JP5372935B2 - ω−不飽和脂肪酸の合成方法 - Google Patents
ω−不飽和脂肪酸の合成方法 Download PDFInfo
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- JP5372935B2 JP5372935B2 JP2010525402A JP2010525402A JP5372935B2 JP 5372935 B2 JP5372935 B2 JP 5372935B2 JP 2010525402 A JP2010525402 A JP 2010525402A JP 2010525402 A JP2010525402 A JP 2010525402A JP 5372935 B2 JP5372935 B2 JP 5372935B2
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- acid
- chain
- unsaturated fatty
- ester
- fatty acids
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Classifications
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- C—CHEMISTRY; METALLURGY
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- 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
- 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
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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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
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
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Description
本発明方法では、脂肪酸はその酸の形またはそのエステル形で処理できる。一つの形から他方の形への変換はメタノリシス、エステル化または加水分解で実行できる。従って、以下では説明を簡単にするために主として酸について説明する。その反応はエステルの場合にもそのまま適用できる。
W. H. Eschenfeldt et al., "Transformation of Fatty Acids Catalyzed by Cytochrome P450 Monooxygenase Enzymes of Candida tropicalis"、Applied and Environmental Microbiology, Oct. 2003, pp 5992-5999
J.C. Mol, Catalytic metathesis of unsaturated fatty acid esters and oil"、Topics in Catalysis, Vol. 27, Nos. 1-4, February 2004 (Plenum Publishing Corporation)
Schrock et al., J. Am. Chem. Soc., 108 (1986), 2771 Basset et al., Angew. Chem., Ed. Engl., 31(1992), 628
Grubbs et al., Angew. Chem., Ed. EngI., 34 (1995), 2039, and Organic Lett., 1 (1999), 953
オレイン酸の発酵
この実施例ではソルビトール、微量元素、尿素およびオレイン酸を含む脱イオン水中でpH=7で少なくとも一つのオキシゲナーゼ酵素を含むイーストを培養する。混合物を120℃で15分間殺菌する。その後、イースト株を培地に接種する。培養中は30℃に維持する。pHを7〜7.5に維持するために水酸化ナトリウム溶液を連続的に加える。48時間培養後、不飽和ジアシッドをジエチルエーテルで抽出して回収する。蒸留して溶剤を除去回収し、再結晶後に9-オクタデセン二酸に対応する融点が69℃の結晶を回収した。
実施例2
エルカ酸の発酵
エルカ酸を用いて実施例1を繰り返した。9-ドコセン二酸が得られる。
9-オクタデセン二酸のクロス-メタセシス
この実施例は9-オクタデセン二酸から9−デセン酸を合成する例を示す。本発明方法の第2段階はエチレンを用いたクロス-メタセシスである。この反応には下記文献に記載のビスピリジン−ルテニウム型の複合触媒に類似したものを使用した。
Chen-Xi Bai et al., Org. Biomol. Chem., (2005), 3, 41 39-4142
9-オクタデセン二酸のクロス-メタセシス
実施例2のジアシッドの9-オクタデセン二酸を用いて実施例3を繰り返した。9-デセン酸と13-テトラデセン酸を実質的に等モル収率で得た。
C18不飽和ジエステルのエテノリシス
窒素でパージした50mlのシュレンク管中に1gのメチル9-オクタデセンジオエート(octadecenedioate)(0.5mmol)と、47mg(7.5×10-2mmol)のAldrichから入手可能な第二世代のHoveyda-Grubbs触媒の(1,3-ビス(2,4,6-トリメチルフェニル)-2-イミダゾリジニリデン)ジクロロ(O-イソプロポキシフェニルメチレン)ルテニウム)(2mlのトルエン溶液)と、ベンゾフェノンナトリウム上で蒸留した15mlのトルエンとを入れる。170mg(6mmol)のエチレンを加え、磁気撹拌下に20℃で3時間反応させる。反応液をガスクロマトグラフィで分析する。不飽和ジエステルの変換率は83%である。2−メチルウンデセジオエートの収率は95%である。メチル9-デセノエートの収率は64%である。
