异长叶烯酮的绿色合成研究

doi:10.3969/j.issn.0253-2417.2015.03.017

林产化学与工业 ›› 2015, Vol. 35 ›› Issue (3): 97-103.doi: 10.3969/j.issn.0253-2417.2015.03.017

异长叶烯酮的绿色合成研究

彭晗¹, 杨丽娟¹, 徐徐², 王石发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

收稿日期:2014-03-25 出版日期:2015-06-25 发布日期:2015-07-03
通讯作者: 王石发,博士生导师,研究领域为天然产物的合成与利用;E-mail:wsfyyq@njfu.com.cn。 E-mail:wsfyyq@njfu.com.cn
作者简介:彭晗(1988—),女,江苏徐州人,硕士,主要从事天然产物提纯与利用的研究工作
基金资助:
国家林业公益性项目(201104015)

Green Synthesis of Isolongifolenone

PENG Han¹, YANG Li-juan¹, XU Xu², WANG Shi-fa¹

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

Received:2014-03-25 Online:2015-06-25 Published:2015-07-03

摘要/Abstract

摘要： 以重质松节油为原料,经三氟化硼乙醚催化异构得到异长叶烯;采用Cu为催化剂、叔丁基过氧化氢(TBHP)为氧化剂、叔丁醇(TBA)为溶剂经烯丙位氧化得到异长叶烯酮。探讨了反应条件对异长叶烯氧化反应的影响,确定了适宜的氧化工艺条件为:Cu粉用量3%(以异长叶烯质量计),TBHP与异长叶烯物质的量比3.5:1,溶剂TBA与异长叶烯的质量比1:1,80 ℃温度下反应12 h,在此工艺条件下,异长叶烯酮得率达93%,纯度98.75%。

关键词: 重质松节油, 异长叶烯, 烯丙位氧化, 异长叶烯酮

Abstract: Isolongifolenone was synthesized by using heavy turpentine as the starting material.Firstly,the heavy turpentine was converted to isolongifolene by isomerization reaction with BF₃ (C₂H₅)₂O as catalyst.Isolongifolenone was finally obtained from isolongifolene by allylic oxidation with tert-butyl hydroperoxide (TBHP) as oxidizer,Cu as catalyst and tert-butyl alcohol (TBA) as solvent.By investigating the influence of different react conditions on the oxidation of isolongifolene,the optimum conditions were determined as follows:the mass fraction of Cu 3% (based on the mass of isolongifolene),the mole ratio of TBHP and isolongifolene 3.5:1,the mass ratio of TBA and isolongifolene 1:1,reaction temperature 80 ℃ and reaction time 12 h.The yield of isofolenone was over 93%,and the purity was 98.75% under these conditions.

Key words: heavy turpentine, isolongifolene, allylic oxidation, isolongifolenone

中图分类号:

TQ35

彭晗, 杨丽娟, 徐徐, 王石发. 异长叶烯酮的绿色合成研究[J]. 林产化学与工业, 2015, 35(3): 97-103.

PENG Han, YANG Li-juan, XU Xu, WANG Shi-fa. Green Synthesis of Isolongifolenone[J]. Chemistry and Industry of Forest Products, 2015, 35(3): 97-103.

