CN113636992A - 一种乙基葫芦巴内酯香料的合成方法 - Google Patents
一种乙基葫芦巴内酯香料的合成方法 Download PDFInfo
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- IUFQZPBIRYFPFD-UHFFFAOYSA-N 5-ethyl-3-hydroxy-4-methyl-2(5H)-furanone Chemical compound CCC1OC(=O)C(O)=C1C IUFQZPBIRYFPFD-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 20
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- 230000002194 synthesizing effect Effects 0.000 title claims description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- FJAKCEHATXBFJT-UHFFFAOYSA-N ethyl 2-oxobutanoate Chemical compound CCOC(=O)C(=O)CC FJAKCEHATXBFJT-UHFFFAOYSA-N 0.000 claims abstract description 22
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 claims abstract description 21
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 20
- 238000004817 gas chromatography Methods 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 81
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 54
- 238000010438 heat treatment Methods 0.000 claims description 42
- -1 3-hydroxy-4-methyl-5-ethyl-5-ethoxycarbonyl-dihydro-furanone Chemical compound 0.000 claims description 32
- 239000012074 organic phase Substances 0.000 claims description 28
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 27
- 238000002390 rotary evaporation Methods 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 26
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 21
- 238000003760 magnetic stirring Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 239000012295 chemical reaction liquid Substances 0.000 claims description 16
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- IHPBMCCSYMBAGR-UHFFFAOYSA-N bromoethane oxolane Chemical compound O1CCCC1.C(C)Br IHPBMCCSYMBAGR-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 13
