CN101868550B - 合成ω-不饱和脂肪酸的方法 - Google Patents
合成ω-不饱和脂肪酸的方法 Download PDFInfo
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- CN101868550B CN101868550B CN200880116900.5A CN200880116900A CN101868550B CN 101868550 B CN101868550 B CN 101868550B CN 200880116900 A CN200880116900 A CN 200880116900A CN 101868550 B CN101868550 B CN 101868550B
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- acid
- fatty acids
- unsaturated fatty
- chain
- acid ester
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Classifications
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C12P7/6436—Fatty acid esters
- C12P7/6445—Glycerides
- C12P7/6472—Glycerides containing polyunsaturated fatty acid [PUFA] residues, i.e. having two or more double bonds in their backbone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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Abstract
本发明涉及由式CH3-(CH2)m-CH＝CH-(CH2)p-COOR的长链单不饱和脂肪酸或脂肪酸酯合成通式CH2＝CH-(CH2)n-COOR的短链ω-不饱和脂肪酸的方法，在式CH3-(CH2)m-CH＝CH-(CH2)p-COOR中，m和p是相同或不同并且为2～11的整数，使得该分子在主链中包含至少10个相邻的碳原子，在通式CH2＝CH-(CH2)n-COOR中，n为2～11的整数且R为H或含有1～4个碳原子的烷基，其中所述方法包括：通过使用含有加氧酶型的酶的微生物进行发酵而对所述长链单不饱和脂肪酸进料进行氧化从而导致形成α，ω-二酸的第一步骤；和使得自第一步骤的产物与乙烯进行催化交叉复分解以形成两种其主链长度相对于所述起始不饱和脂肪酸或脂肪酸酯的主链长度为0.2～0.8、优选为0.35～0.75的短链ω-不饱和脂肪酸的第二步骤。
Description
本发明涉及由天然单不饱和脂肪酸或脂肪酸酯通过复分解合成ω-不饱和脂肪酸或脂肪酸酯的方法。
ω-不饱和酸或ω-不饱和酸酯是在例如羰基化、加氢甲酰基化、尤其是环氧化的整个系列的反应中有用的分子。这些酸通常不是根据用于不饱和酸的化学合成的常用方法制备的，所述常用方法通常产生α-或β-不饱和酸而不是ω-不饱和脂肪酸。因此，在实践中，这种类型的酸源自经历或多或少复杂的处理的更复杂的不饱和酸(尤其是天然来源的脂肪酸)的转化。
因此，已知用于制造11-氨基十一烷酸的工业方法使用从蓖麻油中提取的蓖麻油酸作为原料，其是合成Rilsan
的基础。在这种方法中，通过进料(charge)的热解合成处于其酯形式即十一碳烯酸酯的ω-十一碳烯酸作为中间产物，所述进料的热解伴随着作为副产物的庚醛的形成。这种方法描述于A.Chauvel等人在Editions TECHNIP(1986)中发表的著作“Les Procédés dePétrochimie”中。
另一由“长链”脂肪酸或脂肪酸酯合成“短链”ω-不饱和脂肪酸或脂肪酸酯的方法在于实施这些长链酸与乙烯的交叉复分解，该操作称为乙烯分解(ethenolysis)。在Soon Hyeok Hong等人在Journal of the American ChemicalSociety 2005，127，17160-17161中发表的文章“Prevention of UndesirableIsomerization during Olefin Metathesis”中详细叙述了这种方法，该文章提到了在这种情况下异构化与复分解之间竞争的风险。在J.C.Mol在2004年2月的Topics in Catalysis第17卷，第1-4期，第97-104页中发表的文章“Catalytic metathesis of unsaturated fatty acid esters and oils”中也提到了该方法。