参考文献

[1] PICKENHAGEN W,SCHATKOWSKI D.Isolongifolenyl ethers their preparation and their use:US,006734159B2[P].2004-05-11.
[2] CHOUDHARY M I,MUSHARRAF S G,KHAN M T H,et al.Microbial transformation of isolongifolen-4-one[J].Helvetica Chimica Acta,2003,86(10):3450-3460.
[3] SHIINO M,WATANABE Y,UMEZAWA K.Synthesis of N-substituted N-nitrosohydroxylamines as inhibitors of mushroom tyrosinase[J].Bioorganic & Medicine Chemistry Letters,2001,9(5):1233-1240.
[4] MUTHYALAR S,SHENG S B,CARLSON K E,et al.Bridged bicyclic cores containing a 1,1-diarylethylene motif are high-affinity subtype-selective ligands for the estrogen receptor[J].Medicinal Chemistry,2003,46(9):1589-1602.
[5] 张爱军,约翰·F·卡罗尔,王仕发,等.使用异长叶烯酮和异长叶烯酮类似物驱避节肢动物的方法:中国,200880106609.X[P].2008-07-09. ZHANG Ai-jun,CARROLL F J,WANG Shi-fa,et al.Method for preparation isolongifolenone and its use in repelling arthropods:China,200880106609.X[P].2008-07-09.
[6] 周红,朱定姬,黄冠,等.复合催化剂催化重质松节油合成异长叶烯反应的研究[J].广西师范学院学报:自然科学版,2009,26(4):50-53. ZHOU Hong,ZHU Ding-ji,HUANG Guan,et al.Study on composite catalyst synthesis of ISO longifolene from heavy turpentine reactions[J].Journal of Guangxi Teachers Education University:Natural Science Edition,2009,26(4):50-53.
[7] 謝博進,森口彰人,松原義治.テルペン類の極性非プロトン性溶媒を用いる酸化反応I光学活性 9-オキソイソロンギホレンの新合成法[J].日本化学会誌,1978(6):906-908. SHIEH B J,MORIGUCHI A,MATSURARA Y.Synthesis of optically active 9-oxoisolongifolene[J].Nippon Kagku Kaishi,1978(6):906-908.
[8] 周萍,肖树德.异长叶烯自氧化主产物的结构[J].林产化学与工业,1986,6(2):19-21. ZHOU Ping,XIAO Shu-de.The structure of the major product from the autoxidation of isolongifolene[J].Chemistry and Industry of Forest Products,1986,6(2):19-21.
[9] SRIVASTAVA P K,CHANDRA G.Oxidation of γ-terpinene and isolongifolene with t-butyl chromate[J].Indian Perfumer,1982,26(2):151-153.
[10] 武法文,李磊,徐志红,等.膜法富氧空气用于异长叶烯催化氧化研究[J].南京大学学报:自然科学版,2006,42(2):163-169. WU Fa-wen,LI-Lei,XU Zhi-hong,et al.The application of oxygen-enriched air by gas separation membranes in catalytic oxidation of isolongifolene[J].Journal of Nanjing University:Natural Sciences,2006,42(2):163-169.
[11] 李春,司伊康.烯丙位氧化的几种方法[J].有机化学,2003,23(6):518-525. LI-Chun,SI Yi-kang.Methods of allylic oxidation[J].Chinese Journal of Organic Chemistry,2003,23(6):518-525.

异长叶烯酮的绿色合成研究

Green Synthesis of Isolongifolenone

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 5

编辑推荐

Metrics

本文评价

关于本刊

投稿指南

在线期刊

相关单位

联系我们

[1]	吴陈亮, 王芸芸, 徐徐, 谷文, 王石发. 异长叶烯酮肟的合成及其与金属离子的配位特性[J]. 林产化学与工业, 2019, 39(1): 101-107.
[2]	刘艳方, 芮坚, 徐徐, 谷文, 王石发. 异长叶烯酮磺酸的合成及其催化性能[J]. 林产化学与工业, 2018, 38(2): 133-138.
[3]	芮坚, 杨金来, 蔡涛, 徐徐, 王石发. 异长叶烯基噻唑类化合物的合成及其抑菌、抗肿瘤活性研究[J]. 林产化学与工业, 2016, 36(6): 41-48.
[4]	丁志彬, 孙楠, 张齐, 曹晓琴, 徐徐, 王石发. 手性α-溴代异长叶烯酮的合成研究[J]. 林产化学与工业, 2016, 36(5): 30-36.
[5]	罗金岳;安鑫南;雷福厚. 固体超强酸催化长叶烯制备异长叶烯的研究[J]. 林产化学与工业, 2006, 26(04): 39-42.