巨豆三烯酮前体物的合成及其热解作用

廖付; 田雨农; 李庆祥; 李石头; 许利平; 白冰; 赵振杰; 何文苗

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Citation: . shu

Synthesis of megastigmatrienone precursors and their pyrolysis properties

LIAO Fu ¹ ,
TIAN Yunong ¹ ,
LI Qingxiang ¹ ,
LI Shitou ¹ ,
XU Liping ¹ ,
BAI Bing ² ,
ZHAO Zhenjie ¹ ,
HE Wenmiao ^1,,

1. Technology Center, China Tobacco Zhejiang Industrial Co., Ltd., Hangzhou 310000, China;
2. College of Tobacco Science and Engineering, Zhengzhou University of Light Industry, Zhengzhou 450001, China

Corresponding author: HE Wenmiao, henwenmiao@zjtobacco.com
Received Date: 2024-11-08
Accepted Date: 2024-12-25
Available Online: 2025-08-26

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.
- 3-oxo-α-ionol carbonate,
- megastigmatrienone,
- precursor,
- cigarette flavoring,
- pyrolysis
References
1. [1]
  WU M C,MA Y,YIN J J,et al. Selenium content,chemical composition and volatile components of essential oil and hydrosol from flowers of Cardamine violifolia[J]. Chemistry&Biodiversity,2024,21(2):e202301428.
2. [2]
  VAN H T,NGUYEN T T,TON H T T,et al. Phytochemical composition and antibacterial activity of ethanolic extract from trunk of Rothmannia wittii (Craib) Bremek.(Rubiaceae) newly found in Vietnam[J]. BioTechnologia,2020,101(4):301-307.
3. [3]
  BUGHIO S H,SAMEJO M Q,MEMON S,et al. Chemical composition of the essential oils from Tamarix dioica and determination of its antibacterial activity[J]. International Journal of Food Properties,2018,20:2660-2667.
4. [4]
  RATHER S A,AHMAD MIR N,HUSSAIN P R,et al. Free and glycosidically bound volatile compounds in quince (Cydonia oblonga Mill) from Kashmir,India[J]. Food Chemistry Advances,2024,4:100608.
5. [5]
  ATOLANI O, ADEOSUN C B, OLUYORI A P, et al. Chemical composition and antioxidant activity of the essential oils from white and green leaves of Nigeria-grown Ficus microcarpa[J]. Rasayan Journal of Chemistry,2019, 12(3):1052-1057.
6. [6]
  MAGOME H,ARAI M,OYAMA K,et al. Multiple loss-offunction mutations of carotenoid cleavage dioxygenase 4 reveal its major role in both carotenoid level and apocarotenoid composition in flue-cured mature tobacco leaves[J]. Scientific Reports,2023,13(1):12992.
7. [7]
  张仲文,祖朝龙,张保全,等.土壤理化性质与烤烟巨豆三烯酮含量的灰色关联度分析[J].中国农学通报, 2016,32(9):174-178.
8. [8]
  杨靖,毛多斌,陈芝飞,等. GC-MS/O技术测定卷烟烟气中巨豆三烯酮的香气活力值[J].中国烟草学报, 2016,22,(6):11-17.
9. [9]
  XIE R G,YANG M,PENG Q R,et al. CaCl₂-or MgCl₂-catalyzed allylic oxidations of ionone-like dienes[J]. Synlett,2006,2006(16):2617-2620.
10. [10]
  王建林,杨少龙,许炎妹,等.巨豆三烯酮的合成及表征[J].光谱学与光谱分析,2005,25(3):467-469.
11. [11]
  沈杰,梁德民,沙云菲,等.一种基于新型起始原料的巨豆三烯酮合成方法[J].上海大学学报(自然科学版),2023,29(3):562-568.
12. [12]
  KIM M J,KIM M,KIM S,et al. Feasibility study on the homogeneity and stability of megastigmatrienone isomers for the development of certified reference material[J]. Journal of Food Composition and Analysis,2023,123:105573.
13. [13]
  刘云飞,郭琪,姬小明,等.巨豆三烯酮-β-环糊精包合物的制备及其卷烟加香应用[J].陕西科技大学学报, 2022,40(4):94-99.
14. [14]
  陈振玲,张浩博,周宛虹,等.烟草中3-氧代-α-紫罗兰醇-β-D-吡喃葡萄糖苷的分离鉴定及其热解产物分析[J].烟草科技,2008,41(7):28-31.
15. [15]
  陈敏,董惠忠,沈世豪,等.中心切割反相/反相二维液相色谱-串联质谱法测定烟叶潜香类糖苷[J].质谱学报,2021,42(6):1175-1182.
16. [16]
  李石头,毕一鸣,帖金鑫,等.基于UHPLC法的巨豆三烯酮前体物同分异构体的定量分析及其在不同产地烟叶中的分布情况[J].轻工学报,2023,38(5):83-87.
17. [17]
  张改红,白冰,杨静,等. 3-氧代-α-紫罗兰醇-β-D-葡萄糖苷的合成[J].化学世界,2016,57(5):303-307.
18. [18]
  刘建福,杨华武,李克,等.氧代-α-紫罗兰醇碳酸乙酯的合成及其向卷烟烟气释放巨豆三烯酮的研究[J].中国烟草学报,2001,7(2):13-16.
19. [19]
  MA T T,XU C,LIU F Y,et al. Selective epoxidation and allylic oxidation of olefins catalyzed by BEA-Ti and porphyrin catalysts[J]. Molecular Catalysis,2023,541:113074.
20. [20]
  蒋举兴,孔维松,吴俊,等.香精中巨豆三烯酮E/Z异构体的相对量比和在4种常用气相色谱柱上的出峰顺序[J].云南大学学报(自然科学版),2018,40(5):984-994.
21. [21]
  帖金鑫,张青松,李永生,等.加拿大烟叶与云南KRK26烟叶香气成分差异分析[J].轻工学报,2023, 38(5):74-81.
22. [22]
  李俊丽,叶协锋,赵莉,等.豫中浓香型烤烟香气质量与中性致香成分关系分析[J].山西农业科学,2012, 40(12):1268-1272.
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沈阳化工大学材料科学与工程学院沈阳 110142

Synthesis of megastigmatrienone precursors and their pyrolysis properties

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