在如此描述的方法中应该观察到“短链”ω-不饱和脂肪酸的形成总是伴随着α-烯烃的相伴形成。就该方法的成本而言，这具有必须现场找到这种作为反应副产物的α-烯烃的工业应用的缺点。实际上，由于α-烯烃的市场价格约为单不饱和脂肪酸的市场价格，从财务的观点来看，ω-不饱和脂肪酸必须独自负担所有的合成成本。
通过下面的说明岩芹酸的乙烯分解的方案举例说明该反应。
本发明的目的在于通过提出由天然来源的脂肪酸或脂肪酸酯仅产生“短链”ω-不饱和脂肪酸的方法来克服该缺陷。
在本发明的方法中，脂肪酸可以其酸形式或以其酯形式进行处理。通过甲醇分解、酯化或水解实施从一种形式到另一种形式的转变。为了公开内容的简洁起见，下面的描述将主要针对酸，但应知道该反应可紧接着变换为酯。
本发明的主题是由天然来源的式CH3-(CH2)m-CH＝CH-(CH2)p-COOR的长链单不饱和脂肪酸或脂肪酸酯合成通式CH2＝CH-(CH2)n-COOR的“短链”ω-不饱和脂肪酸或脂肪酸酯的方法，在式CH3-(CH2)m-CH＝CH-(CH2)p-COOR中，m和p是可相同或不同并且为2～11的整数，使得该分子在主链中含有至少10个相邻的碳原子，在通式CH2＝CH-(CH2)n-COOR中，n为2～11的整数且R为H或含有1～4个碳原子的烷基，所述方法包括：通过发酵对长链的主要是单不饱和的脂肪酸或脂肪酸酯进料进行氧化从而导致形成长链α，ω-二酸的第一步骤；和随后的使得自所述第一步骤的产物与乙烯进行交叉复分解以导致形成两种“短链”ω-不饱和脂肪酸或脂肪酸酯的第二步骤。
在本发明的方法中，表述“短链”ω-不饱和脂肪酸或脂肪酸酯意指通常含有数量为5～14个的相邻碳原子的化合物，该数量总是小于用于其合成的单不饱和脂肪酸或脂肪酸酯的主链的碳原子数。ω-不饱和酸的链长度与起始不饱和脂肪酸的链长度之比0.2～0.8，并优选为0.35～0.75，甚至更优选为0.42～0.72，甚至更优选为0.45～0.64。在本发明方法的一个优选变型中，这些ω-不饱和酸或酯每个分子含有6～14个碳原子。
在本发明的方法中，表述“主要是单不饱和的脂肪酸或脂肪酸酯进料”意指具有大于50％，优选大于80％的单不饱和脂肪酸或脂肪酸酯重量含量的进料。
根据所使用的进料和通过发酵进行氧化的条件，得到两种不同的“短链”ω-不饱和脂肪酸作为最终产物，或者，如果所形成的二酸是对称的，则得到单一的“短链”ω-不饱和脂肪酸作为最终产物，这对于该方法的产率来说是特别有利的。
在本发明的方法中，表述“天然来源的长链单不饱和脂肪酸或脂肪酸酯”意指这样的酸或酯，其得自植物或动物界(包括藻类)，更通常得自植物界，并因此是可再生的，且每个分子含有至少10个且优选至少14个碳原子。
作为这样的酸的实例，可提及：C10酸：4-十碳烯酸(顺式-4-癸烯酸)；C12酸：月桂烯酸(顺式-5-十二碳烯酸)和4-十二碳烯酸(顺式-4-十二碳烯酸)；C14酸：肉豆蔻烯酸(顺式-9-十四碳烯酸)、抹香鲸酸(顺式-5-十四碳烯酸)和粗租酸(顺式-4-十四碳烯酸)；C16酸：棕榈油酸(顺式-9-十六碳烯酸)；C18酸：油酸(顺式-9-十八碳烯酸)、反油酸(反式-9-十八碳烯酸)、岩芹酸(顺式-6-十八碳烯酸)、异油酸(顺式-11-十八碳烯酸)和蓖麻油酸(12-羟基-顺式-9-十八碳烯酸)；C20酸：鳕油酸(顺式-9-二十碳烯酸)、巨头鲸鱼酸(顺式-11-二十碳烯酸)、顺式-5-二十碳烯酸和14-羟基-顺式-11-二十碳烯酸(lesquerolic acid)(14-羟基-顺式-11-二十碳烯酸)；和C22酸：鲸蜡烯酸(顺式-11-二十二碳烯酸)和芥酸(顺式-13-二十二碳烯酸)。
通过使用使进料的脂肪酸或脂肪酸酯能够被氧化的微生物例如细菌、真菌或酵母进行发酵而实施第一步骤。优选使用能够通过形成酸-COOH或酯-COOR的三价官能团而将进料氧化的含有加氧酶型的酶的微生物。
该发酵可例如在包含细胞色素P450单加氧酶(monooxygenase enzymes)的热带假丝酵母(Candida tropicalis)菌株的存在下进行，所述热带假丝酵母菌株例如为在如下文献中描述的那些：W.H.Eschenfeldt等人的出版物即2003年10月的Applied and Environmental Microbiology第5992-5999页中发表的“Transformation of Fatty Acids Catalyzed by Cytochrome P450Monooxygenase Enzymes of Candida tropicalis”、以及专利FR2445374、US4474882、US3823070、US3912586、US6660505、US6569670和5254466。
