CN112047911A - 一种呋喃酮的催化合成方法 - Google Patents
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Abstract
本发明公开了一种呋喃酮的催化合成方法,采用特定的肽作为催化剂,以鼠李糖为原料,在磷酸缓冲液和有机溶剂共同作为反应溶剂并共热的条件下,制得呋喃酮,其工艺过程中的水相和有机溶剂可以回收套用。本发明的反应效率高,一步即可得到产品,反应操作简便,条件温和。
Description
技术领域
本发明属于呋喃酮合成技术领域,具体涉及一种呋喃酮的催化合成方法。
背景技术
呋喃酮,学名2,5-二甲基-4-羟基-3(2H)呋喃酮(2,5-Dimethyl-4-Hydroxy-3(2H)Furanone),又称作菠萝酮或草莓酮。1965年,J.O.Rodin等人[J.Food Sci.1965,30(2),280-285.]在菠萝汁萃取液中首次分离出呋喃酮,并确定了其结构,它广泛存在于菠萝、草莓、柑桔等天然产物中。呋喃酮具有强烈的焙烤焦糖香味,极微量就具有明显的增香修饰效果,因而广泛用作食品、烟草、饮料的增香剂。
自然界存在着丰富的糖类资源,天然呋喃酮又是糖类Maillard反应产物之一,因此由糖类物质来制备呋喃酮一直是工业界追求的一个目标。目前为止,已有一些从糖类出发制备呋喃酮的文献报道。1963年,Hodge等人[American Soc.Brewing Chemists Proc.,(1963)84.]将L一鼠李糖在有机仲胺(如二丁胺、六氢吡啶)、醋酸和乙醇介质中加热反应,产物经分离和重结晶可获得收率70-80%的呋喃酮。Decnop等人[EP398417]报道了L-鼠李糖在L-赖氨酸,L-羟脯氨酸条件下在磷酸二氢钠和氢氧化钠中发生反应,呋喃酮收率分别可达38%,63%,而用L-岩藻糖和L-赖氨酸在同样条件下反应收率为61%。Meguro等人[JP0248594]以葡萄糖为原料,经多步反应得到6-脱氧-D-吡喃型葡萄糖,最后与哌啶醋酸回流,得到呋喃酮。Wong等人[J.Org.Chem.,1983,48(20):3493]将D-果糖-1,6-二磷酸酯在酶作用下与α-羟基醛反应得到6-脱氧果糖-1-磷酸酯,进一步水解为6-脱氧果糖,再经哌啶醋酸反应得到呋喃酮。Ken等[JP63307869]报道了在离子交换树脂存在下,有机碱处理6-脱氧己糖得到呋喃酮,收率在80%以上。
发明内容
本发明的目的在于提供一种呋喃酮的催化合成方法。
本发明的技术方案如下:
一种呋喃酮的催化合成方法,包括如下步骤:
(1)将鼠李糖、pH=5-7的磷酸缓冲液、有机溶剂和肽混合,在氮气置换后,加热至回流状态进行反应直至其有机相中的呋喃酮的含量不再变化,反应温度为60-120℃,反应时间为3-6h;上述肽由2-20个氨基酸组成,分子量不超过2000道尔顿;
(2)将步骤(1)所得的物料静置降温,获得有机相和水相;
(3)将步骤(2)所得的有机相中的有机溶剂回收后减压蒸馏获得呋喃酮,水相回收使用。
在本发明的一个优选实施方案中,所述鼠李糖为L构型和/或D构型。
进一步优选的,所述鼠李糖带至少一个结晶水。
在本发明的一个优选实施方案中,所述肽包括丙谷二肽、双甘肽、L-肌肽、谷胱甘肽、胶原三肽、鱼胶原蛋白和大豆低聚肽中的至少一种。
在本发明的一个优选实施方案中,所述有机溶剂包括乙酸丁酯、乙酸乙酯、甲苯、苯和二甲苯。
进一步优选的,所述有机溶剂为乙酸丁酯。
在本发明的一个优选实施方案中,所述磷酸盐缓冲液为NaH2PO4/Na2HPO4缓冲溶液。
在本发明的一个优选实施方案中,所述磷酸盐缓冲液的pH=6-7。
在本发明的一个优选实施方案中,所述鼠李糖和肽的质量比为1∶0.1-5。
在本发明的一个优选实施方案中,所述步骤(1)的反应温度为100℃,反应时间为3h。
本发明的有益效果是:
1、本发明采用特定的肽作为催化剂,以鼠李糖为原料,在磷酸缓冲液和有机溶剂共同作为反应溶剂并共热的条件下,制得呋喃酮,其工艺过程中的水相和有机溶剂可以回收套用。
2、本发明的反应效率高,一步即可得到产品,反应操作简便,条件温和。
附图说明
图1为本发明实施例1制得的呋喃酮重结晶后的GC谱图(乙酯作稀释溶剂)。
具体实施方式
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。
实施例1
(1)将100g一水鼠李糖、600g pH=6-7的NaH2PO4/Na2HPO4缓冲溶液、500g乙酸丁酯和95.8g丙谷二肽混合,在氮气置换后,加热至回流状态进行反应直至其有机相中的呋喃酮的含量不再变化,反应温度为100℃,反应时间为3h;
(2)将步骤(1)所得的物料静置降至室温,获得有机相和水相;
