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化学学报
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化学学报 ›› 2011, Vol. 69 ›› Issue (06): 701-708. 上一篇    下一篇

研究论文

3,4-双取代氧化呋咱衍生物的合成、结构表征及热性能研究

李亚南*，张志忠，周彦水，王伯周，尚雁   

  1. (西安近代化学研究所 西安 710065)
  • 投稿日期:2010-07-19 修回日期:2010-09-17 发布日期:2010-11-10
  • 通讯作者: 李亚南 E-mail:liyananandalee@sina.com
  • 基金资助:

    国防科技工业基础产品创新计划科研专项

Study on the Synthesis, Structure Characterization and Thermal Performance of 3,4-Disubstituted Furoxano Derivatives

LI Ya-Nan, ZHANG Zhi-Zhong, ZHOU Yan-Shui, WANG Bo-Zhou, SHANG Yan   

  1. (Xi an Modern Chemistry Research Instritute, Xi an 710065)
  • Received:2010-07-19 Revised:2010-09-17 Published:2010-11-10
  • Contact: Ya-Nan LI E-mail:liyananandalee@sina.com

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1139

被引次数

18

以自制的偕氯肟基化合物为原料, 通过脱氯化氢、分子间二聚环化及硝化等反应合成了自行设计的8种目标化合物——3,4-二苯基氧化呋咱(1)、3,4-二(吡啶-2 -基)氧化呋咱(2)、3,4-二(吡啶-3 -基)氧化呋咱(3)、3,4-二(吡啶-4 -基)氧化呋咱(4)、3,4-二(吡嗪-2 -基)氧化呋咱(5)、3,4-二(4 -甲氧基苯-1 -基)氧化呋咱(6)、3,4-二(4 -氯苯-1 -基)氧化呋咱(7)及3,4-二(3 ,5 -二硝基苯-1 -基)氧化呋咱(8). 利用红外光谱、核磁共振、质谱、元素分析等手段对8种目标化合物进行了结构表征. 初步考察了不同取代基对二聚反应的影响, 发现取代基的吸电子能力越强, 越有利于形成氧化氰中间体结构, 目标产物收率越高|以化合物5为例, 探讨了反应温度、缚酸剂、缚酸剂浓度、反应介质等对二聚反应的影响, 确定适宜的反应条件为: 反应温度2～10 ℃, 缚酸剂选择3%～5%浓度的Na2CO3或KHCO3, 反应介质为低沸点溶剂, 在此反应条件下, 化合物的收率分别为64.7%, 71.3%, 70.0%, 71.1%, 75.6%, 58.1%, 59.4%, 42.7%|利用差示扫描量热法(DSC)研究了目标化合物的热稳定性, 其中苯基取代衍生物的热稳定性较氮杂环衍生物好.

关键词: 3,4-双取代氧化呋咱衍生物, 二聚反应, 合成, 影响, 热性能

The eight target compounds—3,4-diphenylfuroxan (1), 3,4-bis(pyridine-2 -yl)furoxan (2), 3,4-bis(pyridine-3 -yl)furoxan (3), 3,4-bis(pyridine-4 -yl)furoxan (4), 3,4-bis(pyrazine-2 -yl)furoxan (5), 3,4-bis(4 -methoxybenzene-1 -yl)furoxan (6), 3,4-bis(4 -chlorobenzene-1 -yl)furoxan (7), 3,4-bis(3 ,5 - dinitro-benzene-1 -yl)furoxan (8) were designed and synthesized by putting off hydrochloric, intramolecular dimeric cycliczation and nitration using chloride oxime-based compounds as primary substances. The structures of target compounds were characterized by IR, NMR, MS and elemental analysis. The effect of different substituents to dimeric cycliczation reaction was preliminarily investigated. It was found that the electron withdrawing ability of substituents was stronger, the structures of cyanide oxidation were more easily generated, and the yields of target products were higher. The effects of reaction temperature, deacidification agent, deacidification agent s concentration, reaction medium were studied using compound 5 as researchful object. The suitable reaction conditions were that reaction temperature was usually controlled at 2～10 ℃. Na2CO3 or KHCO3 was usually chosen as deacidification agent, and controlling the concentration at 3%～5%. The reaction medium was chosen low-boiling-point agent. Under suitable conditions, the yields of target compounds were 64.7%, 71.3%, 70.0%, 71.1%, 75.6%, 58.1%, 59.4% and 42.7% respectively. The thermal performance of target compounds were studied using differential scanning calorimetry (DSC). Result show that the thermal stability of phenyl substituted derivatives were better than heterocyclic substituted derivatives.

Key words: 3,4-disubstituted furoxano derivatives, dimerization reaction, synthesis, effect, thermal performance