尽管第二步骤中实施的复分解反应的工业应用相对有限，但其在长时间以前就已经是已知的了，不过，对于二酸却从来没有描述过所述复分解反应。关于其在脂肪酸(酯)的转化中的用途，可参考J.C.Mol在2004年2月的Topics in Catalysis(Plenum Publishing Corporation)第27卷第1-4期中发表的文章“Catalytic metathesis of unsaturated fatty acid esters and oil”。
复分解反应的催化一直是复杂催化体系的许多研究和开发的主题。可提及例如，Schrock等人在J.Am.Chem.Soc.，108(1986)，2771中或Basset等人在Angew.Chem.，Ed.Engl.，31(1992)，628中提出的钨络合物。最近，已出现作为钌-亚苄基络合物的“Grubbs’”催化剂(Grubbs等人的Angew.Chem.，Ed.Engl.，34(1995)，2039和Organic Lett.，1(1999)，953)。该催化为均相催化。还已开发了基于沉积在氧化铝或二氧化硅上的金属(例如铼、钼和钨)的非均相催化剂。最后，已经进行了关于制备固定化催化剂的研究，该固定化催化剂即为其活性成分为均相催化剂的活性成分，尤其是钌-卡宾络合物，但固定在非活性载体上的催化剂。这些研究的目的是提高被带到一起的各反应物之间的反应相对于副反应例如“homometathese”的选择性。它们不仅与催化剂的结构有关，而且还与反应介质和可引入的添加剂的作用有关。
在本发明的方法中，可使用任何活性的和选择性的复分解催化剂。然而，优选使用基于钌和基于铼的催化剂。
通过下文中的短链脂肪族二酸合成的实例举例说明第二步骤。为了使本公开内容简洁起见，下面详细描述的所有机理都以酸形式进行举例说明。然而，所述复分解对于酯是同样有效的并且通常甚至更加有效。同样地，各方案以酸(或酯)的顺式异构体对各反应进行举例说明；所述机理同样可适用于反式异构体。
该第二步骤的使用油二酸(oleic diacid)(或称为α，ω-9-十八碳烯二酸)和乙烯的反应过程如下：
可以看出，在这种情况下，所述方法具有在避免形成副产物，从而仅产生9-癸烯酸方面的最特别的优势。
所述反应过程通过下面的方案1表示。
方案1
在一些发酵条件下，将昆士兰油(macadamia oil)或沙棘油(sea buckthornoil)部分氧化，以由这些油中所含的棕榈油酸产生C16二酸即α，ω-7-十六碳烯二酸。
可以通过下面的机理描述该第二步骤的使用这种二酸和乙烯以产生两种不同的ω-不饱和酸即9-癸烯酸和7-辛烯酸的反应过程：
方案2
月桂烯酸在发酵期间转化为α，ω-5-十二碳烯二酸。该方法的第二步骤根据下面的过程产生两种不同长度的ω-烯属酸即7-辛烯酸和5-己烯酸：
肉豆蔻烯酸在发酵期间转化为α，ω-5-十四碳烯二酸。该方法的第二步骤根据下面的过程产生两种不同长度的ω-烯属酸即9-癸烯酸和5-己烯酸：
通过以下实施例说明本发明。
实施例
实施例1：油酸发酵
在该实施例中，使用含有至少一种加氧酶的酵母。
将该酵母在包含山梨糖醇、痕量元素、尿素和油酸的去离子水介质中在pH＝7下培养。随后将该混合物在120℃下灭菌15分钟。随后将酵母菌株接种到培养基中。将培养物保持在30℃下。不断加入氢氧化钠溶液以将pH维持在7.0-7.5。在培养48小时之后，通过用二乙醚进行萃取而收取不饱和二酸。在通过蒸发除去溶剂之后，收取晶体，该晶体在重结晶之后具有69℃的熔点，即等于对于9-十八碳烯二酸所描述的熔点。
实施例2：芥酸发酵
使用芥酸重复实施例1。得到9-二十二碳烯二酸(9-docosenedioic acid)。
实施例3：9-十八碳烯二酸的交叉复分解
该实施例说明由9-十八碳烯二酸合成9-癸烯酸。该方法的第二步骤为与乙烯的交叉复分解。对于该反应，使用双(吡啶)钌型络合催化剂，例如在Chen-Xi Bai等人的出版物即Org.Biomol.Chem.，(2005)，3，4139-4142中描述的双(吡啶)钌型络合催化剂。该反应在CH2Cl2中、在相对于9-十八碳烯二酸的浓度为1摩尔％的催化剂的存在下、在80℃的温度下进行12小时，其中乙烯的摩尔浓度为9-十八碳烯二酸的摩尔浓度的两倍。通过色谱分析测定产率，9-癸烯酸CH2＝CH-(CH2)7-COOH的产率是基本上等摩尔的(equimolar)。
实施例4：9-二十二碳烯二酸的交叉复分解
用实施例2的二酸即9-二十二碳烯二酸重复实施例3。得到基本上等摩尔产率的9-癸烯酸和13-十四碳烯酸。
