CN1396262A - 环氧芳樟醇或含环氧芳樟醇的混合物的制备方法 - Google Patents
环氧芳樟醇或含环氧芳樟醇的混合物的制备方法 Download PDFInfo
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Abstract
本发明涉及一种制备环氧芳樟醇或含环氧芳樟醇的混合物的方法，其中是在酶的存在下氧化芳樟醇或含有芳樟醇的混合物。
Description
技术领域
本发明涉及制备环氧芳樟醇或含环氧芳樟醇的混合物的方法。
背景技术
环氧芳樟醇是早已公知并且大量使用的芳香物质。并且，环氧芳樟醇以9-元环的呋喃型化合物形式(2-甲基-2-乙烯基-5-(α-羟基异丙基)四氢呋喃，CAS 60047-17-8；顺式和反式：CAS 5989-33-3和34995-77-2)和6-元环的吡喃型化合物形式(2，2，6-三甲基-6-乙烯基四氢-2H-吡喃-3-醇，CAS 14049-11-7；顺式和反式：CAS 14009-71-3和39028-58-5)两种形式存在。其天然存在于精油诸如玫瑰木油和木樨属植物提取物以及果实中(Volatile Compounds in Food，Qualitative and QuantitativeData，第7版，1996，TNO Nutrition and Food Research Institute，Zeist，荷兰)，具有类似花-泥土、轻微的香柠檬气味(Bauer，Garbe，Surburg，Common Fragrance and Flavor Materials，第2版，VCH，Weinheim 1990，p.114)。环氧芳樟醇的香味表现为柑桔、杏、蓝莓、花香方向。
香料领域的技术人员分为三个领域：天然、天然等同和合成香料。对合成香料的兴趣较小，因为顾客对其的接受力不是特别高。在JP A59225176中公开了一个制备天然等同香料的例子。该公开涉及环氧芳樟醇的制备。在该情况下，通过使用强无机酸的化学合成将非天然的起始物质转化为环氧芳樟醇。这类产品仅能作为“天然等同”而不是天然进行归类，因此不得用于制备天然香料。
天然香料，以及也存在于其中的天然香料物质，归为最高价值的一类。还也由天然香料可达到的相当高的价格清楚地表明。此外，顾客对天然产品、并由此对生产这些产品所需的天然香料的兴趣持续增加。
因此，香料工业的一个目标是可获得数量充足质量上乘的天然原料用于天然香料生产。但是，从天然提取物中分离这些不同的原料通常是不经济的。
Demyttenaere公开了一个通过发酵制备环氧芳樟醇的例子(Demyttenaere，J.C.R.，1998，Biotransformation of terpenesby fungi for the puroduction of bioflavors，Meded，-Fac.Landbouwkd.Toegepaste Biol.Wet.，63(4a)，1321-1324，和Demyttenaere，J.C.R.；Willemen，H.M.，1998，Biotransformationof linalool to furanoid and pyranoid linalool oxides bvAspergillus niger，Phytochemistry，47(6)，1029-1036)。其中描述了借助黑色曲霉和青霉属菌株的萜烯醇类的生物转化。但是，该方法的进行非常复杂，转化非常缓慢，并且环氧芳樟醇的收率仅有20-33％。
此外，将酶用于脂肪酸类和烯类中双键的环氧化是已知的(1.PCTWO 91/04333.2.Jarvie，A.W.P.；Overton，N.；St.Pourcain，C.B.，1998，Enzymatic Epoxidation of polybutadiene，Chem.Comm，177-178.3.Lemoult，S.C.；Richardson，P.F.；Roberts，S.M.，1995，Lipase catalyzed Baeyer-Villiger Reactions，J.Chem，Soc.Perkin Trans，I，89-91.4.Rüsch，M.；Warwel，S.，1996，Peroxyfatty acids：lipase catalyzed preparation and expoxidation，Lipid Technology，7，77-80.5.Miurra，Y.；Yamane，T.，1997，Epoxidation of alkanes and cycloalkanes by microbial lipasesimmobilized with photocrosslinkable resin prepolymer，Biotechnol.Lett.，19，7，611-613)。其涉及的双键环氧化与使用过氧化羧酸的化学反应类似。在这些例子中，用脂肪酶(E.C.3.1.1.3，CAS No.9001-62-1，例如来自葱头假单胞菌(Pseudomonas cepacia)，DSM 3959，南极念珠菌(Candida antarctica)，DSM 3855，DSM3908，DSM3909，Humicola lanuginosa，DSM 3819，DSM4109，Humicolabrevispora，DSM 4110，Humicola brevis var.thermoidea，DSM4111，Humicola isolens，DSM 1800)在过氧化氢存在下催化过氧化羧酸的中间形成(WO91/04333)。
