α-蒎烯合成樟脑醌的研究

doi:10.3969/j.issn.1000-2006.2013.03.022

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南京林业大学学报（自然科学版） ›› 2013, Vol. 37 ›› Issue (03): 123-128.doi: 10.3969/j.issn.1000-2006.2013.03.022

α-蒎烯合成樟脑醌的研究

梁志华¹,李好瑾¹,徐徐^1,2,王石发^1,2*

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

出版日期:2013-06-18 发布日期:2013-06-18
基金资助:
收稿日期:2012-08-22 修回日期:2012-10-12
基金项目:国家林业公益性行业科研专项项目(201104015); 国家自然科学基金项目(30972316)
第一作者:梁志华,博士生。*通信作者:王石发,教授,博士。E-mail: wsfyyq@njfu.com.cn。
引文格式:梁志华,李好瑾,徐徐,等. α-蒎烯合成樟脑醌的研究[J]. 南京林业大学学报:自然科学版,2013,37(3):123-128.

Synthesis of camphorquinone from α-pinene

LIANG Zhihua¹, LI Haojin¹, XU Xu^1,2, WANG Shifa^1,2*

1. College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China;
2. Jiangsu Key Lab of Biomass-based Green Fuels and Chemicals, Nanjing 210037, China

Online:2013-06-18 Published:2013-06-18

摘要/Abstract

摘要： 以α-蒎烯为原料,与HCl加成、异构得到2-氯莰烷,再经消除反应得到冰片烯,以丙酮-水混合溶剂为反应介质,高锰酸钾为氧化剂氧化冰片烯,得到樟脑醌。探讨了相转移催化剂及溶剂种类、KMnO₄用量、丙酮与水的体积比,以及溶剂用量、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量之比为3.0:1; 以丙酮-水混合溶剂作为氧化反应介质,丙酮与水的体积比为3:1,丙酮-水混合溶剂与冰片烯的体积质量比为20:1(mL/g); 反应温度为30 ℃; 反应时间4 h。在此工艺条件下,樟脑醌得率达85%以上。采用GC-MS、FTIR、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。

Abstract: Synthesis of camphorquinone was carried out by using α-pinene as the starting material. 2-chlorinated bornane was prepared by addition and isomerization of α-pinene and dry hydrogen chloride, and it was further eliminated HCl in order to obtain bornylene. Camphorquinone was finally obtained by oxidation of bornylene with KMnO₄ in mixed acetone-water solvent. Influences of phase-transfer catalysts and solvent systems, the amount of KMnO₄, acetone/H₂O ratio and the amount of mixed solvent, reaction temperature and reaction time on the oxidation of bornylene were examined in detail, and the suitable oxidation conditions were determined as follows:KMnO₄ was used as the oxidant for oxidizing bornylene into camphorquinone, and KMnO₄/bornylene molar ratio was 3.0:1; acetone/H₂O mixture with a volume ratio 3:1 was used as the solvent, and the solvent/bornylene ratio was 20:1(mL/g); the oxidation of bornylene was conducted at 30 ℃ for 4 h. The yield of camphorquinone was over 85% under the aforesaid conditions, and its chemical structure was determined with GC-MS, FTIR, ¹H NMR, and ¹³C NMR spectra.

中图分类号:

TQ245

梁志华,李好瑾,徐徐,等. α-蒎烯合成樟脑醌的研究[J]. 南京林业大学学报（自然科学版）, 2013, 37(03): 123-128.

LIANG Zhihua, LI Haojin, XU Xu, WANG Shifa. Synthesis of camphorquinone from α-pinene[J].Journal of Nanjing Forestry University (Natural Science Edition), 2013, 37(03): 123-128.DOI: 10.3969/j.issn.1000-2006.2013.03.022.

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α-蒎烯合成樟脑醌的研究

Synthesis of camphorquinone from α-pinene

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