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- INAXVXBDKKUCGI-UHFFFAOYSA-N 4-hydroxy-2,5-dimethylfuran-3-one Chemical compound CC1OC(C)=C(O)C1=O INAXVXBDKKUCGI-UHFFFAOYSA-N 0.000 description 2
- 241000208140 Acer Species 0.000 description 2
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- 239000003054 catalyst Substances 0.000 description 2
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- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
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- 239000003205 fragrance Substances 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- NJUKKNTZXPEWGX-UHFFFAOYSA-N 1-bromoethyl propanoate Chemical compound CCC(=O)OC(C)Br NJUKKNTZXPEWGX-UHFFFAOYSA-N 0.000 description 1
- TYEYBOSBBBHJIV-UHFFFAOYSA-N 2-oxobutanoic acid Chemical compound CCC(=O)C(O)=O TYEYBOSBBBHJIV-UHFFFAOYSA-N 0.000 description 1
- YEBNSRBQIIWQQC-UHFFFAOYSA-N 2-oxoethyl butanoate Chemical compound CCCC(=O)OCC=O YEBNSRBQIIWQQC-UHFFFAOYSA-N 0.000 description 1
- WSCAAQTYXVAFND-UHFFFAOYSA-N 5-ethyl-3-hydroxy-4-methyloxolan-2-one Chemical compound CCC1OC(=O)C(O)C1C WSCAAQTYXVAFND-UHFFFAOYSA-N 0.000 description 1
- 244000099147 Ananas comosus Species 0.000 description 1
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- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 1
- GXCLVBGFBYZDAG-UHFFFAOYSA-N N-[2-(1H-indol-3-yl)ethyl]-N-methylprop-2-en-1-amine Chemical compound CN(CCC1=CNC2=C1C=CC=C2)CC=C GXCLVBGFBYZDAG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0069—Heterocyclic compounds
- C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
