5-甲基糠醇-β-D-葡萄糖苷的合成及热裂解
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摘要
为了开发新型糖苷类香料,首先以D-葡萄糖为原料,合成了溴代四乙酰葡萄糖(Ⅲ),再以5-甲基糠醛(Ⅰ)为原料,经还原制备了5-甲基糠醇(Ⅱ),化合物Ⅱ与Ⅲ进行糖苷化反应,分别采用Koenigs-Knorr法和相转移催化法,合成了5-甲基糠醇-2, 3, 4, 6-四-O-乙酰基-β-D-葡萄糖苷(Ⅳ);最后,将化合物Ⅳ水解,得到目标产物5-甲基糠醇-β-D-葡萄糖苷(Ⅴ)。中间体和产物结构经1HNMR、13CNMR、IR、HRMS确证,并对糖苷Ⅴ的热裂解性能进行了测定。结果表明:两种糖苷化方法所得到的产物均为糖苷Ⅳ,Koenigs-Knorr法更优。Koenigs-Knorr法的最佳反应条件为:n(5-甲基糠醇):n(溴代四乙酰葡萄糖)=1:1.6,n(5-甲基糠醇):n(Ag2CO3)=1:1.5,回流反应4 h,化合物Ⅳ的产率为42.9%。目标糖苷Ⅴ热裂解后能够释放出5-甲基糠醛、5-甲基糠醇等香味成分,可用于食品、烟草等行业。
To develop a new type of glycoside flavor, firstly, 2, 3, 4, 6-tetra-O-acetyl-α-D-glucopyranosyl bromide(Ⅲ) was synthesized from D-glucose. Then, 5-methyl furfuryl alcohol(Ⅱ) was prepared by a reduction reaction of 5-methylfurfural(Ⅰ). Subsequently, a glycosylation reaction between compounds Ⅲand Ⅱ led to 5-methyl furfuryl alcohol-2, 3, 4, 6-tetra-O-acetyl-β-D-glucoside(Ⅳ) by Koenigs-Knorr method and phase transfer catalysis method, respectively. Finally, the target compound 5-methyl furfuryl alcohol-β-D-glucoside(Ⅴ) was obtained by hydrolysis of compound Ⅳ. These compounds were confirmed by 1HNMR, 13 CNMR, IR and HRMS. The thermal pyrolysis of glucoside(Ⅴ) was also studied. The results indicated that the compound Ⅳ synthesized by the two above-mentioned methods was target product, the Koenigs-Knorr method was better than phase transfer catalysis method. The optimal conditions for the preparation of compound Ⅳ by Koenigs-Knorr method were as follows : n(5-methyl furfuryl alcohol) : n(2, 3, 4, 6-tetra-O-acetyl-α-D-glucopyranosyl bromide)=1 : 1.6, n(5-methyl furfuryl alcohol) : n(silver carbonate)=1 : 1.5, refluxing time for 4 h. Under these optimal conditions, the yield of compound Ⅳ reached 42.9%. The synthesized 5-methyl furfuryl alcohol-β-D-glucoside after pyrolysis could release 5-methyl furfural, 5-methyl furfuryl alcohol and other aromatic components, which could be used in food, tobacco and other industries.
To develop a new type of glycoside flavor, firstly, 2, 3, 4, 6-tetra-O-acetyl-α-D-glucopyranosyl bromide(Ⅲ) was synthesized from D-glucose. Then, 5-methyl furfuryl alcohol(Ⅱ) was prepared by a reduction reaction of 5-methylfurfural(Ⅰ). Subsequently, a glycosylation reaction between compounds Ⅲand Ⅱ led to 5-methyl furfuryl alcohol-2, 3, 4, 6-tetra-O-acetyl-β-D-glucoside(Ⅳ) by Koenigs-Knorr method and phase transfer catalysis method, respectively. Finally, the target compound 5-methyl furfuryl alcohol-β-D-glucoside(Ⅴ) was obtained by hydrolysis of compound Ⅳ. These compounds were confirmed by 1HNMR, 13 CNMR, IR and HRMS. The thermal pyrolysis of glucoside(Ⅴ) was also studied. The results indicated that the compound Ⅳ synthesized by the two above-mentioned methods was target product, the Koenigs-Knorr method was better than phase transfer catalysis method. The optimal conditions for the preparation of compound Ⅳ by Koenigs-Knorr method were as follows : n(5-methyl furfuryl alcohol) : n(2, 3, 4, 6-tetra-O-acetyl-α-D-glucopyranosyl bromide)=1 : 1.6, n(5-methyl furfuryl alcohol) : n(silver carbonate)=1 : 1.5, refluxing time for 4 h. Under these optimal conditions, the yield of compound Ⅳ reached 42.9%. The synthesized 5-methyl furfuryl alcohol-β-D-glucoside after pyrolysis could release 5-methyl furfural, 5-methyl furfuryl alcohol and other aromatic components, which could be used in food, tobacco and other industries.