Claims (6)
- 式:CH3−(CH2)m−CH=CH−(CH2)p−COORの長鎖モノ不飽和脂肪酸またはエステル(ここで、mとpは2〜11の整数で、互いに同一でも異なっていてもよく、RはHまたは1〜4の炭素原子を有するアルキル基である)から一般式:CH2=CH−(CH2)n−COORの短鎖のω−不飽和脂肪酸またはエステル(ここで、nは2〜11の整数であり、Rは上記と同じ意味を有する)を合成する方法であって、
第1段階で、原料の長鎖モノ不飽和脂肪酸またはエステルをオキシゲナーゼ型酵素を含んだ微生物を使用した発酵によって酸化させて長鎖のω−ジアシッドまたはジエステルを形成し、
オキシゲナーゼ型酵素を第2段階で、第1段階で生じた生成物をルテニウム−とレニウムとをベースにした触媒の存在下で、エチレンでクロス−メタセシスして、出発原料の不飽和脂肪酸またはエステルの主鎖の長さに対する主鎖の長さの比が0.2〜0.8である2つの短鎖ω−不飽和脂肪酸またはエステルを形成する、ことを特徴とする方法。 - オキシゲナーゼ型酵素がバクテリア、真菌またはイースト菌である請求項1に記載の方法。
- 出発原料の不飽和脂肪酸またはエステルの主鎖の長さに対する主鎖の長さの比が0.35〜0.75である請求項1または2に記載の方法。
- 第1の段階をシトクローム(Cytochrome)P450モノオキシジェナーゼ(Monooxygenase)酵素を含むカンジダトロピカリス(Candida tropicalis)の存在下で実行する請求項1〜3のいずれか一項に記載の方法。
- オレイン酸から9-デセン酸を合成する請求項1〜4のいずれか一項に記載の方法。
- エルカ酸から9−デセン酸と13-テトラデセン酸とを合成する請求項1〜4のいずれか一項に記載の方法。
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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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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 |
EP2984490B1 (en) | 2013-06-14 | 2020-05-20 | Genomatica, Inc. | Methods of producing omega-hydroxylated fatty acid derivatives |
ES2803560T3 (es) | 2014-06-16 | 2021-01-27 | Genomatica Inc | Polipéptidos de fusión relacionados con omega-hidroxilasa con propiedades mejoradas |
WO2016103677A1 (en) * | 2014-12-26 | 2016-06-30 | Kao Corporation | Method for producing omega-hydroxy fatty acid ester and precursor compound thereof |
WO2017101987A1 (en) | 2015-12-15 | 2017-06-22 | REG Life Sciences, LLC | Omega-hydroxylase-related fusion polypeptide variants with improved properties |
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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 |
JPS5765194A (en) * | 1980-10-09 | 1982-04-20 | Daicel Chem Ind Ltd | Microbial preparation of unsaturated dicarboxylic 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 |
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US6660505B2 (en) * | 2000-06-22 | 2003-12-09 | Cognis Corporation | Isolation of carboxylic acids from fermentation broth |
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CN101868550B (zh) | 2013-02-27 |
EP2198036B1 (fr) | 2011-12-21 |
FR2921362B1 (fr) | 2012-09-21 |
ATE538208T1 (de) | 2012-01-15 |
BRPI0816432A2 (pt) | 2014-10-14 |
WO2009047445A1 (fr) | 2009-04-16 |
US20100216198A1 (en) | 2010-08-26 |
JP2010539226A (ja) | 2010-12-16 |
EP2198036A1 (fr) | 2010-06-23 |
CN101868550A (zh) | 2010-10-20 |
FR2921362A1 (fr) | 2009-03-27 |
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