- C11B9/0076—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing less than six atoms
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
本发明公开了一种乙基葫芦巴内酯香料的合成方法,属于香料生产技术领域,相较于现有的类似产品的生产工艺,本发明提供的乙基葫芦巴内酯香料的合成方法,在以乙二酸二乙酯为起始原料,在无水乙醇和氮气保护条件下,经格氏反应制备2‑氧代丁酸乙酯,再在碳酸钾、乙醛作用下环化所需的碳骨架后,得到乙基葫芦巴内酯,减少了工艺流程;反应溶剂和萃取剂回收后进行套用,有利于降低成本,经气相色谱分析产物纯度为98.36%,确保了较高的反应产率。
Description
技术领域
本发明属于香料生产技术领域,具体涉及一种乙基葫芦巴内酯香料的合成方法。
背景技术
乙基葫芦巴内酯又名枫槭呋喃酮,为呋喃类系列香料中的重要香料产品之一,化学名称3-羟基-4-甲基-5-乙基-二氢-呋喃酮,熔点31-35℃,沸点83-86℃(0.5mmHg)。乙基葫芦巴内酯外观为透明的淡黄色至黄色液体,低温时为固体,天然存在于圆叶当归、黑麦、麦芽、咖啡、西红柿、大米、覆盆子、枫树浆等香气成分中,具有甜香、槭树汁香、焦糖和咖啡样的香气,以及牛肉汤样的香味,其香气特征取决于使用浓度,多数配置成10%丙二醇溶液使用。乙基葫芦巴内酯可用于食品用香料,得到了美国食用香料与提取物制造者协会的认可,并经FDA批准可以食用。乙基葫芦巴内酯广泛应用于饮料、糖果、发酵食品、酒类和烘焙食品中,可用于配制焦糖、肉味、坚果、菠萝、草莓、葡萄等香型的食用香精,此外,还可用于烟草香精配方中,用作卷烟香精中可增加烟草的甜香,并改善抽吸口感,是一种优良的增香剂。
乙基葫芦巴内酯可由2-氧代丁酸与甲醇和甲醇钠进行缩合反应,继之再进行脱甲酯基化反应来制取。与乙基葫芦巴内酯属于羟基呋喃酮同族的香料产品4-羟基-2,5-二甲基-3(2H)-呋喃酮(呋喃酮醇)的合成方法主要采用以下合成方法:一是以乳酸乙酯及α-溴代丙酸乙酯为原料,在强碱下醚化,再用三甲基硅烷环化、催化氧化制取。二是在四氰呋喃中以NaH处理乳酸己酯,后加入巴豆腈,经氧化、醇腈裂解得到产物。三是将一缩二乙醇酸二乙甲酯在醇钠作用下与草酸二甲酯环化、氢化、还原酯,再与苯甲酰氯反应、还原制备。四是以1-丁炔-3-醇为原料,与格氏试剂反应,再与乙醛环化得到所需的碳骨架,然后在极性溶剂中先后以臭氧、三苯基膦,最后催化脱水环化制备。现有羟基呋喃酮的合成方法有些路线较长,存在着成本高,反应条件苛刻,操作复杂以及总产率低等缺点。乙基葫芦巴内酯也可以氢氟酸与丙烯醛为起始原料,通过亲核加成,然后水解、酯化制备2-羟基-3-丁烯酸甲酯来制备,由于氢氰酸的毒性,使得该合成方法具有较大的局限性。
发明内容
本发明的目的在于提供一种乙基葫芦巴内酯香料的合成方法,以解决背景技术中的问题。
本发明的目的可以通过以下技术方案实现:一种乙基葫芦巴内酯香料的合成方法,包括如下步骤:
步骤一:将溴乙烷预处理,得到溴乙烷的格氏试剂;预处理的步骤为将溴乙烷用四氢呋喃溶解,得到溴乙烷-四氢呋喃溶液;向烧瓶中通入氮气,在磁力搅拌的条件下,依次加入四氢呋喃、镁粉和碘粒,搅拌均匀;向烧瓶中加入5%量的溴乙烷-四氢呋喃溶液,升温至38-42℃后在磁力搅拌的条件下回流反应,并在1-2h内将95%量的溴乙烷-四氢呋喃溶液缓慢滴加完毕,滴加完毕后继续保温反应25-35min,停止加热并冷却;镁粉和溴乙烷用量的摩尔比为1:1-3;
向烧瓶中加入四氢呋喃和乙二酸二乙酯,磁力搅拌,将乙二酸二乙酯用四氢呋喃溶解;向烧瓶中通入氮气,降低反应温度至-5-0℃,在1.5-2h内缓慢滴加溴乙烷的格氏试剂,滴加完毕后保温反应40-80min,后处理后得到2-氧代丁酸乙酯;
