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林产化学与工业

林产化学与工业 ›› 2013, Vol. 33 ›› Issue (5): 61-66.doi: 10.3969/j.issn.0253-2417.2013.05.012

• 1研究报告 • 上一篇    下一篇

α-蒎烯合成樟脑酸酐的研究

梁志华1, 李好瑾1, 徐徐1,2, 王有祥3, 王石发1,2   

  1. 1. 南京林业大学 化学工程学院, 江苏 南京 210037;2. 江苏省生物质绿色燃料与 化学品重点实验室, 江苏 南京 210037;3. 崇义县林业局, 江西 崇义 341300
  • 收稿日期:2012-08-27 修回日期:1900-01-01 出版日期:2013-10-30 发布日期:2013-10-30
  • 通讯作者: 王石发,教授,博士生导师,研究领域为天然产物化学,有机合成化学;E-mail:wsfyyq@njfu.com.cn。

Synthesis of Camphoric Anhydride from α-Pinene

LIANG Zhi-hua1, LI Hao-jin1, XU Xu1,2, WANG You-xiang3, WANG Shi-fa1,2   

  1. 1. College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China;2. Jiangsu Key Lab ofBiomass-based Green Fuels and Chemicals, Nanjing 210037, China;3. Chongyi Forestry, Chongyi 341300, China
  • Received:2012-08-27 Revised:1900-01-01 Online:2013-10-30 Published:2013-10-30

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摘要： α-蒎烯与干燥HCl加成、异构得到2-氯莰烷,再经消除反应得到冰片烯,以乙酸酐-水混合溶剂为反应介质、高锰酸钾作氧化剂氧化冰片烯,得到樟脑酸酐。探讨了溶剂种类、乙酸酐-水的体积比、KMnO4用量、反应温度、反应时间等对冰片烯氧化反应的影响,确定了适宜的氧化工艺条件：以高锰酸钾为氧化剂,高锰酸钾与冰片烯的物质的量比为2.5:1;以乙酸酐-水混合溶剂作为氧化反应介质,乙酸酐-水的体积比为3:1,溶剂与冰片烯的比为20:1(mL:g),反应温度为 40℃,反应时间 4 h。在此工艺条件下,樟脑酸酐得率达 94% 以上。采用GC-MS、FT-IR、1H NMR、13C NMR 等分析手段对合成所得产物的化学结构进行了分析测定。

关键词: α-蒎烯, 樟脑酸酐, 2-氯莰烷, 冰片烯, 氧化

Abstract: Synthesis of camphoric anhydride was carried out using α-pinene as the starting material. 2-chlorocamphane was prepared by addition and isomerization of α-pinene and dry hydrogen chloride, and it was further eliminated HCl in alkaline condition to obtain bornylene. Camphoric anhydride was finally obtained by oxidation of bornylene with KMnO4 in mixed acetic anhydride-water solvent. Influences of solvent systems, volume ratio of acetic anhydride and water, the amount of KMnO4, reaction temperature and reaction time on the oxidation of bornylene were examined in detail. The suitable oxidation conditions were determined as follows: KMnO4 used as the oxidant for oxidizing bornylene into camphoric anhydride, KMnO4/bornylene molar ratio 2.5:1, acetic anhydride/H2O mixture with a volume ratio of 3:1 used as the solvent, solvent/bornylene ratio 20:1(mL:g), reaction temperature 40℃ and reaction time 4 h. The yield of camphoric anhydride was over 94% under the aforesaid conditions. Its chemical structure was determined with GC-MS, FT-IR, 1H NMR, and 13C NMR spectra.

Key words: α-pinene, camphoric anhydride, 2-chlorocamphane, bornylene, oxidation

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