Please wait a minute...
浙江大学学报(工学版)
J4  2013, Vol. 47 Issue (4): 728-734    DOI: 10.3785/j.issn.1008-973X.2013.04.025
化学与环境工程     
维生素A醋酸酯热处理下结构变化研究
尹红, 俞安, 袁慎峰, 陈志荣
浙江大学 化学工程与生物工程系,浙江 杭州 310027
Structure stability of vitamin A acetate in heating
YIN Hong, YU An, YUAN Shen-feng, CHEN Zhi-rong
Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China
 全文: PDF  HTML
摘要：

通过模拟生产工艺及存储条件,考察维生素A醋酸酯在避光、无氧时热处理条件下的变质情况,研究产物的可能结构及副产物类型.结果表明,维生素A醋酸酯主要发生由热引发的异构化和Diels-Alder环合二聚反应,通过GPC、HPLC-DAD、LC-MS分析检测得到产物结构.利用TS方法计算并比较各维生素A醋酸酯异构体进行二聚反应所需的活化能,得到Diels-Alder反应生成二聚物的环合反应过程为：一分子全反式维生素A醋酸酯经异构化为顺式异构体,该异构体作为亲双烯体与作为双烯体的另一分子全反式维生素A醋酸酯进行反应生成二聚体.利用含微扰效应的分子前沿轨道理论计算区域选择性不同的二聚体的生成微扰能变化值,得到最可能的6种二聚体结构.
Abstract:

The heat-induced degeneration products of vitamin A acetate and the plausible mechanism were analyzed under oxygen-free and light-free condition that vitamin A acetate was processed, stored and used. GPC、HPLC-DAD and LC-MS results showed that two reactions, namely isomerization and Diels-Alder reaction, were predominated in this process. The activation energy of the Diels-Alder reaction between various vitamin A acetate isomers was calculated with the transition state theory. Results showed that the dimers were mainly produced by the Diels-Alder reaction between trans-vitamin A acetate (act as diene) and cis-vitamin A acetate (act as dienophile), where cis-vitamin A acetate was the isomerization product of trans-vitamin A acetate. The most probable structures of the six dimers were presented by comparing the energy change in perturbational molecular orbital theory for different regioselectivity of the Diels-Alder reaction.
出版日期: 2013-04-01
:  TQ 466.1  
基金资助:

国家“863”高技术研究发展计划资助项目（2009AA033301）；浙江省重点科技创新团队计划资助项目（2011R50007）.
通讯作者: 袁慎峰,男,副教授.     E-mail: ysf@zju.edu.cn
作者简介: 尹红（1971—）,女,副教授,从事反应工程和应用化学的研究.E-mail: yinh@zju.edu.cn
服务　　
把本文推荐给朋友
加入引用管理器
E-mail Alert
RSS
作者相关文章　　

引用本文:

尹红, 俞安, 袁慎峰, 陈志荣. 维生素A醋酸酯热处理下结构变化研究[J]. J4, 2013, 47(4): 728-734.

YIN Hong, YU An, YUAN Shen-feng, CHEN Zhi-rong. Structure stability of vitamin A acetate in heating. J4, 2013, 47(4): 728-734.

链接本文:

http://www.zjujournals.com/eng/CN/10.3785/j.issn.1008-973X.2013.04.025    或    http://www.zjujournals.com/eng/CN/Y2013/V47/I4/728

［1］ 李专成.维生素A合成工艺评述［J］.化学工程与装备,2009(2): 95-100.

LI Zhuan-cheng. Review on the vitamin A synthesis process ［J］. Chemical Engineering and Equipment, 2009(2): 95-100.

［2］ 任国谱,颜景超.乳制品中维生素A稳定性的研究进展［J］.中国乳品工业,2009,37(10): 34-38.

REN Guo-pu, YAN Jing-chao. Research advance in stability of Vitamin A in dairy products ［J］.China Dairy Industry, 2009, 37(10): 34-38.

［3］ LOVEDAY S, SINGH H. Recent advances in technologies for vitamin A protection in foods ［J］. Trends in FoodScience and Technology, 2008, 19(12): 657-668.

［4］ CRANK G, PARDIJANTO M S. Photo-oxidations and photosensitized oxidations of vitamin A and its palmitate ester ［J］. Journal of Photochemistry and Photobiology A: Chemistry, 1995, 85 (1/2): 93-100.

［5］ KOZLOV E,IVANOVA R,SAVOSINA L. Oxidation of vitamin A acetate in soybean oil ［J］. Technology, 1971, 5(10): 24-29.

［6］ FAILOUX N, BONNET I, PERRIER E, et al. Effects of light, oxygen and concentration on vitamin A1 ［J］. Journal of Raman Spectroscopy,2004, 35(2): 140-147.