实施例5：不饱和C18二酯的乙烯分解
将1g 9-十八碳烯二酸甲酯(3mmol)、47mg(7.5×10-2mmol)可得自Aldrich公司的第二代Hoveyda-Grubbs催化剂(1，3-双(2，4，6-三甲基苯基)-2-亚咪唑烷基(imidazolidinylidene))二氯(邻-异丙氧基苯基亚甲基)钌)、和15ml通过钠、二苯甲酮蒸馏的甲苯进料到50ml用氮气吹扫的Schlenk管中。加入170mg乙烯(6mmol)并使该混合物在磁性搅拌下、在20℃下反应3小时。通过气相色谱法分析反应混合物。不饱和二酯的转化率为83％。9-癸烯酸甲酯的产率为64％。
Claims (7)
1.由式CH3-(CH2)m-CH＝CH-(CH2)p-COOR的长链单不饱和脂肪酸或脂肪酸酯合成通式CH2＝CH-(CH2)n-COOR的短链ω-不饱和脂肪酸或脂肪酸酯的方法，在式CH3-(CH2)m-CH＝CH-(CH2)p-COOR中，m和p相同或不同并且为2～11的整数，使得该分子在主链中含有至少10个相邻的碳原子，在通式CH2＝CH-(CH2)n-COOR中，n为2～11的整数且R为H或含有1～4个碳原子的烷基，所述方法包括：通过使用含有加氧酶型的酶的微生物进行发酵而对所述长链单不饱和脂肪酸或脂肪酸酯进料进行氧化从而导致形成长链α，ω-二酸或α，ω-二酯的第一步骤；和随后的使得自所述第一步骤的产物与乙烯在基于钌的催化剂和基于铼的催化剂的存在下进行催化交叉复分解以导致形成两种其主链长度相对于所述起始不饱和脂肪酸或脂肪酸酯的主链长度为0.2～0.8的短链ω-不饱和脂肪酸或脂肪酸酯的第二步骤。
2.权利要求1的方法，其中所述微生物为细菌、真菌或酵母。
3.权利要求1的方法，其中所述短链ω-不饱和脂肪酸或脂肪酸酯的主链长度相对于所述起始不饱和脂肪酸或脂肪酸酯的主链长度为0.35～0.75。
4.权利要求1的方法，其特征在于，所述第一步骤在包含细胞色素P450单加氧酶的热带假丝酵母菌株的存在下进行。
5.权利要求1-4任一项的方法，其特征在于，由油酸合成9-癸烯酸。
6.权利要求1～4中任一项的方法，其特征在于，由芥酸合成9-癸烯酸和13-十四碳烯酸。
7.权利要5的方法，其特征在于，由芥酸合成9-癸烯酸和13-十四碳烯酸。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| FR0757694A FR2921362B1 (fr) | 2007-09-20 | 2007-09-20 | Procede de synthese d'acides gras omega-insatures |
| FR0757694 | 2007-09-20 | ||
| PCT/FR2008/051665 WO2009047445A1 (fr) | 2007-09-20 | 2008-09-17 | Procede de synthese d'acides gras omega-insatures |
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| CN101868550A CN101868550A (zh) | 2010-10-20 |
| CN101868550B true CN101868550B (zh) | 2013-02-27 |
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| EP (1) | EP2198036B1 (zh) |
| JP (1) | JP5372935B2 (zh) |
| CN (1) | CN101868550B (zh) |
| AT (1) | ATE538208T1 (zh) |
| BR (1) | BRPI0816432A2 (zh) |
| FR (1) | FR2921362B1 (zh) |
| WO (1) | WO2009047445A1 (zh) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276444B (zh) * | 2011-05-04 | 2013-10-09 | 厦门大学 | 脂肪酸类化合物及其制备方法与应用 |
| US9163267B2 (en) * | 2012-04-11 | 2015-10-20 | REG Life Sciences, LLC | Metathesis transformations of microbially-produced fatty acids and fatty acid derivatives |