引文
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[22]Li Guangliang(李广良). Synthesis of furazolidol esters[J]. Journal of Henan Science and Technology(河南科技), 1997,(2):20.
[23]Sun Bowang(孙柏旺), Zhang Yawen(张雅雯), Qian Donger(钱东尔), et al. A series of furan alcohol esters as sweet flavor precursors and its synthesis method:CN201710052594.4[P]. 2017-01-24.
[24]Zhang Weicheng(张维成), Sun Baoguo(孙宝国), Xu Liruan(徐理阮). Study on the ester flavorings of furoic acid and furfuryl alcohol[J]. Fine Chemicals(精细化工), 1994, 11(6):19-22.
[25]Yang Hongxi(杨洪锡), Xie Wancui(解万翠), Wang Weimin(王维民),etal.Synthesisandcharacterizationofβ-D-glucopyranosides flavor precursors[J]. Food Science(食品科学), 2007, 28(11):179-182.
[26]StephenA,HashmiK,HengstT,etal.Newandeasilyaccessible nitrogenacyclicgold(I)carbenes:Structureandapplicationinthe gold-catalyzed phenol synthesis as well as the hydration of alkynes[J]. Advanced Synthesis&Catalysis, 2010, 352(8):1315-1337.
[27]Zeng Hongyao(曾鸿耀), Liao Liangcong(廖良聪), Wang Yinghong(王英红).One-potsynthesisofper-O-acetylatedglycopyranosyl bromidesfromreducingsugars[J].ChemicalReagents(化学试剂),2013, 35(7):649-652.
[28]Ling Xunli(凌勋利). Synthesis of acetyglycosyl bromide[J]. Journal ofLuoyangNormalUniversity(洛阳师范学院学报),2008,27(2):75-77.
[29]Zhang Gaihong(张改红), Bai Bing(白冰), Yang Jing(杨静). Recent progress in synthesis of glycosides[J]. Chemistry(化学通报), 2014,77(4):306-311.
[30]Igarashi K. The Koenigs-Knorr reaction[J]. Advances in Carbohydrate Chemistry&Biochemistry, 1977, 34:243-283.
[31]LiangJuan(梁娟),WengWeizhi(翁伟智),SongJian(宋健).Synthesisof(2,3-dimethoxy-6-formyl)phenyl-β-D-glucoside[J].Fine Chemicals(精细化工), 2017, 34(5):596-600.
[2]Fernandez-GonzalezM,StefanoRD.Fractionationofglycoside aromaprecursorsinneutralgrapes.Hydrolysisandconversionby Saccharomycescerevisiae[J].Lwt-FoodScienceandTechnology,2004, 37(4):467-473.
[3]Li Yougui(李有桂), Lu Mengmeng(卢梦梦), Zhu Chengfeng(朱成峰),etal.Synthesisandpyrolysisofmethylcyclopentenolone-β-D-glucopyranoside[J]. Tobacco Science&Technology(烟草科技),2015, 48(6):45-51.
[4]ShiYao(史尧).Developmentofanewtypeofglycosides[D].Shanghai:ShanghaiInstituteofTechnology(上海应用技术大学),2016.
[5]Masteli?J, Jerkovi?I,Vinkovi?M. Synthesis of selected naturally occurring glucosides of volatile compounds. Their chromatographic and spectroscopic properties[J]. Croatica Chemica Acta, 2004, 77(3):491-500.
[6]Cheng Dongwei(程东伟). Chemical synthesis,thermal degradation mechanismandappliedintobaccoresearchon geraniol glycosides[D]. Zhanjiang:Guangdong Ocean University(广东海洋大学), 2016.
[7]Xie W C, Yang X H, Zhang C H, et al. Investigation on pyrolysis behavioranddecompositioncompoundsofthreesynthesized glycosidically bond flavor precursors[J]. Thermochimica Acta, 2012,532:2-9.
[8]Zeng S T, Sun S H, Liu S, et al. Synthesis of a-ionyl-β-D-glucoside and its property of flavor release[J]. Journal of Thermal Analysis and Calorimetry, 2014, 115:1049-1056.
[9]Lei Sheng(雷声), Zhao Yingliang(赵英良), Yang Qianxu(杨乾栩),etal.Thermalbehavioranddecompositionkineticsofnerol-β-Dglycoside[J]. Food&Machinery(食品与机械), 2017,33(7):16-19.
[10]Xie W C, Tang J, Gu X H, et al. Thermal decomposition study of menthyl-glycosidebyTGA/SDTA,DSCandsimultaneousPy-GCMS analysis[J]. Journal of Analytical and Applied Pyrolysis, 2007,78(1):180-184.
[11]Huang Xiaofeng(黄小凤), Li Xiaodong(李晓东), Li Zhonglin(李中林). The present situation and prospect of heterocyclic spices[J].Chemistry(化学通报), 1995, 8:1-16.