许多文献公开了以实验室或工厂规模使用脂肪酶，主要用于酯化或酯交换。但是，这些文献没有描述过用酶方法制备呋喃型或吡喃型环氧芳樟醇。
发明内容
本发明的目的是生产环氧芳樟醇或含有环氧芳樟醇的混合物，其可被归类于天然物并可用于生产天然香料。另一个目的是提供明显高于现有技术的收率。特别是要达到大于90％的收率。
已经发现了一种制备环氧芳樟醇或含有环氧芳樟醇的混合物的方法，其特征在于在酶的存在下氧化芳樟醇或含有芳樟醇的混合物。
在根据本发明的方法中可使用D-芳樟醇和L-芳樟醇。这些物质可以纯净的形式使用，或以混合物的形式使用。同样可使用与其它的物质混合的芳樟醇。
适合的其它物质是精油，纯净的或提取的。在一个优选的实施方案中，芳樟醇可存在于精油诸如玫瑰木油、芫荽油、罗勒油、薰衣草油等中。在这些情况下D-芳樟醇或L-芳樟醇也可作为单一物质存在于反应介质中。在反应介质中的D-芳樟醇和L-芳樟醇的混合物当然同样适用于本发明的目的。
根据本发明使用的酶优选是水解酶，特别是脂肪酶或蛋白酶。根据本发明，脂肪酶是适合并特别优选的。尤其优选活动的(mobilized)脂肪酶，例如来自德国Roche Diagnostics，Penzberg的Chirazym C2L2或来自丹麦Novo Nordisk，的Novozym 435。
优选那些可借助下列微生物获得的酶：葱头假单胞菌(Pseudomonas cepacia)，例如DSM 3959，南极念珠菌(Candidaantarctica)，例如DSM 3855、DSM3908、DSM3909，Humicolalanuginosa，例如DSM 3819、DSM4109，Humicola brevispora，例如DSM 4110，Humicola brevis var.thermoidea，例如DSM 4111，Humicola isolens，例如DSM 1800。
优选用酵母菌生产酶。对于本发明的目的，更优选纯培养物形式的念珠菌或这些酵母菌的混合的培养物，特别是南极念珠菌(Candidaantarctica)。因此，最优选将来自南极念珠菌的脂肪酶用于根据本发明的方法。
在根据本发明的方法中，优选在所述酶和氧化剂的存在下进行芳樟醇的氧化。优选过氧化氢。氧化剂可在氧化过程前或期间加入。同样，根据本发明，可选择一定组成的介质和/或反应条件，从而在进行根据本发明方法期间生成所需的氧化剂。尤其，可用酶进行氧化剂的形成。其实例是氧化酶，如葡糖氧化酶。还可以使用非酶催化剂生成过氧化氢。
因此，在根据本发明的变化形式中，例如可选择介质和酶的组合从而在生产过程中就地生成过氧化氢。这可以包括在氧化反应开始前开始过氧化氢的生成，或在氧化反应期间就地发生过氧化氢的生成。根据本发明，例如可以在含水介质中用葡糖氧化酶氧化葡萄糖，用酶方法形成过氧化氢。
除了使用酶和氧化剂，还经常可以在反应溶液中加入溶剂。根据本发明适合的溶剂是酸酯，优选乙酸乙酯。除了这些酯，可形成过氧羧酸的羧酸也可以使用。例如乙酸、甲酸、苯甲酸。更优选乙酸。
根据本发明优选的溶剂是那些借助酶在过氧化氢存在下可形成过酸的溶剂。一个例子是乙酸乙酯，其在过氧化氢存在下借助脂肪酶形成过乙酸中间体。
以根据本发明特别优选的方式，相应地进行下述反应：芳樟醇
环氧芳樟醇
呋喃型化合物 吡喃型化合物
令人惊奇地，可根据所述的本发明的方法制备环氧芳樟醇，其可归类于天然物并因此可用于生产天然香料。此外，还令人惊奇地实现了以大于90％收率的直接方法进行天然环氧芳樟醇的生产。这意味着与先前公开的借助微生物进行的发酵方法相比根据本发明的方法表现出明显的优点，因此适用于工业生产天然环氧芳樟醇。
环氧芳樟醇根据本发明可直接地或在香料中用于广泛的食品领域。特别是用于在需要产生“柑桔”、“杏”和“蓝莓”香味的场合。
具体实施方式
实施例表1
步骤：
| 项 | 数量 | 起始物质 |
| 1 | 100.0ml | 乙酸乙酯，nat. |
| 2 | 7.7g | 芳樟醇，nat. |
| 3 | 6.0ml | 过氧化氢(H2O2，30％) |
| 4 | 0.1g(245个单位) | 脂肪酶Chirazym C2L2(Roche Diagnostics)或Novozym 435(Novo Nordisk) |
将乙酸乙酯(项1)引入装有桨式搅拌器的2升三颈烧瓶中，在缓慢搅拌下加入芳樟醇(项2)、过氧化氢(H2O2，30％，项3)和酶(项4)。在室温下缓慢搅拌混合物(约100-120rpm)。在此过程中每1-2天用GC分析组成。结果：
