γ-己内酯

γ-己内酯
英文名	γ-hexalactone
别名	乙基丁内酯、; γ-乙基正丁内酯、; 4-羟基己酸-γ-内酯、; 1,4-己内酯
识别
CAS号	695-06-7
PubChem	12756
ChemSpider	12232
SMILES	CCC1CCC(=O)O1;
InChI	InChI=1S/C6H10O2/c1-2-5-3-4-6(7)8-5/h5H,2-4H2,1H3;
InChIKey	JBFHTYHTHYHCDJ-UHFFFAOYSA-N
ChEBI	85235
性质
化学式	C6H10O2
摩尔质量	114.14 g·mol−1
外观	无色液体，香豆素似草药气味
熔点	−22.87 °C
沸点	211.41 °C
溶解性（水）	极微溶于水，溶于乙醇和丙二醇
危险性
闪点	>93°C
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

γ-己内酯（英語：γ-hexalactone），别名乙基丁内酯，是一种内酯化合物，化学式C₆H₁₀O₂。天然存在于许多动植物中，同时也是一种可食用香精。

性质与用途

γ-己内酯外观上为无色液体，具有温和香豆素样药草气味或烟草味^[1]，以及甜和浓郁的焦糖样和香豆素样味道^[2]。熔点为-22.87°C、沸点211.41 °C，水中溶解度为32.19 g/L^[1]。

工业上主要用作香精、常用作香豆素的修饰剂，如用在薰衣草、香薇以及用橡苔作香增甜剂等香型中。在食品香精中运用较广，利用其浓甜而带奶甜香味，可用作奶油、蜜香、香荚兰、焦糖、果香和烟草香精。能与香兰素很好协调，以此在香荚兰和奶油香精中来代替不可食用香豆素^[2]。

2015年根据国际日用香精协会（英语：International Fragrance Association）（IFRA）统计，γ-己内酯全球消耗量约为1-10吨^[1]。

自然分布

γ-己内酯在自然界中存在于许多动植物中，如陆地棉^[3]、芒果树^[4]^[5]^[1]、美远志^[6]、百香果、西印度樱桃、杏子、桃、油桃、覆盆子、黑莓、波森莓、茶叶、烟草^[7]等。动物中可见于奶以及奶制品中^[1]。

对于杏子而言，γ-己内酯是成分最多的几种内酯类特征风味物质之一，其存在R和S两种对映异构体，R构型在杏子中占总γ-己内酯含量的69-96%^[8]。

R构型的γ-己内酯是黑斑皮蠹（Trogoderma glabrum）^[9]和谷斑皮蠹（Trogoderma granarium）^[10]的性信息素之一。

在牛肉中，γ-己内酯是牛肉大理石花纹中特征香味成分之一，其由亚油酸经酶转化得到^[11]。

制备

γ-己内酯有多种制备方式，包括^[2]：

山梨酸在85°C醋酸溶液中采用ZnCl₂-浓盐酸（卢卡斯试剂）或SnCl₂-浓盐酸进行还原得到
环氧乙烷和钠代丙二酸酯（Sodio Malonic Ester，Na[CH(COOR)₂]）反应制取得到
正丙醇和丙烯酸甲酯在二叔丁基过氧化物作用下反应得到。

参考资料

^ ^1.0 ^1.1 ^1.2 ^1.3 ^1.4 A.M. Api, D. Belsito, D. Botelho; et al. RIFM fragrance ingredient safety assessment, γ-hexalactone, CAS Registry Number 695-06-7. Food and Chemical Toxicology. 2022, 167 (S1): 113278. doi:10.1016/j.fct.2022.113278.
^ ^2.0 ^2.1 ^2.2 许戈文,李布青. 合成香料产品技术手册. 北京: 中国商业出版社. 1996: 194–195.
^ P. A. Hedin; A. C. Thompson; R. C. Gueldner. A survey of the volatile constituents of cotton lint and waste with regard to byssinosis. Journal of Agricultural and Food Chemistry. 1975-07, 23 (4). doi:10.1021/JF60200A011 （英语）.
^ Jorge A Pino; Judith Mesa; Yamilie Muñoz; M Pilar Martí; Rolando Marbot. Volatile components from mango (Mangifera indica L.) cultivars. Journal of Agricultural and Food Chemistry. 2005-02, 53 (6). doi:10.1021/JF0402633 （英语）.
^ Sagar S. Pandit; Hemangi G. Chidley; Ram S. Kulkarni; Keshav H. Pujari; Ashok P. Giri; Vidya S. Gupta. Cultivar relationships in mango based on fruit volatile profiles. Food Chemistry. 2008-10, 114 (1). doi:10.1016/J.FOODCHEM.2008.09.107.
^ Shuichi Hayashi; Hiromu Kameoka. Volatile compounds of Polygala senega L. var.latifolia Torrey et Gray roots. Flavour and Fragrance Journal. 2006-11, 10 (4). doi:10.1002/FFJ.2730100408.
^ Alan Rodgman, Thomas A. Perfetti. The Chemical Components of Tobacco and Tobacco Smoke,. CRC Press. 2016. ISBN 978-1-4665-1552-9.
^ Elizabeth Guichard, Angelika Kustermann, Armin Mosandl. Chiral flavor compounds from apricots : Distribution of γ-lactone enantiomers and steoredifferentiation of dihydroactinidiolide using multi-dimensional gas chromotography. Journal of Chromatography A. 1990, 498: 396-401. doi:10.1016/S0021-9673(01)84268-0.
^ Elena Arceo, José M. Odriozola, Jesús M. Garcı́a, Alberto González, Pilar Gil. Asymmetric synthesis of (R)-4-hexanolide, the pheromone of Trogoderma glabrum. Tetrahedron: Asymmetry. 2003, 14 (2): 1617-1621. doi:10.1016/S0957-4166(03)00327-6.
^ M. Teresa Nunez, Victor S. Martin. Efficient oxidation of phenyl groups to carboxylic acids with ruthenium tetraoxide. A simple synthesis of (R)-.gamma.-caprolactone, the pheromone of Trogoderma granarium. The Journal of Organic Chemistry. 1990, 55 (6): 1928-1932. doi:10.1021/jo00293a044.
^ Shuji Ueda, Mana Hosoda, Kumi Kasamatsu，; et al. Production of Hydroxy Fatty Acids, Precursors of γ-Hexalactone, Contributes to the Characteristic Sweet Aroma of Beef. Metabolites. 2022, 12 (4): 332. doi:10.3390/metabo12040332.

