河南农业大学烟草学院
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陈发元, 付培培, 赵铭钦, 等. 在线热裂解/气相色谱-质谱分析3-吡啶甲酸茴香酯的热裂解产物[J]. 分析测试学报, 2016,35(7):825-831.
Analysis of Pyrolysates from 3 Pyridine Formic Acid Anisalcohol Ester by On line Pyrolysis/Gas Chromatography-Mass Spectrometry[J]. 2016,35(7):825-831.
采用在线热裂解/气相色谱-质谱(Py/GC-MS)联用技术对3-吡啶甲酸茴香酯进行热裂解分析。通过酰氯化和酯化反应合成了新型目标化合物3-吡啶甲酸茴香酯,其分子式为C14H14NO3。目标化合物的结构经核磁氢谱(1H NMR)、核磁碳谱(13C NMR)、红外光谱(IR)和高分辨质谱(HRMS)进行确证,并通过热重-微热重-差示扫描量热(TG-DTG-DSC)分析方法对目标化合物的热稳定性进行分析。在空气氛围中,将目标化合物分别于300,600,900 ℃下进行热裂解,并通过气相色谱-质谱法对其挥发性热裂解产物进行定性和半定量分析。研究显示:目标化合物共经历了两次失重过程。第一次失重在1299~1589 ℃之间,失重2.3%;第二次失重在158.9~274.9 ℃之间,失重达90.1%,230.1 ℃时失重率最大。热裂解共产生44种产物,包括具有香味特征的大茴香醛、对甲基苯酚、松油醇、D-香茅醇、大茴香醚和茴香醚等化合物。其中裂解温度对裂解产物的种类和相对含量具有明显影响。300 ℃时α-二去氢菖蒲烯的相对含量最高,600,900 ℃时,相对含量最高的分别是大茴香醛和对甲基苯酚。苯甲醛、茴香醚和大茴香醚的相对含量随着温度的升高呈先增加后降低趋势;而对甲基苯酚含量则随着温度的升高而增加。根据主要裂解产物及其相对含量的变化,对目标化合物的裂解机理进行了初步探讨。
The pyrolysis behavior of 3-pyridine formic acid anisalcohol ester was analyzed by on-line pyrolysis/gas chromatography-mass spectrometry(Py/GC-MS).Firstly,target compound 3-pyridine formic acid anisalcohol ester was synthesized by acyl chlorination and esterification.The structure of the target compound was confirmed by 1H NMR,13C NMR,IR and HRMS,and its stability was studied by the method of TG-DTG-DSC.In air atmosphere,target compound was pyrolyzed at 300,600,900 ℃,respectively.The pyrolysis products were analyzed by GC-MS qualitatively and semi quantitatively.The result showed that the target compound experienced two mass loss.The first mass loss occurred between 129.9 ℃ and 158.9 ℃,and the mass loss was 2.3%.The second mass loss was between 158.9 ℃ and 274.9 ℃,the mass loss reached up to 901%,and the mass loss rate peaked at 230.1 ℃.44 kinds of compounds were detected,including flavor characteristic compounds such as 4-methoxy-benzaldehyde,4-methyl-phenol,alpha-terpineol,1-methoxy-4-methyl-benzene and methoxy-benzene.The result also indicated that pyrolysis temperature had significant effects on the type and relative content of pyrolysis products.The relative content of α calacorene was the highest at 300 ℃,and the highest contents of 4-methoxy benzaldehyde and 4-methyl-phenol were at 600 ℃ and 900 ℃,respectively.With the increase of pyrolysis temperature,the relative contents of benzaldehyde, methoxy benzene and 1-methoxy-4-methyl-benzene increased at first and then decreased,and the content of 4-methyl-phenol increased.According to the relative contents of pyrolysis products and their changes,the pyrolysis mechanism of target compound was preliminarily dicussed.
气相色谱-质谱热裂解3-吡啶甲酸茴香酯
gas chromatography-mass spectrometry(GC-MS)pyrolysis3-pyridine formic acid anisalcohol ester
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