JP2000247965A - Conjugated linolic acid ester, its production and its use - Google Patents
Conjugated linolic acid ester, its production and its useInfo
- Publication number
- JP2000247965A JP2000247965A JP11052638A JP5263899A JP2000247965A JP 2000247965 A JP2000247965 A JP 2000247965A JP 11052638 A JP11052638 A JP 11052638A JP 5263899 A JP5263899 A JP 5263899A JP 2000247965 A JP2000247965 A JP 2000247965A
- Authority
- JP
- Japan
- Prior art keywords
- linoleic acid
- conjugated linoleic
- acid ester
- conjugated
- ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 linolic acid ester Chemical class 0.000 title claims abstract description 78
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229960004232 linoleic acid Drugs 0.000 title abstract 7
- 235000013305 food Nutrition 0.000 claims abstract description 41
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 27
- 230000003647 oxidation Effects 0.000 claims abstract description 26
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 17
- 230000032050 esterification Effects 0.000 claims abstract description 15
- 238000005886 esterification reaction Methods 0.000 claims abstract description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 150000002894 organic compounds Chemical group 0.000 claims abstract description 10
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 9
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 8
- 150000003904 phospholipids Chemical class 0.000 claims abstract description 6
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- 150000007524 organic acids Chemical class 0.000 claims abstract description 3
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims description 110
- 229940108924 conjugated linoleic acid Drugs 0.000 claims description 107
- JBYXPOFIGCOSSB-GOJKSUSPSA-N 9-cis,11-trans-octadecadienoic acid Chemical compound CCCCCC\C=C\C=C/CCCCCCCC(O)=O JBYXPOFIGCOSSB-GOJKSUSPSA-N 0.000 claims description 53
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 26
- 229930195729 fatty acid Natural products 0.000 claims description 26
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- 239000004367 Lipase Substances 0.000 claims description 24
- 102000004882 Lipase Human genes 0.000 claims description 24
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- 235000019421 lipase Nutrition 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 150000002632 lipids Chemical class 0.000 claims description 14
- 150000004665 fatty acids Chemical class 0.000 claims description 12
- 229940049918 linoleate Drugs 0.000 claims description 9
- OYHQOLUKZRVURQ-HZJYTTRNSA-M 9-cis,12-cis-Octadecadienoate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O OYHQOLUKZRVURQ-HZJYTTRNSA-M 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- 239000004480 active ingredient Substances 0.000 claims description 4
- 125000000837 carbohydrate group Chemical group 0.000 claims 1
- 125000002328 sterol group Chemical group 0.000 claims 1
- 150000002148 esters Chemical class 0.000 abstract description 16
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 abstract description 4
- 238000006388 chemical passivation reaction Methods 0.000 abstract description 3
- 229930182558 Sterol Natural products 0.000 abstract description 2
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- 150000003432 sterols Chemical class 0.000 abstract description 2
- 235000003702 sterols Nutrition 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 49
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 32
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 20
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- 235000010323 ascorbic acid Nutrition 0.000 description 16
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- 239000008157 edible vegetable oil Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
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- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- LGJMUZUPVCAVPU-UHFFFAOYSA-N beta-Sitostanol Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(C)CCC(CC)C(C)C)C1(C)CC2 LGJMUZUPVCAVPU-UHFFFAOYSA-N 0.000 description 7
- NJKOMDUNNDKEAI-UHFFFAOYSA-N beta-sitosterol Natural products CCC(CCC(C)C1CCC2(C)C3CC=C4CC(O)CCC4C3CCC12C)C(C)C NJKOMDUNNDKEAI-UHFFFAOYSA-N 0.000 description 7