四氢呋喃与乙二酸二乙酯用量的摩尔比为2-5:1;溴乙烷的格氏试剂与乙二酸二乙酯用量的摩尔比为1:0.5-1.5;后处理的步骤为取样进行气相色谱检测,在乙二酸二乙酯含量<0.5%时,将烧瓶温度升至室温,向烧瓶中加入稀盐酸淬灭反应,将反应液转移静置分层,用二氯甲烷萃取2-3次后合并有机相,旋转蒸发并升温至35℃,常压回收二氯甲烷后升温至65℃,再常压回收四氢呋喃剩余底物,将底物用饱和氯化钠溶液洗涤2-3次,加入无水硫酸钠干燥,旋转蒸发并在72-75℃的条件下减压蒸馏;
反应过程如下所示:
步骤二:向烧瓶中加入无水乙醇、碳酸钾和步骤一中制得的2-氧代丁酸乙酯,在磁力搅拌的条件下缩合反应50-70min,后处理后得到3-羟基-4-甲基-5-乙基-5-乙氧羰基-二氢-呋喃酮;
无水乙醇和2-氧代丁酸乙酯用量的体积比为1:5-20;2-氧代丁酸乙酯与碳酸钾用量的摩尔比为1:1-2;后处理的步骤为取样进行气相色谱检测,在2-氧代丁酸乙酯含量<0.5%时,将反应液转移至旋转蒸发仪中旋转蒸发,并升温至79℃常压回收无水乙醇,收集底物,将底物用稀盐酸溶解,磁力搅拌30min后加入0.5-1倍反应液体积的二氯甲烷萃取2-3次,静置分层后合并有机相,将有机相用饱和氯化钠溶液洗涤2-3次,静置分层后将有机相用无水硫酸钠干燥,继续旋转蒸发,升温至35℃常压回收二氯甲烷,收集底物;稀盐酸和碳酸钾用量的摩尔比为1-2:1;
反应过程如下所示:
步骤三:向烧瓶中加入3-羟基-4-甲基-5-乙基-5-乙氧羰基-二氢-呋喃酮和质量分数为5%的氢氧化钠溶液,磁力搅拌并升温至38-42℃,水解反应50-70min,后处理后得到3-羟基-4-甲基-5-乙基-5-羧基-二氢-呋喃酮;
后处理的步骤为取样进行气相色谱检测,在3-羟基-4-甲基-5-乙基-5-乙氧羰基-二氢-呋喃酮的含量<0.5%时,加入稀盐酸直到pH=7,转移反应液静置分层2-2.5h,将水相用二氯甲烷萃取2-3次,合并有机相用饱和氯化钠溶液洗涤2-3次,静置分层后将有机相用无水硫酸钠干燥,旋转蒸发并加热到35℃,常压回收二氯甲烷,收集底物用乙醚结晶,抽滤除去乙醚;
反应过程如下所示:
步骤四:向烧瓶中加入3-羟基-4-甲基-5-乙基-5-羧基-二氢-呋喃酮,在磁力搅拌和150℃的条件下回流反应,后处理后得到乙基葫芦巴内酯香料;
后处理的步骤为将烧瓶中逸出的CO2气体脱酸处理,将剩余反应液旋转蒸发并加热,在90-95℃的条件下减压蒸馏收集馏出物;
反应过程如下所示:
本发明的有益效果:现有技术中与乙基葫芦巴内酯属于羟基呋喃酮同族的香料产品4-羟基-2,5-二甲基-3(2H)-呋喃酮(呋喃酮醇)的合成方法有些路线较长,反应条件苛刻,操作复杂,存在着成本高以及总产率低等缺点。本发明提供的乙基葫芦巴内酯香料的合成方法,在以乙二酸二乙酯为起始原料,在无水乙醇和氮气保护条件下,经格氏反应制备2-氧代丁酸乙酯,再在碳酸钾、乙醛作用下环化所需的碳骨架后,得到乙基葫芦巴内酯,减少了工艺流程;反应溶剂和萃取剂回收后进行套用,有利于降低成本,经气相色谱分析产物纯度为98.36%,确保了较高的反应产率。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1
制备2-氧代丁酸乙酯,包括如下步骤:
将溴乙烷用四氢呋喃溶解,得到溴乙烷-四氢呋喃溶液;向烧瓶中通入氮气,在磁力搅拌的条件下,依次加入四氢呋喃、镁粉和碘粒,搅拌均匀;向烧瓶中加入5%量的溴乙烷-四氢呋喃溶液,升温至38℃后在磁力搅拌的条件下回流反应,并在1h内将95%量的溴乙烷-四氢呋喃溶液缓慢滴加完毕,滴加完毕后继续保温反应25min,停止加热并冷却,得到溴乙烷的格氏试剂;
