浙江白术挥发油化学成分研究

目的：以药材气味为指标，准确区分不同产地、不同炮制品种白术样品；研究浙江白术挥发油的化学成分。方法：采用电子感官Alpha M．O．S传感器矩阵系统，对不同产地及不同炮制品种白术样品的复杂气味基质进行定性；常规硅胶柱层析分离纯化白术挥发油的化学成分，用核磁共振和X-射线衍射法鉴定其结构。结果：不同产地及不同炮制品种的白术样品其气味间存在显著差异，相对比而言，炮制工艺对样品气味特征的影响远比产地差异的作用大。白术内酯I的晶体属正交晶系，空间群为P212121。晶胞参数：a=8．756（1），b=12．012（2），C=12．555（1）h，V=1320．5（2）A^3，Z=4。Dx=1．169g／cm^3。最终可靠因子R1=0、041，wR2=0．1219。独立衍射点为1391个，可观察点（IFl^2≥2σlFl^2）为1328个。结果表明白术内酯I由2个反式联接的椅式六元环和1个五元内酯环组成。晶态下不存在分子内和分子间氢键联系，分子间以范德华力维系其在空间的稳定排列。结论：气味指纹分析技术对不同白术样品具有很高的灵敏度，能够有效的区分具有细小差异的样品；白术内酯I首次从浙江白术中分离得到，白术内酯I单晶首次从白术中制备得到。

Study on the Chemical Constituents of Volatile Oil of Atractylodes macrocephala Koidz.Produced in Zhejiang Province

Objective Based on the odor of medicinal materials, samples of Atractylodes macrocephala Koidz, from different regions and preparation process, were exactly distinguishd. To study the chemical constituents of Volatile Oil of Atractylodes macrocephala Koidz.. Methods With the Alpha M. O. S sensor array system, the complex odor characteristic of samples from different regions and preparation process can be determined quanlitatively;the chemical constituents were isolated and purified by silica gel column chromatography, the structures of the chemical constituents were elucidated by NMR and X - ray diffraction. Results There is significant difference between samples from different regions and preparation process. In comparison to the factor of the region, the preparation process has much bigger effects on the odor of the sample. The crystal belongs to the orthorhombic system with space group P212121. The unit cell parameters are as follows： a =8. 756（ 1 ） ,b = 12. 012（2） ,c = 12. 555（ 1 ）A, Z =4, Dx = 1. 169g/cm3, final R =0. 041, WR2 =0. 1219. There are 1391 unique reflections in which 1328 reflections were observed（ I FI^2 ≥2σ1FI2）. The results indicate that molecule of atractylenolide I consists of two trans - fused six - membered rings which show chair - conformation and a lactone ring five - membered. There is no intramolecular or intermolecular hydrogen bond in the crystal state. The molecules are linked by the van der waals force which retains molecular arrangement steadily in the crystal state; Conclusion This very method, odor characteristic finger - print analysis technique, has very high sensitivity, which can be applied to distinguishing samples of minor differences. At- ractylenolide I was separated from Atractylodes macrocephala Koidz. produced in Zhejiang province for the frist time. The crystal of atractylenolide I was obtained from Atractylodes macrocephala Koidz. for the first time.