- 239000008101 lactose Substances 0.000 description 7
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
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- CASUWPDYGGAUQV-UHFFFAOYSA-M potassium;methanol;hydroxide Chemical compound [OH-].[K+].OC CASUWPDYGGAUQV-UHFFFAOYSA-M 0.000 description 5
- JZNWSCPGTDBMEW-UHFFFAOYSA-N Glycerophosphorylethanolamin Natural products NCCOP(O)(=O)OCC(O)CO JZNWSCPGTDBMEW-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 235000009508 confectionery Nutrition 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- OIPPWFOQEKKFEE-UHFFFAOYSA-N orcinol Chemical compound CC1=CC(O)=CC(O)=C1 OIPPWFOQEKKFEE-UHFFFAOYSA-N 0.000 description 4
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- 239000000758 substrate Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000021615 conjugation Effects 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 3
- 235000020778 linoleic acid Nutrition 0.000 description 3
- JBXYCUKPDAAYAS-UHFFFAOYSA-N methanol;trifluoroborane Chemical compound OC.FB(F)F JBXYCUKPDAAYAS-UHFFFAOYSA-N 0.000 description 3
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- 230000001590 oxidative effect Effects 0.000 description 3
- KZJWDPNRJALLNS-VJSFXXLFSA-N sitosterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CC[C@@H](CC)C(C)C)[C@@]1(C)CC2 KZJWDPNRJALLNS-VJSFXXLFSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KILNVBDSWZSGLL-KXQOOQHDSA-N 1,2-dihexadecanoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCCCCCCCCCC KILNVBDSWZSGLL-KXQOOQHDSA-N 0.000 description 2
- SLKDGVPOSSLUAI-PGUFJCEWSA-N 1,2-dihexadecanoyl-sn-glycero-3-phosphoethanolamine zwitterion Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP(O)(=O)OCCN)OC(=O)CCCCCCCCCCCCCCC SLKDGVPOSSLUAI-PGUFJCEWSA-N 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- 239000005909 Kieselgur Substances 0.000 description 2
- 102100037611 Lysophospholipase Human genes 0.000 description 2
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- 239000007800 oxidant agent Substances 0.000 description 1
- 210000000496 pancreas Anatomy 0.000 description 1
- WTJKGGKOPKCXLL-RRHRGVEJSA-N phosphatidylcholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCCC=CCCCCCCCC WTJKGGKOPKCXLL-RRHRGVEJSA-N 0.000 description 1
- 150000008104 phosphatidylethanolamines Chemical class 0.000 description 1
- 150000003905 phosphatidylinositols Chemical class 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 235000020991 processed meat Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 235000021067 refined food Nutrition 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 210000004767 rumen Anatomy 0.000 description 1
- 235000015500 sitosterol Nutrition 0.000 description 1
- NLQLSVXGSXCXFE-UHFFFAOYSA-N sitosterol Natural products CC=C(/CCC(C)C1CC2C3=CCC4C(C)C(O)CCC4(C)C3CCC2(C)C1)C(C)C NLQLSVXGSXCXFE-UHFFFAOYSA-N 0.000 description 1
- 235000011888 snacks Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、新規な共役リノー
ル酸エステル、その製造法、該共役リノール酸エステル
を有効成分とする抗酸化剤、及び該共役リノール酸エス
テルを添加して脂質成分の酸化抑制作用を賦与した飲食
品に関する。本発明の共役リノール酸エステルは、飲
料、デザート、乳製品、調理食品、菓子類、パン類、麺
類等の一般的な加工食品からソース、ドレッシング等の
調味料や、健康食品、サプリメント食品まで幅広い分野
の飲食品に利用できる。本発明の共役リノール酸エステ
ルを飲食品に添加することにより、飲食品の保存中の脂
質成分の酸化抑制作用を賦与することができ、また、飲
食品摂取後に生体内で起こる脂質成分の酸化をも抑制す
ることができる。TECHNICAL FIELD The present invention relates to a novel conjugated linoleic acid ester, a method for producing the same, an antioxidant containing the conjugated linoleic acid ester as an active ingredient, and the oxidation of lipid components by adding the conjugated linoleic acid ester. The present invention relates to a food or drink having an inhibitory action. The conjugated linoleic acid ester of the present invention can be used in a wide range of applications from beverages, desserts, dairy products, cooked foods, confectionery, breads, noodles, and other general processed foods to sauces, dressings and other seasonings, health foods, and supplement foods. It can be used for food and drink in the field. By adding the conjugated linoleic acid ester of the present invention to foods and drinks, it is possible to impart the effect of inhibiting the oxidation of lipid components during storage of the foods and drinks, and to prevent the oxidation of lipid components occurring in vivo after ingestion of foods and drinks. Can also be suppressed.