GC结果列于表2，计算乙酸的百分面积(除了使用乙酸的情况)。表2
F：呋喃型化合物/P：吡喃型化合物
| 芳樟醇(GC-％) | 环氧芳樟醇F，反式和顺式(GC-％) | 环氧芳樟醇P，反式和顺式(GC-％) | 环氧芳樟醇-环氧化物(GC-％) | 乙酸(GC-％) | |
| 前体 | 99.3 | - | - | - | - |
| 1天 | 5.1 | 32.9 | 4.2 | 57.1 | 19.7 |
| 2天 | 0 | 56.5 | 6.5 | 36.3 | 22.1 |
| 5天 | 0 | 79.8 | 9.1 | 9.0 | 24.2 |
| 7天 | 0 | 83.3 | 9.6 | 5.6 | 25.4 |
呋喃型和吡喃型环氧芳樟醇的总收率约93％。
含有环氧芳樟醇的有机相的蒸馏提纯(10-塔板的塔)得到纯度99％(GC)呋喃型环氧芳樟醇产物。其就器官感觉而言在味道和气味上可与天然等同产物的标准相媲美。
尽管在前面为了说明对本发明进行了详细描述，但是应理解这些细节仅用于说明的目的，在不背离权利要求限定的本发明的精神和范围的条件下本领域的技术人员可作出变化。
Claims (36)
1.一种制备环氧芳樟醇或含有环氧芳樟醇的混合物的方法，包括在酶的存在下氧化芳樟醇或含芳樟醇的混合物形成反应混合物的步骤。
2.根据权利要求1的方法，其中使用D-芳樟醇、L-芳樟醇或含有D-芳樟醇或L-芳樟醇的精油、或这些物质的混合物。
3.根据权利要求1的方法，其中使用来自酵母菌或细菌的酶。
4.根据权利要求3的方法，其中使用来自南极念珠菌菌株、Pseudomonoas sp.、Humico1a sp.、Mucor miehi或含有这些酵母菌的混合培养物的酶。
5.根据权利要求4的方法，其中使用来自南极念珠菌的酶。
6.根据权利要求3的方法，其中所述的酶是脂肪酶。
7.根据权利要求1的方法，其中在一种或多种氧化剂存在下进行氧化反应。
8.根据权利要求7的方法，其中在反应之前或期间加入氧化剂。
9.根据权利要求7的方法，其中在反应之前或期间在反应混合物中产生氧化剂。
10.根据权利要求7的方法，其中在氧化反应之前或期间在催化剂存在下产生氧化剂。
11.根据权利要求1的方法，其中所述的酶用作催化剂。
12.根据权利要求1的方法，其中所述的酶是葡糖氧化酶(GOD)。
13.根据权利要求7的方法，其中以0.1-80％的量将氧化剂加入反应介质中。
14.根据权利要求7的方法，其中所述的氧化剂是过氧化氢。
15.根据权利要求1的方法，其中在反应介质中加入溶剂。
16.根据权利要求15的方法，其中所述的溶剂是羧酸或羧酸酯。
17.根据权利要求16的方法，其中所述的溶剂是乙酸乙酯或乙酸。
18.环氧芳樟醇，其通过制备环氧芳樟醇或含环氧芳樟醇的混合物的方法制备，该方法包括在酶的存在下氧化芳樟醇或含有芳樟醇的混合物形成反应混合物的步骤。
19.根据权利要求18的环氧芳樟醇，其中使用D-芳樟醇、L-芳樟醇或含有D-芳樟醇或L-芳樟醇的精油、或这些物质的混合物。
20.根据权利要求18的环氧芳樟醇，其中使用来自酵母菌或细菌的酶。
21.根据权利要求20的环氧芳樟醇，其中使用来自南极念珠菌菌株、Pseudomonoas sp.、Humicola sp.、Mucor miehi或含有这些酵母菌的混合培养物的酶。
22.根据权利要求21的环氧芳樟醇，其中使用来自南极念珠菌的酶。
23.根据权利要求18的环氧芳樟醇，其中所述的酶是脂肪酶。
24.根据权利要求18的环氧芳樟醇，其中在一种或多种氧化剂存在下进行氧化反应。
25.根据权利要求24的环氧芳樟醇，其中在反应之前或期间加入氧化剂。
26.根据权利要求24的环氧芳樟醇，其中在反应之前或期间在反应混合物中产生氧化剂。
27.根据权利要求24的环氧芳樟醇，其中在氧化反应之前或期间在催化剂存在下产生氧化剂。
28.根据权利要求18的环氧芳樟醇，其中所述的酶用作催化剂。
29.根据权利要求18的环氧芳樟醇，其中所述的酶是葡糖氧化酶(GOD)。
30.根据权利要求24的环氧芳樟醇，其中以0.1-80％的量将氧化剂加入反应介质中。
31.根据权利要求24的环氧芳樟醇，其中所述的氧化剂是过氧化氢。
32.根据权利要求18的环氧芳樟醇，其中在反应介质中加入溶剂。
33.根据权利要求32的环氧芳樟醇，其中所述的溶剂是羧酸或羧酸酯。
34.根据权利要求33的环氧芳樟醇，其中所述的溶剂是乙酸乙酯或乙酸。
35.一种含有香料的食品，其含有环氧芳樟醇，该环氧芳樟醇通过制备环氧芳樟醇或含环氧芳樟醇的混合物的方法制备，所述的方法包括在酶的存在下氧化芳樟醇或含芳樟醇的混合物形成反应混合物的步骤。
36.含有环氧芳樟醇的香料组合物，该环氧芳樟醇通过制备环氧芳樟醇或含环氧芳樟醇的混合物的方法制备，所述的方法包括在酶的存在下氧化芳樟醇或含芳樟醇的混合物形成反应混合物的步骤。