［7］ ZYGOURA P, MOYSSIA T, BADEKA A, et al. Shelf life of whole pasteurized milk in Greece: effect of packaging material ［J］. Food Chemistry, 2004, 87(1): 1-9.

［8］ FRANK E, RUNGE R. Use of microcalorimetry in monitoring stability studies. example: vitamin A esters ［J］. Journal of Agricultural and Food Chemistry, 2000, 48(1): 47-55.

［9］ BAREND V, CHRISTOPH F. Diels-alder reactions. Part III. condensation of methyl trans-β-formylcrotonate with retinol acetate, with a note on the structure and stereochemistry of kitol ［J］. Journal of Chemical Society Perkin Transactions 1, 1973(6): 590-595.

［10］ BURGER B, GARBERS C. The structure of Kitol ［J］. Chemical Communications, 1965(22): 588-589.

［11］ CHARLEGS I, HUPESHC D, EDGARL E. The structure of Kitol ［J］. Chemical Communications, 1966 (1): 28-29.

［12］ SCHLOTTERBECK G, TSENG L H, HANDEL H, et al. Direct on-line coupling of capillary HPLC with 1H-NMR spectroscopy for the structural determination of retinyl acetate dimers: 2D NMR spectroscopy in the nanoliter scale ［J］. Analytical Chemistry, 1997, 69(7): 1421-1425.

［13］ HELMUT S. Separation and determination of the cis-trans of the vitamin A esters by high-performance liquid chromatography ［J］. Journal of Chromatography, 1981, 206(2): 319-326.

［14］ 邢其毅,裴伟伟,徐瑞秋,等.基础有机化学［M］.3版.北京：高等教育出版社,2005:167-169.

［15］ 马良,陈万锁,鲁波,等.手性α-烯丙基苯甲醇的立体选择性合成研究［J］.浙江大学学报:工学版,2006,40(1): 162-166.

MA Liang, CHEN Wan-suo, LU Bo, et al. Stereoselective synthesis of chiral α-allylbenzyl alcohol ［J］. Journal of Zhejiang University: Engineering Science, 2006, 40(1): 162-166.

［16］ 胡秀贞. 狄尔斯-阿尔德反应［J］.大学化学,1988, 3(5): 25-30.

HU Xiu-zhen. Diels-Alder reaction ［J］.Chemistry, 1988, 3(5): 25-30.

［17］ PETER V, MICHAEL D, RAPHAEL M O, et al. Secondary orbital interactions determining regioselectivity in the Diels-Alder reaction. 5. Thio-Substituted 1,3-Butadienes ［J］. The Journal of Organic Chemistry, 1983, 48(25): 5051-5054.

［18］ 周贺志,韩长日.Diels-Alder反应中的区域选择性与次级轨道效应［J］.安徽大学学报：自然科学版,1992(4): 73-78.

ZHOU He-zhi, HAN Chang-ri. The selectivity and subprime orbit the area effects on Diels-Alder reaction ［J］. Anhui University Journal: Science Edition, 1992(4): 73-78.

［19］ 仇丹,陈志荣,李浩然.热处理过程中β-胡萝卜素的副产物分析［J］.食品科学,2008,29（10）: 444-448.

QIU Dan, CHEN Zhi-rong, LI Hao-ran. Analysis of β-carotene byproducts during thermal processing ［J］.Food Science, 2008,29（10）: 444-448.

［20］ 韩长日,方渡.微扰分子轨道理论与Diels-Alder反应［J］.湖北师范学报:自然科学版,1986,5(2): 39-58.

HAN Chang-ri, FANG Du. Perturbational molecular orbital theory and Diels-Alder reaction ［J］. Hubei Normal Journal: Science Edition, 1986, 5(2): 39-58.

［21］ 徐珍珍.一些Diels-Alder反应的立体选择性的理论研究［D］.大连：辽宁师范大学,2008: 22-43.

XU Zhen-zhen. Theoretical investigation of the stereoselectivity of some Diels-Alder reactions \
[D\]. Dalian: Liaoning Normal University, 2008: 22-43.

［22］ 格里菲斯.颜色与有机分子结构［M］.侯毓汾,吴祖望,胡家振,等,译.北京：化学工业出版社,1985: 25-37.

［23］ 黄量,于德泉.紫外光谱在有机化学中的应用（上册）［M］.北京：科学出版社,2000: 45-119.
[1] 尹红, 俞安, 盛财平, 袁慎峰, 陈志荣. 三丁酸甘油酯中维生素A热处理反应产物研究[J]. J4, 2013, 47(12): 2170-2175.