【０００２】[0002]
【従来の技術】飲食品の抗酸化成分及び抗酸化剤につい
ては従来より広範囲に研究が進められてきた。ここで、
飲食品の抗酸化とは、飲食品中に存在する脂質成分の酸
化を抑制することを意味する。飲食品中の脂質成分の酸
化を抑制する目的で飲食品の原材料や食品添加物等とし
て使用されている代表的な抗酸化成分及び抗酸化剤とし
ては、トコフェロール（ビタミンＥ）、アスコルビン酸
（ビタミンＣ）、アスコルビン酸パルミテート、ポリフ
ェノール、クエン酸等が挙げられる。また、タンパク質
やアミノ酸と糖質とから生成される褐変物質（メイラー
ド反応生成物）にも抗酸化活性があることが知られてい
る。2. Description of the Related Art Antioxidant components and antioxidants in foods and drinks have been extensively studied. here,
Antioxidation of foods and beverages means that oxidation of lipid components present in foods and beverages is suppressed. Typical antioxidant components and antioxidants used as raw materials or food additives for foods and drinks for the purpose of suppressing the oxidation of lipid components in foods and drinks include tocopherol (vitamin E), ascorbic acid (vitamin C), ascorbic acid palmitate, polyphenol, citric acid and the like. It is also known that browning substances (Maillard reaction products) produced from proteins and amino acids and carbohydrates also have antioxidant activity.
【０００３】上記の抗酸化成分及び抗酸化剤は、酸化抑
制対象の飲食品の種類に応じて、適宜選択して使用され
ている。しかしながら、その効果は充分であるとは言え
ず、多くの飲食品においては、遮光容器を用いて光の透
過を低下させたり、窒素ガス等の不活性ガスで容器内の
空気を置換する等の手段により酸化抑制を試みている現
状にある。このような飲食品の抗酸化技術は、飲食品の
賞味期限に影響することから、食品産業上の大きな課題
である。[0003] The above-mentioned antioxidant components and antioxidants are appropriately selected and used in accordance with the type of food or drink to be inhibited. However, the effect cannot be said to be sufficient, and in many foods and beverages, light transmission is reduced by using a light-shielding container, or air in the container is replaced with an inert gas such as nitrogen gas. At present, oxidation suppression is being attempted by means. Such an antioxidant technology of food and drink affects the expiration date of the food and drink, and thus is a major problem in the food industry.
【０００４】飲食品において流通保存中に生成する酸化
生成物は、飲食品と共に摂取されてヒト生体内の細胞に
損傷を与え、老化を促進したり、悪性腫瘍を引き起こす
原因になると考えられている。また、飲食品を摂取した
後にヒト生体内で生じる脂質成分の酸化生成物も人体を
構成する細胞に対し同様の悪影響を及ぼすと考えられて
いる。従って、流通保存中の飲食品中の脂質成分の酸化
を抑制し、酸化生成物の生体内への摂取を防ぐことと同
様に、飲食品の摂取後に生体内で起こる脂質成分の酸化
を抑制し、細胞の損傷を防ぐことが重要とされ、このよ
うな効果を有する飲食品用の抗酸化剤が望まれている。[0004] Oxidation products generated during storage of food and drink during distribution are considered to be ingested together with the food and drink, causing damage to cells in the human body, promoting aging and causing malignant tumors. . In addition, it is considered that oxidation products of lipid components generated in a human body after ingestion of food or drink have a similar adverse effect on cells constituting the human body. Therefore, as well as suppressing the oxidation of lipid components in food and drink during distribution storage and preventing the ingestion of oxidation products into the living body, it suppresses the oxidation of lipid components occurring in the living body after ingestion of food and drink. It is important to prevent cell damage, and antioxidants for foods and drinks having such an effect are desired.
【０００５】一方、共役リノール酸は主にチーズや肉加
工製品中に微量に存在し、抗癌性や抗酸化活性を有する
と報告されており、食品成分として有用な物質として期
待されている。共役リノール酸については、飲食品にお
ける存在や含量等について研究が進められているが、飲
食品中での存在形態についてはほとんど研究が進められ
ておらず、わずかに生体内では遊離状態で存在すること
やトリグリセリド画分及びリン脂質画分に存在すること
が明らかにされているにすぎない。On the other hand, conjugated linoleic acid is reported to be present in trace amounts mainly in cheese and processed meat products, and is reported to have anticancer and antioxidant activities, and is expected as a useful substance as a food ingredient. Conjugated linoleic acid has been studied for its presence and content in foods and drinks, but little has been studied for its form in foods and drinks, and it is slightly free in vivo. And it is only shown that they are present in the triglyceride and phospholipid fractions.
