巨豆三烯酮前体物的合成及其热解作用
Synthesis of megastigmatrienone precursors and their pyrolysis properties
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摘要: 为解决巨豆三烯酮合成困难、稳定性差的问题,以α-紫罗兰酮为原料,通过还原、酯化及烯丙位氧化3步反应,合成了4种3-氧代-α-紫罗兰醇碳酸酯类巨豆三烯酮前体物,并对其合成条件进行优化;通过热重分析(TG-DTG)、在线热裂解-气相色谱-质谱联用(Py-GC-MS)技术和卷烟加香释放分析,对合成化合物的热解释放规律进行研究。结果表明:以Cu+为催化剂,在叔丁基过氧化氢的氧化作用下,以中等至较高产率得到了目标化合物;3-氧代-α-紫罗兰醇碳酸酯的失重区间约为160~350℃;在300℃、600℃和900℃温度下,该类化合物均可裂解释放巨豆三烯酮和相应的醇类香味物质;当添加量为0.1%时,4种3-氧代-α-紫罗兰醇碳酸酯释放的巨豆三烯酮的量较空白卷烟提高约6倍;3-氧代-α-紫罗兰醇碳酸酯在受热时,会优先断裂烯丙醇酯键,脱水生成巨豆三烯酮,可增加卷烟烟气的甜润感,并有效掩盖杂气,从而提升卷烟的整体品质。
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关键词:
- 3-氧代-α-紫罗兰醇碳酸酯 /
- 巨豆三烯酮 /
- 前体物 /
- 卷烟加香 /
- 热裂解
Abstract: In order to solve the problems of difficult synthesis and poor stability of megastigmatrienone, four 3-oxo- α-ionol carbonates were synthesized as precursors of megastigmatrienone using α-ionone as raw material via a threestep reaction of reduction, esterification, and allylic oxidation. The synthesis conditions were optimized, and the thermal release behaviors of the synthesized compounds were studied by thermogravimetric analysis, on-line pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS), and cigarette flavor release analysis. The results showed that using Cu+ as the catalyst and TBHP as the oxidant, the target compounds were successfully obtained in moderate to high yields. The weight loss interval of 3-oxo-α-ionol carbonates was approximately 160 ~ 350 ℃. At temperatures of 300 ℃, 600 ℃, and 900 ℃, these compounds could pyrolyze to release megastigmatrienone and corresponding alcoholic flavor substances. At an addition level of 0. 1%, the release amount of megastigmatrienone from the four 3-oxo-α-ionol carbonates was up to 6 times higher than that of blank cigarettes. Mechanistic studies indicated that upon heating, 3-oxo-α-ionol carbonates preferentially cleaved the allylic alcohol ester bond, followed by dehydration to generate megastigmatrienone. This process can enhance the sweet and smooth sensation of cigarette smoke, effectively mask off-flavors, and thus improve the overall quality of cigarettes.-
Key words:
- 3-oxo-α-ionol carbonate /
- megastigmatrienone /
- precursor /
- cigarette flavoring /
- pyrolysis
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