苯基烯醛呈香物质的合成、热解及其抗氧化活性研究

doi:10.6023/cjoc202603005

摘要/Abstract

苯基烯醛类化合物因分子中含有芳环、醛基等致香基团, 在香精香料领域具有重要应用, 是一类关键的呈香物质. 以无水乙醇为溶剂, 乙酸钠为碱性试剂, 通过苯乙醛与不同烷基醛的交叉羟醛缩合反应, 合成了6种新型苯基烯醛类化合物. 采用核磁共振(¹H NMR、¹³C NMR)、红外光谱(IR)和高分辨质谱(HRMS)对目标化合物的结构进行了表征. 通过感官评价小组评价了它们的香气特征. 利用热重-微商热重分析(TG-DTG)和热解-气相色谱/质谱联用技术(Py-GC/ MS)分析了它们的热行为. TG-DTG分析确定了90%质量损失对应的温度范围和最大质量损失速率对应的温度. 结果表明, 除化合物3d外, 其余5种化合物均满足加热不燃烧卷烟中香味成分的挥发性要求. 在400 ℃下进行的Py-GC/MS结果表明, 所有6种化合物均发生部分热解, 生成多种有助于丰富香韵的芳香产物. 抗氧化活性研究显示, 所有6种化合物均表现出显著的抗氧化活性. 其中, 化合物3c对ABTS^＋•自由基的清除能力最强, 化合物3e对DPPH•自由基的清除效率最高. 本研究为开发新型、特别是适用于加热不燃烧卷烟的风味物质提供了新的候选化合物, 其在烟草产品配方以及食品添加剂等领域具有良好的应用前景.

关键词: 羟醛缩合, 苯基烯醛, 香精香料, 热行为, 抗氧化

Phenylalkenal compounds, due to the presence of aroma-contributing groups such as aromatic rings and aldehyde groups in their molecular structure, are a key class of odorants with significant applications in the flavor and fragrance industry. A series of six novel phenylalkenals were synthesized via a cross-aldol condensation of phenylacetaldehyde with various alkyl aldehydes using sodium acetate as a base in anhydrous ethanol. The resulting compounds were characterized by nuclear magnetic resonance (¹H NMR, ¹³C NMR), infrared spectroscopy (IR), and high-resolution mass spectrometry (HRMS). Their odor characteristics were evaluated by a sensory panel. Their thermal behaviors were analyzed by thermogravimetry-derivative thermogravimetry (TG-DTG), and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). TG-DTG analysis deter- mined the temperature range corresponding to 90% mass loss and the temperature at the maximum mass loss rate for each compound. The results revealed that, with the exception of compound 3d, the other five compounds satisfied the volatility requirements for flavor compounds in heat-not-burn (HNB) cigarettes. Additionally, Py-GC/MS studies at 400  ℃ showed that all six compounds underwent partial pyrolysis, generating various aromatic products that contributed to flavor profiles. The antioxidant evaluation revealed that all six compounds exhibited significant antioxidant activity. Notably, compound 3c demonstrated the strongest scavenging capacity toward ABTS^＋•, while compound 3e showed the highest scavenging efficiency against DPPH•. This study provides new candidate compounds for the development of novel flavor substances, particularly those suitable for HNB cigarettes, with promising potential in areas such as tobacco product formulation and food additives.

Key words: aldol condensation, phenylalkenal, flavor and fragrance, thermal behavior, antioxidation

引用此文

许嘉龙, 王旭锋, 岳亭廷, 李媛媛, 姬小明, 程彪. 苯基烯醛呈香物质的合成、热解及其抗氧化活性研究[J]. 有机化学, 2026, 46(8): 3202-3211.

Jialong Xu, Xufeng Wang, Tingting Yue, Yuanyuan Li, Xiaoming Ji, Biao Cheng. Synthesis, Pyrolysis, and Antioxidant Activity of Phenylalkenal Odorants[J]. Chinese Journal of Organic Chemistry, 2026, 46(8): 3202-3211.

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Compound	Odor description
3a	Balsamic fragrance; cocoa fragrance
3b	Balsamic fragrance; cocoa fragrance
3c	Citrus green fragrance; cocoa fragrance
3d	Citrus green fragrance; rose fragrance
3e	Vanilla-like; sweet spicy
3f	Fresh floral; sweet spicy

Compound	Odor description
3a	Balsamic fragrance; cocoa fragrance
3b	Balsamic fragrance; cocoa fragrance
3c	Citrus green fragrance; cocoa fragrance
3d	Citrus green fragrance; rose fragrance
3e	Vanilla-like; sweet spicy
3f	Fresh floral; sweet spicy

Compound	T_range^a/℃	T_p^b/℃
3a	83~304	211
3b	94~348	213
3c	92~459	221
3d	118~524	255
3e	187~321	293
3f	92~338	294

Compound	T_range^a/℃	T_p^b/℃
3a	83~304	211
3b	94~348	213
3c	92~459	221
3d	118~524	255
3e	187~321	293
3f	92~338	294

Peak	r.t./min	Pyrolysis product	Match	Relative content/%
1	8.38	Octanal	98	8.3
2	12.78	Octanoic acid	96	22.5
3	17.79	2-Phenyldecanal	85	17.7
4	18.15	Compound 3a	96	30.2