Page 154 - 《精细化工》2021年第5期

·1008· 精细化工 FINE CHEMICALS 第 38 卷

2.3 催化剂的回收利用 of clinical application of borneol[J]. Modern Journal of Integrated
在适宜反应条件下（环己烷用量 35 mL，反应 Traditional Chinese and Western Medicine (现代中西医结合杂志),
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温度为 120 ℃，离子液体为松节油质量的 8%，α- [2] ALMEIDA J R, SOUZA G R, SILVA J C, et al. Borneol, a bicyclic
蒎烯和乙酸的物质的量比为 1∶3，反应时间 8 h） monoterpene alcohol, reduces nociceptive behavior and inflammatory
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进行催化剂[Bmim-SO 3 H]HSO 4 重复使用性能考察，
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结果见图 3。从图 3 可以看出，离子液体重复使用 Pharmacological effects of borneol and isoborneol in mice and
到第 3 次时，α-蒎烯的转化率降至 99.76%，而正龙 rabbits[J]. West China Journal of Pharmaceutical Sciences (华西药学
脑的选择性也从 39.83%降至 35.45%，表明[Bmim- 杂志), 1989, 4(1): 23-25.
[4] SIEGEL S, KRAMMER G, BERTRAM H J, et al. Citrus juice sacs
SO 3 H]HSO 4 具有较高的催化活性和稳定性。造成上 with aroma addition: US 20090148586A1[P]. 2009-06-11.
述 α-蒎烯转化率和正龙脑选择性降低的原因可能是 [5] YUAN X M (袁晓敏), ZHANG P H (张平辉), ZHAO Z D (赵振东),
在回收利用过程中，离子液体有部分损失。 et al. Research advances in the catalysts for synthesis of borneol
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Synthesis of borneol from α-pinene catalyzed by solid superacid
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7-11, 28.
图 3 催化剂重复使用次数对催化剂活性的影响 [9] WANG H L (王鹤林), JIANG L H (蒋丽红), WANG Y M (王亚明),
2–
Fig. 3 Effect of reuse of catalyst on catalyst activity et al. Preparation of SO 4 /TiO 2-Al 2O 3 soild superacid catalyst and its
catalytic activity for borneol synthesis[J]. Material Review (材料导
3 结论 报), 2017, 31(22): 43-49.
[10] YANG Y W (杨义文), CHEN H Z (陈慧宗), LI L (李蕾). Synthesis
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of borneol from α-pinene catalyzed by solid superacid S 2O 8 /ZrO 2-
通过两步法合成了 4 种阴离子不同的咪唑类离
NiO[J]. Advances in Fine Petrochemicals (精细石油化工进展),
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子液体，并用 FTIR、HNMR、 CNMR、TG、Hammett 2009, 10(9): 36-39.
对离子液体进行结构表征。对比 4 种离子液体，阴 [11] LIU S W, XIE C X, YU S T, et al. Esterification of α-pinene and
–
离子为 HSO 4 的离子液体酸性最强且对正龙脑的选 acetic acid using acidic ionic liquids as catalysts[J]. Catalysis
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择性最好。 [12] JI K H (季开慧), LIU S W (刘仕伟), XIE C X (解从霞), et al.
对[Bmim-SO 3 H]HSO 4 催化 α-蒎烯酯化-皂化反 Synthesis of bornyl acetate from α-pinene catalyzed by acidic ionic
liquid[J]. Chemistry and Industty of Forest Products (林产化学与工
应进行研究，在环己烷用量为 35 mL，温度 120 ℃，
业), 2008, 28(4): 34-38.
催化剂用量为松节油质量的 8%，n(α-蒎烯)∶n(乙 [13] ZHANG Q H, ZHANG S G, DENG Y Q. Recent advances in ionic
酸)=1∶3，反应时间为 8 h 时，正龙脑的选择性为 liquid catalysis[J]. Green Chemistry, 2011, 13(10): 2619-2637.
39.83%，且占总龙脑的 92.56%。其中离子液体的作 [14] LIU Y, XIAO W, XIA S Q, et al. SO 3H-functionalized acidic ionic
+ – liquids as catalysts for the hydrolysis of cellulose[J]. Carbohydrate
用是提供 H ，使 α-蒎烯质子化形成碳正离子，HSO 4 Polymers, 2013, 92(1): 218-222.
稳定非经典碳正离子，与乙酸根形成络合物，使生 [15] TAO F R, ZHUANG C, CUI Y Z, et al. Dehydration of glucose into
成正龙脑的反应更容易发生。 5-hydroxymethylfurfural in SO 3H-functionalized ionic liquids[J].
Chinese Chemical Letters, 2014, 25(5): 757-761.
[Bmim-SO 3 H]HSO 4 重复使用到第 3 次仍具有较
[16] COLE A C, JENSEN J L, NTAI I, et al. Novel bronsted acidic ionic
高的活性，α-蒎烯的转化率在 99%以上，正龙脑的 liquids and their use as dual solvent-catalysts[J]. J Am Chem Soc,
选择性为 35.45%。 2002, 124(21): 5962-5963.
[17] HAJIPOUR A R, KHAZDOOZ L, RUOHO A E, et al. Bronsted
α-蒎烯酯化存在扩环和开环反应的竞争，离子
acidic ionic liquid as an efficient catalyst for acetylation of alcohols
液体作为催化剂并引入环己烷，促进了 α-蒎烯开环 and phenols[J]. Journal of the Chinese Chemical Society, 2009, 56(2):
生成龙脑的反应且提高了正龙脑的含量。本文为 α- 398-403.
[18] XU Z J, WAN H, MIAO J M, et al. Reusable and efficient
蒎烯酯化-皂化法高选择性合成正龙脑提供了新思路。
polystyrene-supported acidic ionic liquid catalyst for esterifications[J].
Journal of Molecular Catalysis A: Chemical, 2010, 332(1/2): 152-157.
参考文献：
[1] JIANG J C (姜建昌), CAO L (曹雷), YAO Y J (姚瑜洁), et al. Survey （下转第 1022 页）