(3)将步骤(2)所得的有机相进行旋蒸浓缩,回收乙酸丁酯,进一步减压蒸馏得到25g呋喃酮(收率35%,含量90%,经过95%乙醇重结晶,含量达到99.7%,如图1所示,熔点:77-80℃),水相回收使用。
实施例2
将步骤(1)中的丙谷二肽替换为其他肽,且反应时间、肽与鼠李糖的质量比发生变化,其余同实施例1,实验结果如下表1所示。
表1不同肽催化下鼠李糖制备呋喃酮的反应情况
注:a.胶原三肽为一种含有甘氨酸、脯氨酸(或羟脯氨酸)外加一个其他氨基酸的三肽。其结构可以简单的表示为Gly-x-y,其平均分子量为280道尔顿。
b.从深海鳕鱼新鲜的鱼皮、鱼鳞中通过生物酶定向剪切技术提取,主要为I型胶原蛋白,产品富含19种氨基酸,分子量在800-1200道尔顿(来源于江苏鑫瑞生物科技有限公司)。
c.由大豆蛋白酶解制得,主要由2-10个氨基酸组成的短链多肽,分子量在1000道尔顿以下(来源于江苏鑫瑞生物科技有限公司)。
以上所述,仅为本发明的较佳实施例而已,故不能依此限定本发明实施的范围,即依本发明专利范围及说明书内容所作的等效变化与修饰,皆应仍属本发明涵盖的范围内。
Claims (10)
1.一种呋喃酮的催化合成方法,其特征在于:包括如下步骤:
(1)将鼠李糖、pH=5-7的磷酸缓冲液、有机溶剂和肽混合,在氮气置换后,加热至回流状态进行反应直至其有机相中的呋喃酮的含量不再变化,反应温度为60-120℃,反应时间为3-6h;上述肽由2-20个氨基酸组成,分子量不超过2000道尔顿;
(2)将步骤(1)所得的物料静置降温,获得有机相和水相;
(3)将步骤(2)所得的有机相中的有机溶剂回收后减压蒸馏获得呋喃酮,水相回收使用。
2.如权利要求1所述的催化合成方法,其特征在于:所述鼠李糖为L构型和/或D构型。
3.如权利要求2所述的催化合成方法,其特征在于:所述鼠李糖带至少一个结晶水。
4.如权利要求1所述的催化合成方法,其特征在于:所述肽包括丙谷二肽、双甘肽、L-肌肽、谷胱甘肽、胶原三肽、鱼胶原蛋白和大豆低聚肽中的至少一种。
5.如权利要求1所述的催化合成方法,其特征在于:所述有机溶剂包括乙酸丁酯、乙酸乙酯、甲苯、苯和二甲苯。
6.如权利要求5所述的催化合成方法,其特征在于:所述有机溶剂为乙酸丁酯。
7.如权利要求1所述的催化合成方法,其特征在于:所述磷酸盐缓冲液为NaH2PO4/Na2HPO4缓冲溶液。
8.如权利要求1所述的催化合成方法,其特征在于:所述磷酸盐缓冲液的pH=6-7。
9.如权利要求1至8中任一权利要求所述的催化合成方法,其特征在于:所述鼠李糖和肽的质量比为1∶0.1-5。
10.如权利要求1至8中任一权利要求所述的催化合成方法,其特征在于:所述步骤(1)的反应温度为100℃,反应时间为3h。
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CN202010991773.6A CN112047911B (zh) | 2020-09-18 | 2020-09-18 | 一种呋喃酮的催化合成方法 |
US17/478,998 US12071417B2 (en) | 2020-09-18 | 2021-09-20 | Method for catalytically synthesizing furaneol |
EP21197834.1A EP3971172A1 (en) | 2020-09-18 | 2021-09-20 | Method for catalytically synthesizing furaneol |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3629293A (en) * | 1967-09-18 | 1971-12-21 | Lever Brothers Ltd | Synthesis of 5-methyl-4-hydroxy-2 3-dihydrofuran-3-one |
US5149840A (en) * | 1989-05-18 | 1992-09-22 | Unilever Patent Holdings B.V. | Hydroxy furanone preparation |
WO2008067997A1 (en) * | 2006-12-05 | 2008-06-12 | Isobionics B.V. | Preparation of 4-hydroxy-2,5-dimethyl-2,3-dihydrofuran-3-one |
WO2008148737A2 (en) * | 2007-06-04 | 2008-12-11 | Nestec S.A. | Baked composition |
