无机化学重点实验室 西安 710069)
  • 收稿日期:2006-08-22 修回日期:2007-09-19 发布日期:2008-03-18
  • 通讯作者: 赵建社

Microwave Irradiation Synthesis and the Crystal Structure of 6-Acetylpyridine-2-carboxamides

SU Bi-Yun,ZHAO Jian-She*,ZHAO Peng   

  1. (Shaanxi Key Laboratory of Physico-inorganic Chemistry, Department of Chemistry, Northwest Univer-sity, Xi'an 710069)
  • Received:2006-08-22 Revised:2007-09-19 Published:2008-03-18
  • Contact: ZHAO Jian-She*,

2,6-二甲基吡啶经氧化、酯化、Claisen酯缩合后制得新型化合物2-乙酯基-6-乙酰基吡啶(4), 用其作为前驱体, 与一系列小分子脂肪胺: 甲胺、乙胺、乙二胺在微波条件下生成3个吡啶酰胺化合物5, 6, 7. 通过元素分析, 1H NMR, IR和MS对这些化合物进行了表征. 对6-乙酰基-N-甲基吡啶-2-甲酰胺(5)的X射线晶体衍射研究表明: 其属于正交晶系, Pca2(1)空间群, 晶胞参数a=2.2784(2) nm, b=0.4350(4) nm, c=0.9267(3) nm; αβγ=90°; Dc=1.288 Mg•m-3, V=0.91856(14) nm3. 实验还发现: 2-乙酯基-6-乙酰基吡啶与脂肪胺及芳香胺缩合时会发生两类不同的反应, 小分子脂肪胺选择与酯基发生胺解反应, 而芳香胺则率先在乙酰基上发生席夫碱缩合. 对这两类有趣的反应机理进行了深入探讨.

关键词: 晶体结构, 2-乙酯基-6-乙酰基吡啶, 席夫碱缩合, 小分子脂肪胺, 芳香胺, 胺解反应

A new unsymmetric compound 2-carbethoxy-6-acetylpyridine (4) was synthesized from the starting material 2,6-dimethylpyridine through four reaction steps, and then a series of 6-acetylpyridine-2-carboxamides 57 were prepared by the microwave irradiation from the precursor 4. These compounds have been determined by the elemental analysis, 1H NMR, IR and MS spectra. The single crystal X-ray study of 6-acetyl-N-methylpyridine-2-carboxamide (5) indicates that 5 belongs to or-thorhombic system, Pca2(1) space group, with a=2.2784(2) nm, b=0.4350(4) nm, c=0.9267(3) nm, αβγ=90°; Dc=1.288 Mg•m-3, V=0.91856(14) nm3. The experiments suggest that different types of organic amines can result in different types of reactions and products when they react with the same precursor 2-carbethoxy-6-acetylpyridine under the same conditions, i.e., aliphatic amine affords amidation while aromatic amine leads to Schiff-base condensation.

Key words: small aliphatic amine molecule, 2-carbethoxy-6-acetylpyridine, aromatic amine, crystal structure, Schiff-base condensation, amidation reaction