[12]Zhang Weicheng(张维成), Sun Baoguo(孙宝国), Xu Liruan(徐理阮).Thearomacharacteristicsoffuranesters[J].Speciality Petrochemicals(精细石油化工), 1994,(41):41-43.
[13]Wang Chaoyang(汪朝阳). Recent advances in synthesis of domestic perfumes with furan ring[J]. Guangzhou Chemical Industry(广州化工), 2001, 29(1):13-15.
[14]Moon J K, Shibamoto T. Role of roasting conditions in the profile of volatileflavorchemicalsformedfromcoffeebeans[J].Journalof Agricultural and Food Chemistry, 2009, 57(13):5823-5831.
[15]SpillmanP,PollnitzAP,LiacopoulosD,etal.Formationand degradationoffurfurylalcohol,5-methylfurfurylalcohol,vanillyl alcohol,andtheirethylethersinbarrel-agedwines[J].Journalof Agricultural and Food Chemistry, 1998, 46(2):657-663.
[16]Liang Jingjing, Xie Jianchun, Li Hou, et al. Aroma constituents in Shanxiagedvinegarbeforeandafteraging[J].Journalof Agricultural and Food Chemistry, 2016, 64(40):7597-7605.
[17]WangHui(王辉),ChenXiaoyun(陈孝云),HeHuihui(何惠慧).Research on synthesis of furfuryl furoate[J]. Chemical Reagents(化学试剂), 2005, 27(8):477-478,481.
[18]Wang Geyun(王歌云), Liu Xiujuan(刘秀娟), Li Lianbin(厉连斌).Synthesisofperfumefurfurylbutyrateanditscharacterization[J].Fine Chemicals(精细化工), 2004, 21(8):589-590.
[19]Liu Xiujuan(刘秀娟), Wang Geyun(王歌云), Li Lianbin(厉连斌).Synthesisoffurfurylcarboxylate[J].ChemicalWord(化学世界),2003,(8):419-421.
[20]Yao Lihong(姚立红), Su Changan(苏长安), Deng Min(邓敏), et al.Synthesis ofα-furfuryl carboxylates[J]. Fine Chemicals(精细化工),1999, 16(1):16-19.
[21]Zhou Jianwei(周建伟), Liu Junling(刘俊玲). Synthesis of the ester of furfuryl alcohol by furfural[J]. Chemical Engineer(化学工程师),2001, 85(4):6-7.
[22]Li Guangliang(李广良). Synthesis of furazolidol esters[J]. Journal of Henan Science and Technology(河南科技), 1997,(2):20.
[23]Sun Bowang(孙柏旺), Zhang Yawen(张雅雯), Qian Donger(钱东尔), et al. A series of furan alcohol esters as sweet flavor precursors and its synthesis method:CN201710052594.4[P]. 2017-01-24.
[24]Zhang Weicheng(张维成), Sun Baoguo(孙宝国), Xu Liruan(徐理阮). Study on the ester flavorings of furoic acid and furfuryl alcohol[J]. Fine Chemicals(精细化工), 1994, 11(6):19-22.
[25]Yang Hongxi(杨洪锡), Xie Wancui(解万翠), Wang Weimin(王维民),etal.Synthesisandcharacterizationofβ-D-glucopyranosides flavor precursors[J]. Food Science(食品科学), 2007, 28(11):179-182.
[26]StephenA,HashmiK,HengstT,etal.Newandeasilyaccessible nitrogenacyclicgold(I)carbenes:Structureandapplicationinthe gold-catalyzed phenol synthesis as well as the hydration of alkynes[J]. Advanced Synthesis&Catalysis, 2010, 352(8):1315-1337.
[27]Zeng Hongyao(曾鸿耀), Liao Liangcong(廖良聪), Wang Yinghong(王英红).One-potsynthesisofper-O-acetylatedglycopyranosyl bromidesfromreducingsugars[J].ChemicalReagents(化学试剂),2013, 35(7):649-652.
[28]Ling Xunli(凌勋利). Synthesis of acetyglycosyl bromide[J]. Journal ofLuoyangNormalUniversity(洛阳师范学院学报),2008,27(2):75-77.
[29]Zhang Gaihong(张改红), Bai Bing(白冰), Yang Jing(杨静). Recent progress in synthesis of glycosides[J]. Chemistry(化学通报), 2014,77(4):306-311.
[30]Igarashi K. The Koenigs-Knorr reaction[J]. Advances in Carbohydrate Chemistry&Biochemistry, 1977, 34:243-283.
[31]LiangJuan(梁娟),WengWeizhi(翁伟智),SongJian(宋健).Synthesisof(2,3-dimethoxy-6-formyl)phenyl-β-D-glucoside[J].Fine Chemicals(精细化工), 2017, 34(5):596-600.
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