中华医学超声杂志

应用化学 ›› 2010, Vol. 27 ›› Issue (07): 806-810.DOI: 10.3724/SP.J.1095.2010.90660

• 研究论文 • 上一篇    下一篇

3,5-二甲基-4-碘吡唑钾配合物的合成、结构及肟化中间体结构的量化

王建忠1,赵海燕1,邢永恒1*,王强2,王永成2   

  1. (1.辽宁师范大学化学化工学院 大连 116029;2.西北师范大学化学化工学院 兰州)
  • 收稿日期:2009-10-11 修回日期:2009-12-29 出版日期:2010-07-10 发布日期:2010-07-10
  • 通讯作者: 邢永恒,男,博士,教授; E-mail:yhxing2000@yahoo.com; 研究方向：生物无机及无机药物配位化学
  • 基金资助:
    国家自然科学基金(20771051)和辽宁省教育厅2007年度创新团队计划(2007T093)资助项目

Synthesis, Structure of 4-Iodo-3,5-dimethyl-pyrazole Potassium and Quantum Chemistry Calculation of Intermediate of Oximation

WANG Jian-Zhong1, ZHAO Hai-Yan1, XING Yong-Heng1*, WANG Qiang2, WANG Yong-Cheng2   

  1. (1.College of Chemistry and Chemical Engineering,Liaoning Normal University,Dalian 116029;
    2.College of Chemistry and Chemical Engineering,Northwest Normal University,Lanzhou)
  • Received:2009-10-11 Revised:2009-12-29 Published:2010-07-10 Online:2010-07-10

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摘要：

以乙酰丙酮为起始原料，经过肟化反应得到3-肟基戊二酮(1)，再将其与水合肼缩合环化、还原、重氮化及碘代反应合成了标题化合物。 通过元素分析、红外光谱、核磁共振光谱测试技术表征了它的结构。 用MP2方法，在6-311++G(d,p)基组水平上对化合物1及其可能异构体4-羟基-3-亚硝基-3-烯-1-戊酮(1b)的分子结构进行了全参数优化计算，得到了它们的平衡几何构型。 探讨了肟化反应机理。 利用X射线单晶衍射法测定了钾化合物的晶体结构，为单斜晶系，P21/c空间群，晶胞参数为a=0.77645(10) nm,b=2.0361(2) nm,c=1.05761(13) nm,β=107.806(2)°,V=1591.9(3) nm3,Z=4,Dc=2.012 g/cm3,F(000)=904,结构计算的最终偏离因子R1=0.0398。

关键词: 乙酰丙酮, 配合物, 反应机理, 量子化学, 3,5-二甲基-4-碘吡唑

Abstract:

A new potassium compound of 4-iodo-3,5-dimethyl-pyrazole was synthesized with acetylacetone and hydrazine hydrate as the starting materials via oximation, condensation cyclization, reduction, diazotization and iodination. The compound was characterized by elemental analysis, IR, and 1H NMR. The reaction mechanism of oximation was studied with the program of Gaussian 03, at the MP2/6-311++ G(d,p) level. The stable geometric configurations of acetylacetone-3-oxime(1) and its intermediate of 4-hydroxy-3-nitrosopent-3-en-2-one(1b) were confirmed at the same calculation level. Furthermore, the crystal structure was determined by single-crystal X-ray diffraction analysis. The crystal is monoclinic, P21/c space group， with crystal parameters a=0.77645(10) nm,b=2.0361(2) nm,c=1.05761(13) nm, β=107.806(2)°, V=1591.9(3) m3,Z=4,Dc=2.012 g/cm3，F(000)=904, R1=0.0398.

Key words: acetylacetone, complex, reaction mechanism, quantum chemistry, 4-iodo-3,5-dimethyl-pyrazole

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