向烧瓶中加入四氢呋喃和乙二酸二乙酯,磁力搅拌,将乙二酸二乙酯用四氢呋喃溶解;向烧瓶中通入氮气,降低反应温度至-5℃,在1.5h内缓慢滴加溴乙烷的格氏试剂,滴加完毕后保温反应40min,取样进行气相色谱检测,在乙二酸二乙酯含量<0.5%时,将烧瓶温度升至室温,向烧瓶中加入稀盐酸淬灭反应,将反应液转移静置分层,用二氯甲烷萃取2次后合并有机相,旋转蒸发并升温至35℃,常压回收二氯甲烷后升温至65℃,再常压回收四氢呋喃剩余底物,将底物用饱和氯化钠溶液洗涤2次,加入无水硫酸钠干燥,旋转蒸发并在72℃的条件下减压蒸馏,得到2-氧代丁酸乙酯。
实施例2
制备2-氧代丁酸乙酯,包括如下步骤:
将溴乙烷用四氢呋喃溶解,得到溴乙烷-四氢呋喃溶液;向烧瓶中通入氮气,在磁力搅拌的条件下,依次加入四氢呋喃、镁粉和碘粒,搅拌均匀;向烧瓶中加入5%量的溴乙烷-四氢呋喃溶液,升温至40℃后在磁力搅拌的条件下回流反应,并在1.5h内将95%量的溴乙烷-四氢呋喃溶液缓慢滴加完毕,滴加完毕后继续保温反应30min,停止加热并冷却,得到溴乙烷的格氏试剂;
向烧瓶中加入四氢呋喃和乙二酸二乙酯,磁力搅拌,将乙二酸二乙酯用四氢呋喃溶解;向烧瓶中通入氮气,降低反应温度至-3℃,在2h内缓慢滴加溴乙烷的格氏试剂,滴加完毕后保温反应60min,取样进行气相色谱检测,在乙二酸二乙酯含量<0.5%时,将烧瓶温度升至室温,向烧瓶中加入稀盐酸淬灭反应,将反应液转移静置分层,用二氯甲烷萃取3次后合并有机相,旋转蒸发并升温至35℃,常压回收二氯甲烷后升温至65℃,再常压回收四氢呋喃剩余底物,将底物用饱和氯化钠溶液洗涤3次,加入无水硫酸钠干燥,旋转蒸发并在74℃的条件下减压蒸馏,得到2-氧代丁酸乙酯。
实施例3
制备2-氧代丁酸乙酯,包括如下步骤:
将溴乙烷用四氢呋喃溶解,得到溴乙烷-四氢呋喃溶液;向烧瓶中通入氮气,在磁力搅拌的条件下,依次加入四氢呋喃、镁粉和碘粒,搅拌均匀;向烧瓶中加入5%量的溴乙烷-四氢呋喃溶液,升温至42℃后在磁力搅拌的条件下回流反应,并在2h内将95%量的溴乙烷-四氢呋喃溶液缓慢滴加完毕,滴加完毕后继续保温反应35min,停止加热并冷却,得到溴乙烷的格氏试剂;
向烧瓶中加入四氢呋喃和乙二酸二乙酯,磁力搅拌,将乙二酸二乙酯用四氢呋喃溶解;向烧瓶中通入氮气,降低反应温度至0℃,在2h内缓慢滴加溴乙烷的格氏试剂,滴加完毕后保温反应80min,取样进行气相色谱检测,在乙二酸二乙酯含量<0.5%时,将烧瓶温度升至室温,向烧瓶中加入稀盐酸淬灭反应,将反应液转移静置分层,用二氯甲烷萃取3次后合并有机相,旋转蒸发并升温至35℃,常压回收二氯甲烷后升温至65℃,再常压回收四氢呋喃剩余底物,将底物用饱和氯化钠溶液洗涤3次,加入无水硫酸钠干燥,旋转蒸发并在75℃的条件下减压蒸馏,得到2-氧代丁酸乙酯。
实施例4
制备3-羟基-4-甲基-5-乙基-5-乙氧羰基-二氢-呋喃酮,包括如下步骤:
向烧瓶中加入无水乙醇、碳酸钾和实施例2中制得的2-氧代丁酸乙酯,在磁力搅拌的条件下缩合反应50min,取样进行气相色谱检测,在2-氧代丁酸乙酯含量<0.5%时,将反应液转移至旋转蒸发仪中旋转蒸发,并升温至79℃常压回收无水乙醇,收集底物,将底物用稀盐酸溶解,磁力搅拌30min后加入0.5倍反应液体积的二氯甲烷萃取2次,静置分层后合并有机相,将有机相用饱和氯化钠溶液洗涤2次,静置分层后将有机相用无水硫酸钠干燥,继续旋转蒸发,升温至35℃常压回收二氯甲烷,收集底物,得到3-羟基-4-甲基-5-乙基-5-乙氧羰基-二氢-呋喃酮。
实施例5
制备3-羟基-4-甲基-5-乙基-5-乙氧羰基-二氢-呋喃酮,包括如下步骤:
向烧瓶中加入无水乙醇、碳酸钾和实施例2中制得的2-氧代丁酸乙酯,在磁力搅拌的条件下缩合反应60min,取样进行气相色谱检测,在2-氧代丁酸乙酯含量<0.5%时,将反应液转移至旋转蒸发仪中旋转蒸发,并升温至79℃常压回收无水乙醇,收集底物,将底物用稀盐酸溶解,磁力搅拌30min后加入0.5倍反应液体积的二氯甲烷萃取3次,静置分层后合并有机相,将有机相用饱和氯化钠溶液洗涤3次,静置分层后将有机相用无水硫酸钠干燥,继续旋转蒸发,升温至35℃常压回收二氯甲烷,收集底物,得到3-羟基-4-甲基-5-乙基-5-乙氧羰基-二氢-呋喃酮。
