以(-)β蒎烯为原料，经选择性氧化合成(+)诺蒎酮，分析了在不同氧化剂及溶剂体系下β蒎烯的氧化行为。研究了β蒎烯与高锰酸钾摩尔比、硫酸与高锰酸钾摩尔比、溶剂类型、反应温度、反应时间等因素对β蒎烯氧化转化率和诺蒎酮产物选择性的影响。结果表明，左旋β蒎烯选择性氧化合成右旋诺蒎酮适宜的氧化工艺条件：β蒎烯与高锰酸钾摩尔比为1∶3，硫酸与高锰酸钾摩尔比0.054∶1,以丙酮为溶剂，反应温度为15~25 ℃，反应时间为5 h。此条件下β蒎烯转化率为94.15 %，诺蒎酮选择性为89.19 %，诺蒎酮得率为83.97 %，纯度为95.29 %，比旋光度为[α]18D+33.86°(c 1.01, CHCl3)。另外，采用IR、GC-MS、1H NMR和13C NMR等对诺蒎酮结构进行了表征。
Abstract
(+)nopinone was synthesized through selective oxidation of (-)βpinene, and the oxidation behavior of βpinene under different oxidants and solvents system were examined. Effects of the molar ratios of βpinene/KMnO4 and H2SO4/KMnO4, types of solvents, reaction temperature and time on the conversion of βpinene and selectivity of (+)nopinone were investigated. The results showed that the suitable oxidation conditions of (-)βpinene into (+)nopinone were as follows: βpinene/KMnO4 molar ratio 1∶3, H2SO4/KMnO4 molar ratio 0.054∶1, acetone was used as the solvent, reaction temperature 15—25 ℃, and reaction time 5 h. The conversion of βpinene, selectivity of oxidation, yield of (+)nopinone, specific rotation and purity of obtained product were 94.15 %, 89.19 %, 83.97 %, [α]18D+33.86°(c 1.01, CHCl3), and 95.29 %, respectively. The structure of (+)nopinone was determined by IR, 1H NMR, 13C NMR and GCMS spectra.
{{custom_sec.title}}
{{custom_sec.title}}
{{custom_sec.content}}
参考文献
[1]秦民坚,徐珞珊. 滑叶山姜的挥发油成分[J]. 中草药,1999(10):734-734.
[2]江苏省植物研究所. 新华本草纲要:第一卷[M]. 上海:上海科学技术出版社,1988.
[3]Silva Junior R C, Ferreira V F, Pinheiro S. The stereoselective synthesis of nopinone based triazole ketones[J]. Tetrahedron: Asymmetry, 2004, 15: 3719-3722.
[4]Campos K R, Journet M, Cai D W, et al. A practical synthesis for the core structure of a family of selective prostaglandin D2 receptor antagonists[J]. J Org Chem, 2003, 68: 2338-2342.
[5]Campos K R, Lee S, Journet M, et al. A general method for the highly diastereoselective, kinetically controlled alkylation of (+)nopinone[J]. Tetrahedron Letters, 2002, 43: 6957-6959.
[6]Goralski C T, Chrisman W, Hasha D L, et al. Boranes in synthesis—Ⅶ. Synthesis of 2dialkylamino6,6dimethylbicyclo [3.1.1] heptan3ols from (R)(+)nopinone. Chiral auxiliaries for the addition of diethylzinc to aromatic aldehydes[J]. Tetrahedron: Asymmetry, 1997, 8(23): 3863-3871.
[7]Liu C, Sowa J R. Synthesis of (1R)(+)nopinone(1S)verbenonederived chiral annulated indenes via electrocyclic reactions[J]. Tetrahedron Letters, 1996, 37(40): 7241-7244.
[8]Boger D L, Mullican M D, Hellberg M R, et al. Preparation of optically active functionalized cisΔ61octalones[J]. J Org Chem, 1985, 50(11): 1904-1911.
[9]Baucherel X, Uziel J, Juge S. Unexpected catalyzed C=C bond cleavage by molecular oxygen promoted by a thiyl radical[J]. J Org Chem, 2001, 66(13): 4504-4510.
[10]Chang W S, Shia K S, Liu H J, et al. The first total synthesis of xenitorins B and C: assignment of absolute configuration[J]. Organic & Biomolecular Chemistry, 2006, 4: 3751-3753.
[11]Malkov A V, Bella M, Langer V, et al. PINDY: a novel, pinenederived bipyridine ligand and its application in asymmetric, copper(Ⅰ)catalyzed allylic oxidation[J]. Organic Letters, 2000, 2(20): 3047-3049.
[12]Yasuhiko I, Isao N. Preparation of (+)nopinone: JP, 60146843[P]. 1985-08-02.
[13]李家其,郭丹,尹笃林,等. 苯甲酸氧钒催化过氧化氢氧化β蒎烯的研究[J]. 林产化学与工业,2008,28(2):97-100.
[14]Mayer C F, Crandall J K. The pyrolysis of nopinone[J]. J Org Chem, 1970, 35(8): 2688-2690.
[15]金建忠,沈敏敏. β蒎烯氧化反应研究进展[J]. 广州化学,2006,31(3):51-56.
[16]William A D, Kobayashi Y. Synthesis of tetrahydrocannabinols based on an indirect 1,4addition strategy[J]. J Org Chem, 2002, 67(25): 8771-8782.
[17]Hon Y S, Lin S W, Lu L, et al. The mechanistic study and synthetic applications of the base treatment in the ozonolytic reactions[J]. Tetrahedron, 1995, 51(17): 5019-5034.
[18]Krzeminski M P, Wojtczak A. Chiral terpene auxiliaries. Part 1: Highly enantioselective reduction of ketones with borane catalyzed by an oxazaborolidine derived from (-)βpinene[J]. Tetrahedron Letters, 2005, 46: 8299-8302.
[19]Kozmina N, Paquete L A. (1R,5S)(+)nopinone of high enantiomeric purity[J]. Synthetic communication, 1996, 26(10): 2027-2030.
[20]Winstein S, Holness N J. Neighboring carbon and hydrogen. ⅩⅧ. Solvolysis of the nopinyl pbromobenzenesulfonates[J]. JACS, 1955, 77: 3054-3060.
[21]Sauer A M, Crowe W E, Laine R A, et al. Efficient and economic asymmetric synthesis of nootkatone, tetrahydronootkatone, their precursors and Derivatives: US, 7112700[P]. 2006-09-26.
[22]姜红宇,哈成勇,金建忠,等. 用β蒎烯为原料合成高纯度对异丙基苯酚[J]. 林产化学与工业,2004,24(4):53-55.
[23]Coxon J M, Garland R P, Hartshorn M P. Some derivatives of nopinone[J]. Aust J Chem, 1970, 23: 1069-1071.
基金
收稿日期：2009-04-10修回日期：2009-12-14基金项目：国家自然科学基金项目(30571468);国家自然科学基金重点项目(30430580)作者简介：刘兵(1984—),硕士生。*王石发(通信作者),教授。Email: wsfyyq@njfu.com.cn。引文格式：刘兵,敖汪伟,杨杨,等. 左旋β蒎烯选择性氧化合成右旋诺蒎酮的研究[J]. 南京林业大学学报:自然科学版,2010,34(2):89-94.
PDF(730890 KB)