| FR3001964B1 (fr) | 2013-02-08 | 2015-02-20 | Arkema France | Synthese de compose insature ramifie par metathese croisee |
| SI2984490T1 (sl) | 2013-06-14 | 2020-10-30 | Genomatica, Inc. | Metode proizvodnje derivatov omega hidroksilirane maščobne kisline |
| EP3087179B1 (en) | 2014-06-16 | 2020-04-08 | Genomatica, Inc. | Omega-hydroxylase-related fusion polypeptides with improved properties |
| JP6794108B2 (ja) * | 2014-12-26 | 2020-12-02 | 花王株式会社 | ω−ヒドロキシ脂肪酸エステルおよびその前駆体化合物の製造方法 |
| WO2017101987A1 (en) | 2015-12-15 | 2017-06-22 | REG Life Sciences, LLC | Omega-hydroxylase-related fusion polypeptide variants with improved properties |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4474882A (en) * | 1980-10-09 | 1984-10-02 | Daicel Chemical Industries, Ltd. | Microbiological process for the preparation of unsaturated dicarboxylic acids |
| EP0444264A2 (de) * | 1990-03-02 | 1991-09-04 | Hüls Aktiengesellschaft | Katalysatoren für die Metathese von Olefinen und funktionalisierten Olefinen |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3823070A (en) * | 1971-12-23 | 1974-07-09 | Hasegawa T Co Ltd | Process for producing a straight chain dicarboxylic acid,an omega-hydroxy fatty acid,and an omega-1-keto fatty acid |
| DE3916550A1 (de) * | 1989-05-20 | 1990-11-22 | Henkel Kgaa | Verwendung ausgewaehlter oleophiler ether in wasser-basierten bohrspuelungen vom o/w-emulsionstyp sowie entsprechende bohrspuelfluessigkeiten mit verbesserter oekologischer vertraeglichkeit |
| US5254466A (en) * | 1989-11-06 | 1993-10-19 | Henkel Research Corporation | Site-specific modification of the candida tropicals genome |
| US6569670B2 (en) * | 1999-09-30 | 2003-05-27 | Cognis Corporation | Fermentation process |
| US6660505B2 (en) * | 2000-06-22 | 2003-12-09 | Cognis Corporation | Isolation of carboxylic acids from fermentation broth |
| CA2441980C (en) * | 2001-03-26 | 2011-07-19 | Dow Global Technologies Inc. | Metathesis of unsaturated fatty acid esters or unsaturated fatty acids with lower olefins |
