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林产化学与工业

林产化学与工业 ›› 2016, Vol. 36 ›› Issue (5): 15-22.doi: 10.3969/j.issn.0253-2417.2016.05.003

• 研究报告 • 上一篇    下一篇

草酸龙脑酯手性异构体的合成及谱学性质对比研究

袁晓敏1, 陈金凤2, 衣晓庆1, 赵振东1,3, 张平辉1, 陈玉湘1,3, 徐士超1,3   

  1. 1. 中国林业科学研究院 林产化学工业研究所;生物质化学利用国家工程实验室;国家林业局 林产化学工程重点开放性实验室;江苏省 生物质能源与材料重点实验室, 江苏 南京 210042;
    2. 福建省香产品质量检验中心, 福建 泉州 362600;
    3. 中国林业科学研究院 林业新技术研究所, 北京 100091
  • 收稿日期:2015-12-29 出版日期:2016-10-25 发布日期:2016-11-05
  • 通讯作者: 赵振东,研究员,博士生导师,主要从事萜类化学、天然产物化学、应用化学、松树病虫害化学等方面的研究与利用;E-mail:zdzhao@189.cn。 E-mail:zdzhao@189.cn
  • 作者简介:袁晓敏(1990-),女,河南安阳人,硕士生,主要从事应用化学研究
  • 基金资助:
    农业科学技术成果转化资金项目（2013GB24320604）

Synthesis and Spectral Properties of Chiral Isomers of Dibornyl Oxalate

YUAN Xiao-min1, CHEN Jin-feng2, YI Xiao-qing1, ZHAO Zhen-dong1,3, ZHANG Ping-hui1, CHEN Yu-xiang1,3, XU Shi-chao1,3   

  1. 1. Institute of Chemical Industry of Forest Products, CAF;National Engineering Lab. for Biomass Chemical Utilization;Key and Open Lab. of Forest Chemical Engineering, SFA;Key Lab. of Biomass Energy and Material, Jiangsu Province, Nanjing 210042, China;
    2. Fujian Quality Inspection Center for Incense Products, Quanzhou 362600, China;
    3. Research Institute of Forestry New Technology, CAF, Beijing 100091, China
  • Received:2015-12-29 Online:2016-10-25 Published:2016-11-05

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摘要： 分别以左旋龙脑（艾片）、右旋龙脑（冰片）、艾片及冰片组成的外消旋龙脑为原料，与草酰氯发生间接酯化反应合成了3种光学活性的草酸龙脑酯，经乙醇重结晶后GC纯度99.9%，通过手性液相色谱分析证明合成的消旋龙脑酯中同时含有左旋体、内消旋体和右旋体，其质量比近似为1：2：1。利用二维核磁共振技术1H-1H COSY、HSQC及HMBC等手段对左旋的草酸龙脑酯的碳原子及氢原子进行归属，并采用GC-MS、FT-IR、1H NMR、13C NMR等对比研究了所合成的左旋、右旋及消旋的草酸龙脑酯的谱学性质，还进一步对比了合成的消旋龙脑酯与人工混合而成的外消旋体的谱学特征。结果表明：左旋、右旋及人工混合的外消旋的草酸龙脑酯虽然旋光性不同，但其谱学性质没有明显的差别，而由外消旋龙脑与草酰氯合成得到的消旋产物中所含的内消旋体，其分子两侧的碳氢原子却表现出比较明显的核磁化学环境及谱学性质差异，主要体现在8-与8’-、3-与3’-位上的氢及1-与1’-、3-与3’-、11-与11’-位上的碳的化学位移值不相等。

关键词: 光学活性, 龙脑, 草酰氯, 草酸龙脑酯, 谱学性质

Abstract: Dibornyl oxalates with different optical activity were synthesized by indirect esterification method from different chiral borneol with oxalyl chloride, and the target products could be easily purified to 99.9% (GC) through recrystallization with alcohol. The composition of the synthesized dibornyl oxalates were analyzed by chiral high-performance liquid chromatography (HPLC), and it was proved that there were (-)-dibornyl oxalate, mesomer and (+)-dibornyl oxalate in the synthesized racemic dibornyl oxalate, and the mass ratio was nearly 1:2:1. The location of hydrogen and carbon atoms in (-)-dibornyl oxalate was determined by means of 1H-1H COSY, HSQC and HMBC, and the spectra of different chiral dibornyl oxalate were contrasted including GC-MS, IR, 1H NMR and 13C NMR. Furthermore, the synthetic racemic dibornyl oxalate was compared with the mixture of equal (+) and (-) dibornyl oxalates. The results showed that the spectral properties of (+), (-) and racemic dibornyl oxalate were similar, however these oxalates could be distinguished via optical activity. The mesomer, which contained in the synthesized racemic dibornyl oxalate from the reaction of racemic borneol and oxalyl chloride, owned different nuclear magnetic chemical environment and spectral properties of the carbon and hydrogen atoms on both sides. This reflected in the different chemical shifts of the hydrogen atoms on 8-and 8'-, 3-and 3'-, and the carbon atoms on 1-and 1'-, 3-and 3'-as well as 11-and 11'-positions.

Key words: optically active, borneol, oxalyl chloride, dibornyl oxalate, spectral properties

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