【０００６】脂肪酸の共役化については古くから研究が
進められており、ウシの反芻胃中で微生物的に共役脂肪
酸が生成することや、油脂の代表的な加工工程である水
添反応の中間反応生成物として共役脂肪酸がわずかに生
成することがわかっている。また、光化学反応や単なる
加熱によってもわずかに脂肪酸の共役化が進行すること
がわかっているが、その生成物の主成分が共役リノール
酸であるか否かについては明確にされていない。[0006] Conjugation of fatty acids has been studied for a long time, and the formation of conjugated fatty acids microbiologically in the rumen of cattle and the intermediate reaction of hydrogenation, which is a typical processing step of fats and oils, have been studied. It has been found that conjugated fatty acids are slightly produced as products. Further, it is known that the conjugation of the fatty acid slightly proceeds by a photochemical reaction or simple heating, but it is not clear whether the main component of the product is conjugated linoleic acid.
【０００７】[0007]
【発明が解決しようとする課題】上記の現状に鑑み、本
発明は、共役リノール酸を水酸基又はエステル結合を１
個以上有する有機化合物とエステル化又はエステル交換
することにより得られ、より高い抗酸化活性を有する共
役リノール酸エステルを提供することを課題とする。ま
た、本発明は、該共役リノール酸エステルの製造法、該
共役リノール酸エステルを有効成分とする抗酸化剤、及
び該共役リノール酸エステルを添加して脂質成分の酸化
抑制作用を賦与した飲食品を提供することを課題とす
る。SUMMARY OF THE INVENTION In view of the above situation, the present invention relates to a method for forming a conjugated linoleic acid with a hydroxyl group or an ester bond.
It is an object of the present invention to provide a conjugated linoleic acid ester obtained by esterification or transesterification with an organic compound having at least one linoleic acid and having higher antioxidant activity. Further, the present invention provides a method for producing the conjugated linoleic acid ester, an antioxidant containing the conjugated linoleic acid ester as an active ingredient, and a food or drink having the conjugated linoleic acid ester added to impart an effect of inhibiting the oxidation of lipid components. The task is to provide
【０００８】[0008]
【課題を解決するための手段】本発明者らは、上記のよ
うに抗酸化活性を有する共役リノール酸を、水酸基又は
エステル結合を１個以上有する有機化合物とエステル化
又はエステル交換することにより、共役リノール酸より
も更に優れた抗酸化活性を有する共役リノール酸エステ
ルに変換できることを見出し、本発明を完成した。Means for Solving the Problems The present inventors esterify or transesterify conjugated linoleic acid having antioxidant activity with an organic compound having at least one hydroxyl group or ester bond as described above. They have found that they can be converted into conjugated linoleic acid esters having more excellent antioxidant activity than conjugated linoleic acid, and completed the present invention.
【０００９】以下、本発明を詳細に説明する。本発明に
おいて提供される共役リノール酸エステルは、共役リノ
ール酸と、水酸基又はエステル結合を１個以上有する有
機化合物とがエステル結合した次の一般式で示される新
規な共役リノール酸エステルである。Hereinafter, the present invention will be described in detail. The conjugated linoleic acid ester provided in the present invention is a novel conjugated linoleic acid ester represented by the following general formula in which conjugated linoleic acid and an organic compound having at least one hydroxyl group or ester bond are ester-bonded.
【００１０】[0010]
【化２】R1-COO-R2 [I] （式中、R1は、共役二重結合を１個有し、C17H32で表さ
れる脂肪族炭化水素基であり、R2は水酸基又はエステル
結合を１個以上有する有機化合物残基である。）## STR2 ## R 1 -COO-R 2 [I ] ( In the formula, R 1 has one conjugated double bond, an aliphatic hydrocarbon group represented by C 17 H 32, R 2 Is an organic compound residue having at least one hydroxyl group or ester bond.)
【００１１】また、本発明は、共役リノール酸と、水酸
基又はエステル結合を１個有する有機化合物とをエステ
ル化又はエステル交換することよりなる前記共役リノー
ル酸エステルの製造法に関する。さらに、本発明は前記
共役リノール酸エステルを有効成分とする抗酸化剤に関
する。またさらに、本発明は前記共役リノール酸エステ
ルを添加して脂質成分の酸化抑制作用を賦与した飲食品
に関する。The present invention also relates to a method for producing the conjugated linoleic acid ester, comprising esterifying or transesterifying a conjugated linoleic acid with an organic compound having one hydroxyl group or one ester bond. Furthermore, the present invention relates to an antioxidant containing the conjugated linoleic acid ester as an active ingredient. Still further, the present invention relates to a food or drink having the conjugated linoleic acid ester added to impart an effect of inhibiting oxidation of lipid components.
