焦甜香料2,4-二羟基-2,5-二甲基-3(2H)-呋喃酮的制备及加香应用  

Synthesis and flavoring application of caramel like 2,4-dihydroxy-2,5-dimethyl-3(2H)-furan-3-one

作　　者：白冰 赵明林 何静 杨静 张改红 杨靖 BAI Bing;ZHAO Minglin;HE Jing;YANG Jing;ZHANG Gaihong;YANG Jing(School of Food and Biological Engineering,Zhengzhou University of Light Industry,Zhengzhou 450000,Henan,China)

机构地区：[1]郑州轻工业大学食品与生物工程学院,河南郑州450000

出　　处：《精细化工》2023年第8期1776-1782,共7页Fine Chemicals

基　　金：河南省科技攻关计划项目(192102110212)。

摘　　要：呋喃酮经乙酰氧化反应和Novozym435脂肪酶脱乙酰基反应合成了2,4-二羟基-2,5-二甲基-3(2H)-呋喃酮。目标产物结构经1HNMR、^(13)CNMR和HRMS确证,利用热裂解-气相色谱-质谱联用法对其在卷烟中的迁移、裂解行为进行了模拟测定,并将其添加到卷烟中进行感官评价。结果表明,乙酰氧化反应最优条件为:呋喃酮10 mmol、甲苯为溶剂、无水四乙酸铅为乙酰氧化试剂、n(无水四乙酸铅)∶n(呋喃酮)=3∶1、反应温度90℃、反应时间6 h。脱乙酰基反应的最佳条件为:底物浓度为0.8 mol/L、Novozym435脂肪酶用量为底物质量(500 mg)的10%、2.8 m L磷酸盐缓冲溶液(pH为8.0)为溶剂、反应温度为40℃、反应时间12 h。在上述条件下,产物产率分别为90%和79%。目标产物在卷烟中以直接迁移为主,同时可裂解释放出具有焦甜香气的香味物质2,3-二氢-3,5-二羟基-6-甲基-4(H)吡喃-4-酮、呋喃酮、麦芽酚等;目标产物以卷烟烟丝质量的0.002%加入到卷烟中,可以显著提升焦甜香韵、改善口感;添加目标产物卷烟与对照卷烟烟气危害指数无显著差别,表明其在卷烟中使用安全。2,4-Dihydroxy-2,5-dimethyl-3(2H)-furan-3-one was synthesized from furanone via acetyloxidation reaction and Novozym435 lipase deacetylation reaction,and confirmed by 1HNMR,^(13)CNMR and HRMS.The product obtained was then added into cigarettes,analyzed for its migration and thermal pyrolysis behavior by simulation using pyrolysis-gas chromatography-mass spectrometry as well as for sensory appraisal.The results indicated that the optimal reaction conditions were 10 mmol furanone,toluene as solvent,anhydrous lead tetraacetate as acetyloxidation reagent,n(anhydrous lead tetraacetate)∶n(furanone)=3∶1,reaction temperature 90℃,reaction time 6 h,while the optimal conditions of deacetylating reaction were as follows:substrate concentration of 0.8 mol/L,dosage of Novozym435 lipase being 10%of substrate mass(500 mg),2.8 mL phosphate buffer solution(pH 8.0)as solvent,reaction temperature 40℃,and reaction time 12 h.Under the above conditions,the product yields reached 90%and 79%,respectively.The target product was distributed in the cigarettes mainly through direct migration and pyrolyzed into substances with scorching sweet aroma,such as 2,3-dihydro-3,5-dihydroxy-6-methyl-4(H)-furan-4-one,furanone,maltol and other aromatic components.The target product was added into the cigarette with 0.002%of the mass of cut tobacco,which could significantly improve the flavor and enhance the caramel aroma quality.Meanwhile,there was no significant difference in smoke hazard index between cigarettes added with the target product and the control,which indicated its safety for usage in cigarettes.

关 键 词：2 4-二羟基-2 5-二甲基-3(2H)-呋喃酮 焦甜香 合成 热裂解 Novozym435脂肪酶 香精与香料 

分 类 号：TS264.3[轻工技术与工程—发酵工程]