乙基麦芽酚丁二酸双酯的合成、热解及抗氧化研究

doi:10.6023/cjoc202311011

有机化学 ›› 2024, Vol. 44 ›› Issue (5): 1526-1534.DOI: 10.6023/cjoc202311011 上一篇下一篇

研究论文

乙基麦芽酚丁二酸双酯的合成、热解及抗氧化研究

于兆锦^a,†, 张展^b,†, 王海洋^a, 王波^c, 付光明^a, 张瑛^a, 杨晓朋^a^,^*(), 董爱君^c^,^*(), 姬小明^a^,^*()

a 河南农业大学烟草学院河南省香精香料与调香工程技术研究中心郑州 450046
b 河南中烟工业有限责任公司技术中心郑州 450000
c 湖北中烟工业有限责任公司技术中心武汉 430030

收稿日期:2023-11-09 修回日期:2024-01-18 发布日期:2024-02-07
作者简介:
†共同第一作者
基金资助:
湖北中烟工业有限责任公司(2021JSXL3JS2C032); 河南农业大学博士科研资金(30501420)

Study on Synthesis, Pyrolysis and Antioxidation of Ethyl Maltol Succinate Diester

Zhaojin Yu^a,†, Zhan Zhang^b,†, Haiyang Wang^a, Bo Wang^c, Guangming Fu^a, Ying Zhang^a, Xiaopeng Yang^a(), Aijun Dong^c(), Xiaoming Ji^a()

a Flavors and Fragrance Engineering & Technology Research Center of Henan Province, College of Tobacco Science, Henan Agricultural University, Zhengzhou 450046
b Technology Center, China Tobacco Henan Industrial Co., Ltd., Zhengzhou 450000
c Technology Center, China Tobacco Hubei Industrial Co., Ltd., Wuhan 430030

Received:2023-11-09 Revised:2024-01-18 Published:2024-02-07
Contact: *E-mail: xiaopengyang@henau.edu.cn; 19281034@qq.com; xiaomingji@henau.edu.cn
About author:
†These authors contributed equally to this work.
Supported by:
China Tobacco Hubei Industrial Co., Ltd.(2021JSXL3JS2C032); Doctoral Scientific Research Fund of Henan Agricultural University(30501420)

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摘要/Abstract

为了开发具有稳定性的焦甜香韵化合物, 以丁二酸酐、香味醇和乙基麦芽酚为原料, 两步法得到9种乙基麦芽酚丁二酸双酯类化合物2-乙基-4-氧代-4H-吡喃-3-基苯乙基丁二酸酯(5a)~2-乙基-4-氧代-4H-吡喃-3-基(2-甲基烯丙基)丁二酸酯(5i), 并对其进行结构鉴定、热稳定性和体外抗氧化性研究. 结果表明, 化合物5a~5i具有焦甜香韵, 同时还兼具其它香韵. 化合物5a和2-乙基-4-氧代-4H-吡喃-3-基丁二酸肉桂酯(5b)最大失重率的温度高于原料的温度, 热解时能产生大量乙基麦芽酚和香味醇等物质. 化合物5a的1,1-二苯基-2-三硝基苯肼(DPPH)和•OH清除能力高于化合物5b~5i和乙基麦芽酚. 综上所述, 化合物5a具有焦甜香韵, 且表现出较高的热稳定性和体外抗氧化能力, 为提高香料的稳定性和拓展其多功能应用开辟了新的途径.

关键词: 乙基麦芽酚, 酯化, 热裂解, 抗氧化, 香料香精

In order to develop burnt sweet fragrance compounds with stability. In this paper, nine ethyl maltol succinate diester compounds 2-ethyl-4-oxo-4H-pyran-3-yl phenethyl succinate (5a)~2-ethyl-4-oxo-4H-pyran-3-yl (2-methylallyl) succinate (5i) were obtained by a two-step method using succinic anhydride, flavor alcohols and ethyl maltol as raw materials, and were subjected to structural characterization, thermal stability and in vitro antioxidant studies. The results showed that compounds 5a~5i possessed a burnt sweet fragrance as well as other fragrances. Compounds 5a and cinnamyl (2-ethyl-4-oxo- 4H-pyran-3-yl) succinate (5b) had a highest weight loss at a temperature higher than that of raw materials, and a large amount of substances such as ethyl maltol and flavor alcohols were produced during pyrolysis. The 1,1-diphenyl-2-picrylhydrazyl (DPPH) and •OH scavenging abilities of compound 5a are higher than those of compounds 5b~5i and ethyl maltol. In summary, compound 5a has a burnt sweet fragrance, and exhibits high thermal stability and in vitro antioxidant capacity. This work may provide a new method to improve the stability of spices and expand their multifunctional application.