【００１２】[0012]
【発明の実施の形態】本発明で用いられる共役リノール
酸の起源は特に限定されず、例えば、植物油由来のリノ
ール酸をニッケル等の金属やアルカリ等を触媒として用
いて共役化したもの、乳及び乳製品より精製したもの、
肉及び肉製品より精製したものを使用することができ
る。本発明において共役リノール酸とエステル化又はエ
ステル交換するために用いられる水酸基又はエステル結
合を１個以上有する有機化合物としては、例えば、ホス
ファチジルエタノールアミン、ホスファチジルコリン、
ホスファチジルセリン、ホスファチジルイノシトール、
ホスファチジン酸、ホスファチジルグリセロール、スフ
ィンゴミエリン等のリン脂質、コレステロール、β−シ
トステロール等のステロール、ショ糖、乳糖等の糖類、
アスコルビン酸等の有機酸を挙げることができる。DETAILED DESCRIPTION OF THE INVENTION The origin of the conjugated linoleic acid used in the present invention is not particularly limited. For example, conjugated linoleic acid derived from vegetable oil using a metal such as nickel or an alkali as a catalyst, milk and Purified from dairy products,
Purified meat and meat products can be used. Examples of the organic compound having one or more hydroxyl groups or ester bonds used for esterification or transesterification with conjugated linoleic acid in the present invention include, for example, phosphatidylethanolamine, phosphatidylcholine,
Phosphatidylserine, phosphatidylinositol,
Phosphatidic acid, phosphatidylglycerol, phospholipids such as sphingomyelin, cholesterol, sterols such as β-sitosterol, sucrose, sugars such as lactose,
Organic acids such as ascorbic acid can be mentioned.
【００１３】本発明においてエステル化又はエステル交
換に用いられる触媒の種類は特に限定されず、例えば、
ナトリウムメトキシドや水酸化カリウム等のアルカリ触
媒、塩酸や硫酸等の酸触媒、リパーゼやホスホリパーゼ
等のエステルの加水分解反応を触媒する酵素等を触媒と
して用いることができるが、触媒として上記のエステル
の加水分解反応を触媒する酵素を用いて加水分解反応の
逆反応を利用すると、その反応中に新たな共役化が起き
ず、反応の制御が容易となるので好ましい。また、エス
テルの加水分解反応を触媒する酵素としては反応効率の
点からリパーゼ又はホスホリパーゼが好ましく、例え
ば、ブタ膵臓起源のリパーゼや、Mucor 属、Candida
属、Rhizopus属等のカビ起源のリパーゼ等を用いること
が好ましい。触媒としてリパーゼを用いる場合は、固定
化又は化学的に脂肪酸修飾したものを用いるとリパーゼ
の安定性が高まり、特に好ましい。ここで、リパーゼを
固定化する方法としては、シリカゲル、珪藻土、イオン
交換樹脂等の担体に、共有結合、イオン結合、物理的吸
着等によって酵素を結合させる担体結合法、グルタルア
ルデヒド等の２個又はそれ以上の官能基をもつ試薬を介
して酵素と担体を結合させる架橋法、ゲル格子、半透
膜、リポソーム、中空繊維等に酵素を封じ込める包括法
等が例示できる。また、リパーゼに化学的に脂肪酸を修
飾する方法としては、トリエチルアミン等を触媒とし脂
肪酸クロライドを直接酵素の官能基に結合させる方法、
脂肪酸クロライドからジメチルスルホニオ (ＤＳＰ) と
の活性エステルを調製し穏和な反応で酵素分子のリジン
残基及びＮ−末端に脂肪酸を結合させる方法等が例示で
きる。In the present invention, esterification or esterification
The type of catalyst used for the replacement is not particularly limited, for example,
Alkali contact with sodium methoxide and potassium hydroxide
Medium, acid catalysts such as hydrochloric acid and sulfuric acid, lipase and phospholipase
Enzymes that catalyze the hydrolysis of esters such as
The above ester can be used as a catalyst.
Hydrolysis using an enzyme that catalyzes the hydrolysis of
When the reverse reaction is used, new conjugation occurs during the reaction.
This is preferable because the reaction can be easily controlled. Also,
As an enzyme that catalyzes the hydrolysis of
Lipases or phospholipases are preferred from the point of view.