[:0-1] 1.0 ^1.1 ^1.2 ^1.3 ^1.4 A.M. Api, D. Belsito, D. Botelho; et al. RIFM fragrance ingredient safety assessment, γ-hexalactone, CAS Registry Number 695-06-7. Food and Chemical Toxicology. 2022, 167 (S1): 113278. doi:10.1016/j.fct.2022.113278.

[:1-2] 2.0 ^2.1 ^2.2 许戈文,李布青. 合成香料产品技术手册. 北京: 中国商业出版社. 1996: 194–195.

[3] P. A. Hedin; A. C. Thompson; R. C. Gueldner. A survey of the volatile constituents of cotton lint and waste with regard to byssinosis. Journal of Agricultural and Food Chemistry. 1975-07, 23 (4). doi:10.1021/JF60200A011 （英语）.

[4] Jorge A Pino; Judith Mesa; Yamilie Muñoz; M Pilar Martí; Rolando Marbot. Volatile components from mango (Mangifera indica L.) cultivars. Journal of Agricultural and Food Chemistry. 2005-02, 53 (6). doi:10.1021/JF0402633 （英语）.

[5] Sagar S. Pandit; Hemangi G. Chidley; Ram S. Kulkarni; Keshav H. Pujari; Ashok P. Giri; Vidya S. Gupta. Cultivar relationships in mango based on fruit volatile profiles. Food Chemistry. 2008-10, 114 (1). doi:10.1016/J.FOODCHEM.2008.09.107.

[6] Shuichi Hayashi; Hiromu Kameoka. Volatile compounds of Polygala senega L. var.latifolia Torrey et Gray roots. Flavour and Fragrance Journal. 2006-11, 10 (4). doi:10.1002/FFJ.2730100408.

[7] Alan Rodgman, Thomas A. Perfetti. The Chemical Components of Tobacco and Tobacco Smoke,. CRC Press. 2016. ISBN 978-1-4665-1552-9.

[8] Elizabeth Guichard, Angelika Kustermann, Armin Mosandl. Chiral flavor compounds from apricots : Distribution of γ-lactone enantiomers and steoredifferentiation of dihydroactinidiolide using multi-dimensional gas chromotography. Journal of Chromatography A. 1990, 498: 396-401. doi:10.1016/S0021-9673(01)84268-0.

[9] Elena Arceo, José M. Odriozola, Jesús M. Garcı́a, Alberto González, Pilar Gil. Asymmetric synthesis of (R)-4-hexanolide, the pheromone of Trogoderma glabrum. Tetrahedron: Asymmetry. 2003, 14 (2): 1617-1621. doi:10.1016/S0957-4166(03)00327-6.

[10] M. Teresa Nunez, Victor S. Martin. Efficient oxidation of phenyl groups to carboxylic acids with ruthenium tetraoxide. A simple synthesis of (R)-.gamma.-caprolactone, the pheromone of Trogoderma granarium. The Journal of Organic Chemistry. 1990, 55 (6): 1928-1932. doi:10.1021/jo00293a044.

[11] Shuji Ueda, Mana Hosoda, Kumi Kasamatsu，; et al. Production of Hydroxy Fatty Acids, Precursors of γ-Hexalactone, Contributes to the Characteristic Sweet Aroma of Beef. Metabolites. 2022, 12 (4): 332. doi:10.3390/metabo12040332.

[1]

[2]

[3]

[4]

[5]

[6]

[7]

[8]

[9]

[10]

[11]