合成冰片草酸酯中间体成分气相色谱分析方法的研究与应用  

Gas Chromatographic Methodology and Its Application to Analyze Intermediate Oxalates of Synthetic Borneol

作　　者：袁晓敏[1,2,3,4] 张平辉 涂永元[5] 王婧 李冬梅 赵振东[1,2,3,4,6] 

机构地区：[1]中国林业科学研究院 林产化学工业研究所 [2]生物质化学利用国家工程实验室 [3]国家林业局林产化学工程重点开放性实验室 [4]江苏省 生物质能源与材料重点实验室,江苏南京210042 [5]福建省香产品质量检验中心,福建泉州362600 [6]中国林业科学研究院 林业新技术研究所,北京100091

出　　处：《林产化学与工业》2017年第5期93-100,共8页Chemistry and Industry of Forest Products

基　　金：国家林业局林业科技成果推广项目([2015]30号)

摘　　要：以自制的草酸二葑醇酯(DFO)、草酸二龙脑酯(DBO)、草酸二异龙脑酯(DIBO)、草酸龙脑异龙脑酯(BIBO)、草酸龙脑葑醇酯(BFO)和草酸异龙脑葑醇酯(IBFO)等为对照物质,建立了用气相色谱分析合成冰片主要草酸酯中间体的定性方法,以DFO和DBO为标准样品测定合成冰片中间体含量的外标定量方法。研究表明:气相色谱程序升温条件对中间体成分的分离影响较大,且对照物质DFO及DBO等进行气相色谱分析时需在正己烷等惰性溶剂中才能稳定存在和检测。通过对照样品加入法、合成混合酯样品谱图比对法等进行气相色谱分析,定性鉴定出合成冰片酯液中的主要中间体成分依次出峰顺序为:DFO、BFO、IBFO、DBO、BIBO和DIBO,保留时间依次为46.46、49.92、50.75、53.68、54.42和54.89 min。分别以DFO和DBO为外标物质,在质量浓度为1~25 g/L和5~25 g/L范围内建立的外标曲线回归方程为y1=93 622x1-48 633,y2=99 480x2-55 787,相关系数为r1=0.998 9和r2=0.999 2。平均加标回收率分别为103.2%和106.9%,相对标准偏差分别为1.72%和0.76%。应用建立的定性分析方法和定量分析方法检测了4个合成冰片酯液样品中的主要草酸酯中间体成分的组成及含量,结果表明该方法可满足科研及工业生产中对草酸酯中间体组成及含量的定性、定量测定,操作更为简单的峰面积归一化法可以根据需求进行选用。While the synthesized difenchyl oxalate（ DFO）,dibornyl oxalate（ DBO）,diisobornyl oxalate（ DIBO）,bornyl isobornyl oxalate（ BIBO）, bornyl fenchyl oxalate（ BFO）, and isobornyl fenchyl oxalate（ IBFO） were used as reference substances,the qualitative and quantitative analytic methodologies were studied and established for the main intermediates ofborneol by gas chromatography（ GC）,and then an external reference calibration curve method was also established to determine quantitatively difenchyl,dibornyl oxalates or the similar oxalate intermediates. As the results,it was shown that,difenchyl and dibornyl oxalates as reference substances must be dissolved in an inert solvent such as hexane,and the separation performance of the intermediate oxalates may be influenced obviously by the programmed temperature conditions. By means of reference substance addition and chromatogram comparison methods,the intermediate oxalates of synthetic borneol were separated and identified or predicted to be as difenchyl oxalate（ DFO）,bornyl fenchyl oxalate（ BFO）,isobornyl fenchyl oxalate（ IBFO）,dibornyl oxalate（ DBO）,bornyl isobornyl oxalate（ BIBO）,diisobornyl oxalate（ DIBO） with the retention time of 46. 46,49. 92,50. 75,53. 68,54. 42 and 54. 89 min etc. The calibration curves for fenchyl and dibornyl oxalates were plotted linearly in the ranges of 1-25 g/L and 5-25 g/L as y = 93 622 x-48 633（ r1= 0. 998 9） and y = 99 480 x-55 787（ r2= 0. 999 2）,by which their mean recoveries were determined as 103. 2% and 106. 9% with the relative standard deviations（ RSDs） 1. 72% and0. 76%,respectively. It is considered that the established qualitative GC method and quantitative mathematic equations would supply the demand to determine either qualitative components or quantitative contents of intermediate oxalates in research fields or industry production process. The common peak area normalization method would also be selected for the content determination for convenience.

关 键 词：合成冰片 草酸酯中间体 气相色谱方法 外标曲线法 

分 类 号：TQ351.4[化学工程]