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| CN107129475A (zh) * | 2017-04-27 | 2017-09-05 | 上海应用技术大学 | 一种呋喃型氧化芳樟醇的制备方法 |
| CN109734554A (zh) * | 2019-02-25 | 2019-05-10 | 江苏暨明医药科技有限公司 | 一种反式-薄荷基-2,8-二烯-1-醇的合成工艺 |
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| CN1925826A (zh) * | 2003-05-08 | 2007-03-07 | 弗莱克特瑞尔公司 | 新型芳香衍生物 |
| JP2008133233A (ja) * | 2006-11-29 | 2008-06-12 | Noevir Co Ltd | Ｗｎｔ５ａ産生促進剤、養毛剤 |
| EP2075320A1 (de) * | 2007-12-17 | 2009-07-01 | Symrise GmbH & Co. KG | Verfahren zur Herstellung eines Aromakonzentrates sowie ein Aromakonzentrat |
| US8158180B2 (en) | 2007-12-17 | 2012-04-17 | Symrise Gmbh & Co. Kg | Process for the preparation of a flavoring concentrate |
| KR101664355B1 (ko) * | 2014-07-24 | 2016-10-11 | 농업회사법인조인주식회사 | 오일의 오메가-3 지방산 함량을 증가시키는 칸디다 안타르티카 5k-11 균주 및 이를 이용하여 제조된 발효 오일 |
| US20170191086A1 (en) * | 2015-12-30 | 2017-07-06 | Natura Cosméticos S.A. | Process for the transformation of essential oils comprising linalol |
| CN114058650A (zh) * | 2021-11-16 | 2022-02-18 | 北京化工大学 | 一种双酶偶联反应系统制备环氧植物油的方法 |
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| AU639494B2 (en) | 1989-09-12 | 1993-07-29 | Novo Nordisk A/S | A process for preparing peroxycarboxylic acids using an enzyme catalyst |
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| CN107129475A (zh) * | 2017-04-27 | 2017-09-05 | 上海应用技术大学 | 一种呋喃型氧化芳樟醇的制备方法 |
| CN107129475B (zh) * | 2017-04-27 | 2019-05-31 | 上海应用技术大学 | 一种呋喃型氧化芳樟醇的制备方法 |
| CN109734554A (zh) * | 2019-02-25 | 2019-05-10 | 江苏暨明医药科技有限公司 | 一种反式-薄荷基-2,8-二烯-1-醇的合成工艺 |
| CN109734554B (zh) * | 2019-02-25 | 2021-11-23 | 江苏暨明医药科技有限公司 | 一种反式-薄荷基-2,8-二烯-1-醇的合成工艺 |
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| RU2001129789A (ru) | 2003-10-10 |
| JP2002191391A (ja) | 2002-07-09 |
| BR0105071A (pt) | 2002-12-10 |
| US20020086376A1 (en) | 2002-07-04 |
| AU8922401A (en) | 2002-05-09 |
| HUP0104565A2 (en) | 2002-08-28 |
| DE10055092A1 (de) | 2002-05-08 |
| MXPA01011280A (es) | 2002-05-14 |
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| HU0104565D0 (en) | 2002-01-28 |
| KR20020035755A (ko) | 2002-05-15 |
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