| FR2896498B1 (fr) * | 2006-01-24 | 2008-08-29 | Inst Francais Du Petrole | Procede de co-production d'olefines et de diesters ou de diacides a partir de corps gras insatures. |
-
2007
- 2007-09-20 FR FR0757694A patent/FR2921362B1/fr not_active Expired - Fee Related
-
2008
- 2008-09-17 AT AT08836942T patent/ATE538208T1/de active
- 2008-09-17 JP JP2010525402A patent/JP5372935B2/ja not_active Expired - Fee Related
- 2008-09-17 CN CN200880116900.5A patent/CN101868550B/zh not_active Expired - Fee Related
- 2008-09-17 BR BRPI0816432-0A2A patent/BRPI0816432A2/pt not_active Application Discontinuation
- 2008-09-17 US US12/678,622 patent/US20100216198A1/en not_active Abandoned
- 2008-09-17 WO PCT/FR2008/051665 patent/WO2009047445A1/fr active Application Filing
- 2008-09-17 EP EP08836942A patent/EP2198036B1/fr not_active Not-in-force
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4474882A (en) * | 1980-10-09 | 1984-10-02 | Daicel Chemical Industries, Ltd. | Microbiological process for the preparation of unsaturated dicarboxylic acids |
| EP0444264A2 (de) * | 1990-03-02 | 1991-09-04 | Hüls Aktiengesellschaft | Katalysatoren für die Metathese von Olefinen und funktionalisierten Olefinen |
Non-Patent Citations (2)
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| J.C.Mol.Catalytic metathesis of unsaturated fatty acid esters and oils.《Topic in catalysis》.2004,第27卷(第1期),97－104. * |
| Warwel S et al.Polymers and surfactants on the basis of renewable resources.《Chemosphere》.2001,第43卷39-48. * |
Also Published As
| Publication number | Publication date |
|---|---|
| US20100216198A1 (en) | 2010-08-26 |
| WO2009047445A1 (fr) | 2009-04-16 |
| EP2198036A1 (fr) | 2010-06-23 |
| CN101868550A (zh) | 2010-10-20 |
| EP2198036B1 (fr) | 2011-12-21 |
| FR2921362B1 (fr) | 2012-09-21 |
| JP5372935B2 (ja) | 2013-12-18 |
| JP2010539226A (ja) | 2010-12-16 |
| BRPI0816432A2 (pt) | 2014-10-14 |
| FR2921362A1 (fr) | 2009-03-27 |
| ATE538208T1 (de) | 2012-01-15 |
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