US20170079316A1 (en) * | 2014-05-19 | 2017-03-23 | Nestec S.A. | Mechanical generation of flavour compositions |
CN107235941A (zh) * | 2016-03-28 | 2017-10-10 | 苏州禾研生物技术有限公司 | 一种呋喃酮的合成方法 |
CN108047175A (zh) * | 2017-12-25 | 2018-05-18 | 武汉桀升生物科技有限公司 | 一种呋喃酮的合成方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS63307869A (ja) | 1987-01-20 | 1988-12-15 | San Ei Chem Ind Ltd | ヒドロキシフラノン類の製法 |
JPH0762024B2 (ja) | 1988-08-10 | 1995-07-05 | 長谷川香料株式会社 | D−グルコフラノース又はd−キシロフラノース誘導体の製法 |
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- 2020-09-18 CN CN202010991773.6A patent/CN112047911B/zh active Active
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- 2021-09-20 EP EP21197834.1A patent/EP3971172A1/en not_active Withdrawn
- 2021-09-20 US US17/478,998 patent/US12071417B2/en active Active
Patent Citations (7)
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US3629293A (en) * | 1967-09-18 | 1971-12-21 | Lever Brothers Ltd | Synthesis of 5-methyl-4-hydroxy-2 3-dihydrofuran-3-one |
US5149840A (en) * | 1989-05-18 | 1992-09-22 | Unilever Patent Holdings B.V. | Hydroxy furanone preparation |
WO2008067997A1 (en) * | 2006-12-05 | 2008-06-12 | Isobionics B.V. | Preparation of 4-hydroxy-2,5-dimethyl-2,3-dihydrofuran-3-one |
WO2008148737A2 (en) * | 2007-06-04 | 2008-12-11 | Nestec S.A. | Baked composition |
US20170079316A1 (en) * | 2014-05-19 | 2017-03-23 | Nestec S.A. | Mechanical generation of flavour compositions |
CN107235941A (zh) * | 2016-03-28 | 2017-10-10 | 苏州禾研生物技术有限公司 | 一种呋喃酮的合成方法 |
CN108047175A (zh) * | 2017-12-25 | 2018-05-18 | 武汉桀升生物科技有限公司 | 一种呋喃酮的合成方法 |
Non-Patent Citations (2)
Title |
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A.F.PISARNITSKII,ET AL.: "Methylpentoses are probable precursors of furanones in fruits", 《APPLIED BIOCHEMISTRY AND MICROBIOLOGY》 * |
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CN112047911B (zh) | 2023-01-13 |
US20220089558A1 (en) | 2022-03-24 |
EP3971172A1 (en) | 2022-03-23 |
US12071417B2 (en) | 2024-08-27 |
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