3-吡咯甲酸乙酯衍生物的制备及其热裂解产物研究  

Synthesis of Derivate of 3-Pyrrole Ethyl Formate and Study on Its Pyrolysates

作　　者：陶陶[1] 赵华新[2] 姬小明[1] TAO Tao, ZHAO Hua- xin2, JI Xiao - ming(1. Tobacco College, Henan Agriculture University, Zhengzhou 450002, Henan, China; 2. College of Life Sciences, Henan Agriculture University, Zhengzhou 450002, Henan, China)

机构地区：[1]河南农业大学烟草学院,河南郑州450002 [2]河南农业大学生命科学学院,河南郑州450002

出　　处：《香料香精化妆品》2017年第6期22-28,共7页Flavour Fragrance Cosmetics

基　　金：河南省科技厅重点科技攻关项目(编号152102210058)

摘　　要：以D-(+)-氨基葡萄糖盐酸盐为原料,通过环合、氧化和烷基化等系列反应,合成了新型化合物N-异丙基-2-甲基-5-甲酰基-3-吡咯甲酸乙酯,其分子式为C12H17NO3。此化合物的结构经1H NMR、13C NMR、IR和HR-MS等波谱技术进行确证,通过热重-微分热重-差示扫描量热(TG-DTG-DSC)研究了该化合物的热失重变化,并采用热裂解/气相色谱-质谱(Py/GC-MS)分析了该化合物的热裂解产物。研究显示,该化合物共经历两次失重过程。第一次失重在30℃至108.4℃之间,失重率为0.90%;第二次失重在108.4℃至280.0℃之间,失重率达到98.58%,在175.0℃时失重率最大。300、600和900℃下共裂解出54种化合物,其中含有吡嗪、己醛、环己酮、2,5-二甲基吡嗪、2,5-二甲基吡咯和苯甲醛等多种香味成分。300℃时,乙酸的相对含量最高,600和900℃时,2-甲基吡咯的相对含量最高。根据主要裂解产物,初步探讨了该化合物可能的热裂解机理。New compound,5-formyl-N-isopropyl-2-methyl-3-pyrrole ethyl formate was synthesized through cyclization,oxidation and alkylation reaction by using D-（＋）-glucosamine hydrochloride as raw material.The formula of this compound was C12 H17 NO3.Its structure was confirmed by 1 H NMR,13 C NMR,IR and HR-MS spectra and its thermal stability was studied by themogravimetry-derivative themogravimetry-differential scanning calorimetry（TG-DTG-DSC）.The pyrolytic products of this new compound were analyzed by pyrolysis/gas chromatography-mass spectrometry（Py/GC-MS）.The results showed that it underwent twice mass loss processes.The first mass loss step occurred from 30 ℃ to 108.4 ℃and the mass loss was 0.90%.The second mass loss step happened between 108.4 and 280.0 ℃ and the mass loss reached up to 98.58%.The top mass loss occurred at 175.0 ℃.A total of 54 pyrolysates were detected at 300,600 and 900 ℃,including aroma substances of pyrazine,hexanal,cyclohexanone,2,5-dimethyl pyrazine,2,5-dimethyl pyrrole and benzaldehyde.The highest relative mass content of acetic acid was obtained at 300 ℃ and the highest content of 2-methyl pyrrole was showed at 600 and 900 ℃.Possible pyrolytic mechanism of this compound was preliminarily discussed based on the relative mass contents of pyrolysates.

关 键 词：合成 N-异丙基-2-甲基-5-甲酰基-3-吡咯甲酸乙酯 热裂解/气相色谱-质谱法 

分 类 号：TQ655[化学工程—精细化工]