实施例6
制备3-羟基-4-甲基-5-乙基-5-乙氧羰基-二氢-呋喃酮,包括如下步骤:
向烧瓶中加入无水乙醇、碳酸钾和实施例2中制得的2-氧代丁酸乙酯,在磁力搅拌的条件下缩合反应70min,取样进行气相色谱检测,在2-氧代丁酸乙酯含量<0.5%时,将反应液转移至旋转蒸发仪中旋转蒸发,并升温至79℃常压回收无水乙醇,收集底物,将底物用稀盐酸溶解,磁力搅拌30min后加入1倍反应液体积的二氯甲烷萃取3次,静置分层后合并有机相,将有机相用饱和氯化钠溶液洗涤3次,静置分层后将有机相用无水硫酸钠干燥,继续旋转蒸发,升温至35℃常压回收二氯甲烷,收集底物,得到3-羟基-4-甲基-5-乙基-5-乙氧羰基-二氢-呋喃酮。
实施例7
制备乙基葫芦巴内酯,包括如下步骤:
向烧瓶中加入实施例5中制得的3-羟基-4-甲基-5-乙基-5-乙氧羰基-二氢-呋喃酮和质量分数为5%的氢氧化钠溶液,磁力搅拌并升温至38℃,水解反应50min,取样进行气相色谱检测,在3-羟基-4-甲基-5-乙基-5-乙氧羰基-二氢-呋喃酮的含量<0.5%时,加入稀盐酸直到pH=7,转移反应液静置分层2h,将水相用二氯甲烷萃取2次,合并有机相用饱和氯化钠溶液洗涤2次,静置分层后将有机相用无水硫酸钠干燥,旋转蒸发并加热到35℃,常压回收二氯甲烷,收集底物用乙醚结晶,抽滤除去乙醚得到3-羟基-4-甲基-5-乙基-5-羧基-二氢-呋喃酮,用新的烧瓶在磁力搅拌和150℃的条件下回流反应,将烧瓶中逸出的CO2气体脱酸处理,将剩余反应液旋转蒸发并加热,在90℃的条件下减压蒸馏收集馏出物,得到乙基葫芦巴内酯。
实施例8
制备乙基葫芦巴内酯,包括如下步骤:
向烧瓶中加入实施例5中制得的3-羟基-4-甲基-5-乙基-5-乙氧羰基-二氢-呋喃酮和质量分数为5%的氢氧化钠溶液,磁力搅拌并升温至40℃,水解反应60min,取样进行气相色谱检测,在3-羟基-4-甲基-5-乙基-5-乙氧羰基-二氢-呋喃酮的含量<0.5%时,加入稀盐酸直到pH=7,转移反应液静置分层2.5h,将水相用二氯甲烷萃取3次,合并有机相用饱和氯化钠溶液洗涤3次,静置分层后将有机相用无水硫酸钠干燥,旋转蒸发并加热到35℃,常压回收二氯甲烷,收集底物用乙醚结晶,抽滤除去乙醚得到3-羟基-4-甲基-5-乙基-5-羧基-二氢-呋喃酮,用新的烧瓶在磁力搅拌和150℃的条件下回流反应,将烧瓶中逸出的CO2气体脱酸处理,将剩余反应液旋转蒸发并加热,在90℃的条件下减压蒸馏收集馏出物,得到乙基葫芦巴内酯。
实施例9
制备乙基葫芦巴内酯,包括如下步骤:
向烧瓶中加入实施例5中制得的3-羟基-4-甲基-5-乙基-5-乙氧羰基-二氢-呋喃酮和质量分数为5%的氢氧化钠溶液,磁力搅拌并升温至42℃,水解反应70min,取样进行气相色谱检测,在3-羟基-4-甲基-5-乙基-5-乙氧羰基-二氢-呋喃酮的含量<0.5%时,加入稀盐酸直到pH=7,转移反应液静置分层2.5h,将水相用二氯甲烷萃取3次,合并有机相用饱和氯化钠溶液洗涤3次,静置分层后将有机相用无水硫酸钠干燥,旋转蒸发并加热到35℃,常压回收二氯甲烷,收集底物用乙醚结晶,抽滤除去乙醚得到3-羟基-4-甲基-5-乙基-5-羧基-二氢-呋喃酮,用新的烧瓶在磁力搅拌和150℃的条件下回流反应,将烧瓶中逸出的CO2气体脱酸处理,将剩余反应液旋转蒸发并加热,在95℃的条件下减压蒸馏收集馏出物,得到乙基葫芦巴内酯。
对比例1:
在实施例8的基础上,不用饱和氯化钠溶液洗涤,其余步骤一致,制备出乙基葫芦巴内酯。
对比例2:
在实施例8的基础上,用二氯甲烷萃取一次,其余步骤一致,制备出乙基葫芦巴内酯。
对实施例7-9和对比例1-2进行性能测试,用气相色谱分析产物纯度,结果如表1所示:
表1
项目 | 实施例7 | 实施例8 | 实施例9 | 对比例1 | 对比例2 |
产物纯度/% | 98.23 | 98.36 | 98.35 | 96.12 | 93.33 |