Key words: ethyl maltol, esterification, pyrolysis, antioxidant, flavors and fragrances

引用此文

于兆锦, 张展, 王海洋, 王波, 付光明, 张瑛, 杨晓朋, 董爱君, 姬小明. 乙基麦芽酚丁二酸双酯的合成、热解及抗氧化研究[J]. 有机化学, 2024, 44(5): 1526-1534.

Zhaojin Yu, Zhan Zhang, Haiyang Wang, Bo Wang, Guangming Fu, Ying Zhang, Xiaopeng Yang, Aijun Dong, Xiaoming Ji. Study on Synthesis, Pyrolysis and Antioxidation of Ethyl Maltol Succinate Diester[J]. Chinese Journal of Organic Chemistry, 2024, 44(5): 1526-1534.

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参考文献 22

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Yield/% of 3	Yield/% of 5	Odor description of 5
83	46	Burnt sweet fragrance, rose fragrance, herb fragrance
80	55	Burnt sweet fragrance, alco- hol fragrance, bean aroma, herb fragrance
85	56	Burnt sweet fragrance, frui- ty flavour, nut fragrance
81	44	Burnt sweet fragrance, frui- ty flavour, nut fragrance
87	57	Burnt sweet fragrance, alco- hol fragrance, fruity flavour
87	62	Sour flavor, burnt sweet fragrance, spicy fragrance
86	46	Burnt sweet fragrance, sour flavor, fat wax fragrance
82	50	Burnt sweet fragrance, ba- ked fragrance, spicy frag- rance, fat wax fragrance
85	49	Burnt sweet fragrance, gra- ss fragrance, fruity flavour, sour flavor

Yield/% of 3	Yield/% of 5	Odor description of 5
83	46	Burnt sweet fragrance, rose fragrance, herb fragrance
80	55	Burnt sweet fragrance, alco- hol fragrance, bean aroma, herb fragrance
85	56	Burnt sweet fragrance, frui- ty flavour, nut fragrance
81	44	Burnt sweet fragrance, frui- ty flavour, nut fragrance
87	57	Burnt sweet fragrance, alco- hol fragrance, fruity flavour
87	62	Sour flavor, burnt sweet fragrance, spicy fragrance
86	46	Burnt sweet fragrance, sour flavor, fat wax fragrance
82	50	Burnt sweet fragrance, ba- ked fragrance, spicy frag- rance, fat wax fragrance
85	49	Burnt sweet fragrance, gra- ss fragrance, fruity flavour, sour flavor

Peak	Retention time/min	Pyrolysis product	Structure	Match	Relative content/%
Peak	Retention time/min	Pyrolysis product	Structure	Match	300 ℃	350 ℃	400 ℃
Compound 5a
1	9.12	Succinic anhydride		91	0.10	0.56	2.15
2	11.78	Phenethyl alcohol		94	6.64	10.42	12.40
3	15.23	Ethyl maltol		94	79.88	82.98	83.47
4	31.58	4-((2-Ethyl-4-oxo-4H-pyran-3-yl)oxy)- 4-oxobutanoic acid		90	1.53	0.32	—
Compound 5b
1	16.36	Ethyl maltol		94	77.81	79.98	81.41
2	19.39	Cinnamyl alcohol		96	11.10	12.30	15.11
3	31.51	4-((2-Ethyl-4-oxo-4H-pyran-3-yl)oxy)- 4-oxobutanoic acid		91	1.17	0.92	0.09
4	36.15	4-(Cinnamyloxy)-4-oxobutanoic acid		98	2.97	0.09	—

Peak	Retention time/min	Pyrolysis product	Structure	Match	Relative content/%
Peak	Retention time/min	Pyrolysis product	Structure	Match	300 ℃	350 ℃	400 ℃
Compound 5a
1	9.12	Succinic anhydride		91	0.10	0.56	2.15
2	11.78	Phenethyl alcohol		94	6.64	10.42	12.40
3	15.23	Ethyl maltol		94	79.88	82.98	83.47
4	31.58	4-((2-Ethyl-4-oxo-4H-pyran-3-yl)oxy)- 4-oxobutanoic acid		90	1.53	0.32	—
Compound 5b
1	16.36	Ethyl maltol		94	77.81	79.98	81.41
2	19.39	Cinnamyl alcohol		96	11.10	12.30	15.11
3	31.51	4-((2-Ethyl-4-oxo-4H-pyran-3-yl)oxy)- 4-oxobutanoic acid		91	1.17	0.92	0.09
4	36.15	4-(Cinnamyloxy)-4-oxobutanoic acid		98	2.97	0.09	—

乙基麦芽酚丁二酸双酯的合成、热解及抗氧化研究

Study on Synthesis, Pyrolysis and Antioxidation of Ethyl Maltol Succinate Diester

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