由表1可以看出,本发明提供的合成方法获得的乙基葫芦巴内酯纯度较高。
需要说明的是,在本文中,诸如第一和第二等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来,而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。而且,术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含,从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素,而且还包括没有明确列出的其他要素,或者是还包括为这种过程、方法、物品或者设备所固有的要素。
尽管已经示出和描述了本发明的实施例,对于本领域的普通技术人员而言,可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型,本发明的范围由所附权利要求及其等同物限定。
Claims (7)
1.一种乙基葫芦巴内酯香料的合成方法,其特征在于,包括如下步骤:
步骤一:将溴乙烷预处理,得到溴乙烷的格氏试剂;向烧瓶中加入四氢呋喃和乙二酸二乙酯,将乙二酸二乙酯用四氢呋喃溶解,通入氮气,降温至-5-0℃,滴加溴乙烷的格氏试剂,滴加完毕后保温反应40-80min,后处理后得到2-氧代丁酸乙酯;
步骤二:向烧瓶中加入无水乙醇、碳酸钾和2-氧代丁酸乙酯,磁力搅拌反应50-70min,后处理后得到3-羟基-4-甲基-5-乙基-5-乙氧羰基-二氢-呋喃酮;
步骤三:向烧瓶中加入3-羟基-4-甲基-5-乙基-5-乙氧羰基-二氢-呋喃酮和质量分数为5%的氢氧化钠溶液,磁力搅拌并升温至38-42℃,水解反应50-70min,后处理后得到3-羟基-4-甲基-5-乙基-5-羧基-二氢-呋喃酮;
步骤四:向烧瓶中加入3-羟基-4-甲基-5-乙基-5-羧基-二氢-呋喃酮,在磁力搅拌和150℃的条件下回流反应,后处理后得到乙基葫芦巴内酯香料。
2.根据权利要求1所述的一种乙基葫芦巴内酯香料的合成方法,其特征在于,步骤一中所述预处理的步骤为将溴乙烷用四氢呋喃溶解制备溴乙烷-四氢呋喃溶液;通入氮气和磁力搅拌,依次加入四氢呋喃、镁粉和碘粒,搅拌均匀;向烧瓶中加入5%量的溴乙烷-四氢呋喃溶液,升温至38-42℃后在磁力搅拌的条件下回流反应,并在1-2h内将95%量的溴乙烷-四氢呋喃溶液缓慢滴加完毕,滴加完毕后继续保温反应25-35min,停止加热并冷却。
3.根据权利要求2所述的一种乙基葫芦巴内酯香料的合成方法,其特征在于,所述镁粉和溴乙烷用量的摩尔比为1:1-3。
4.根据权利要求1所述的一种乙基葫芦巴内酯香料的合成方法,其特征在于,步骤一中所述四氢呋喃与乙二酸二乙酯用量的摩尔比为2-5:1;溴乙烷的格氏试剂与乙二酸二乙酯用量的摩尔比为1:0.5-1.5。
5.根据权利要求1所述的一种乙基葫芦巴内酯香料的合成方法,其特征在于,步骤一中后处理的步骤为取样进行气相色谱检测,在乙二酸二乙酯含量<0.5%时,将烧瓶温度升至室温,向烧瓶中加入稀盐酸淬灭反应,将反应液转移静置分层,用二氯甲烷萃取2-3次后合并有机相,旋转蒸发并升温至35℃,常压回收二氯甲烷后升温至65℃,再常压回收四氢呋喃剩余底物,将底物用饱和氯化钠溶液洗涤2-3次,加入无水硫酸钠干燥,旋转蒸发并在72-75℃的条件下减压蒸馏。
6.根据权利要求1所述的一种乙基葫芦巴内酯香料的合成方法,其特征在于,步骤二中无水乙醇和2-氧代丁酸乙酯用量的体积比为1:5-20;2-氧代丁酸乙酯与碳酸钾用量的摩尔比为1:1-2。
7.根据权利要求1所述的一种乙基葫芦巴内酯香料的合成方法,其特征在于,步骤四中后处理的步骤为将烧瓶中逸出的CO2气体脱酸处理,将剩余反应液旋转蒸发并加热,在90-95℃的条件下减压蒸馏收集馏出物。
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