For example, lipase of pig pancreas origin,MucorGenus,Candida
Genus,RhizopusUse of lipase derived from molds such as genera
Is preferred. If lipase is used as the catalyst,
Lipase can be obtained by using chemically modified or chemically modified fatty acids.
Is particularly preferred because of increased stability. Where lipase
The method of immobilization is silica gel, diatomaceous earth, ion
Covalent bond, ionic bond, physical absorption
Glutarua, a carrier binding method that binds enzymes by attachment
Via a reagent having two or more functional groups such as aldehyde
Cross-linking method to bind enzyme and carrier, gel lattice, semi-permeable
Inclusion method that entraps enzymes in membranes, liposomes, hollow fibers, etc.
Etc. can be exemplified. Also, lipases are chemically modified with fatty acids.
As a decorating method, triethylamine or the like
A method of directly linking fatty acid chloride to a functional group of an enzyme,
From fatty acid chloride to dimethylsulfonio (DSP)
Lysine of the enzyme molecule in a mild reaction
For example, a method of binding a fatty acid to a residue and an N-terminal is exemplified.
Wear.
【００１４】エステル化又はエステル交換反応は、例え
ば、有機溶媒中又は基質のみの水分が 0.1％以下の微水
系にて、温度を酵素の至適温度に調整し、上記触媒を添
加して、共役リノール酸エステルが生成してくるまで反
応を行えばよい。また、リン酸緩衝液等の適当な緩衝液
中で基質及び触媒を混合攪拌することで共役リノール酸
エステルを生成させることができる。さらに、有機溶媒
と緩衝液を適当な比率で混合した溶液中において基質及
び触媒を混合攪拌して共役リノール酸エステルの生成を
進行させることもできる。In the esterification or transesterification reaction, for example, the temperature is adjusted to the optimum temperature of the enzyme in an organic solvent or a microaqueous system in which only the substrate has a water content of 0.1% or less. The reaction may be performed until a linoleic acid ester is produced. Also, a conjugated linoleic acid ester can be produced by mixing and stirring a substrate and a catalyst in an appropriate buffer such as a phosphate buffer. Further, the formation of the conjugated linoleic acid ester can be advanced by mixing and stirring the substrate and the catalyst in a solution in which the organic solvent and the buffer are mixed at an appropriate ratio.
【００１５】エステル化又はエステル交換により得られ
る生成物は基質に比べて極性が低下しているため、例え
ば、シリカゲルカラム、シリカゲル薄層プレート等を用
い、常法にて容易に分画することができ、分画された生
成物を濃縮乾固することにより共役リノール酸エステル
を得ることができる。Since the product obtained by esterification or transesterification has a lower polarity than that of the substrate, it can be easily fractionated by a conventional method using, for example, a silica gel column or a silica gel thin plate. The conjugated linoleic acid ester can be obtained by concentrating and drying the fractionated product to dryness.
【００１６】本発明では、このようにして得られた共役
リノール酸エステルをそのまま粉末の状態で、油脂その
他の溶媒に溶解した状態で、あるいは乳化させた状態
で、抗酸化剤として用いることができる。そして、本発
明の抗酸化剤は、飲食品あるいは飼料に添加したり、生
体に投与される。生体内での酸化抑制に用いる場合は、
カプセル、顆粒、錠剤、乳液、油液等の形状にすればよ
い。生体内での抗酸化剤として用いるときは、成人で１
日２〜50mgを数回に分けて経口投与するとよい。なお、
共役リノール酸エステルには急性毒性はない。In the present invention, the conjugated linoleic acid ester thus obtained can be used as an antioxidant in the form of a powder, dissolved in fats and oils or other solvents, or emulsified. . Then, the antioxidant of the present invention is added to food or drink or feed or administered to a living body. When used for inhibiting oxidation in vivo,
It may be in the form of capsules, granules, tablets, emulsions, oils and the like. When used as an antioxidant in vivo, 1 adult
It may be preferable to orally administer 2 to 50 mg per day in several divided doses. In addition,
Conjugated linoleate has no acute toxicity.
【００１７】さらに、本発明の共役リノール酸エステル
を飲食品に添加して脂質成分の酸化抑制作用を賦与した
飲食品とするには、例えば、食用油、マーガリン、バタ
ーその他の油脂に、共役リノール酸エステルを直接添加
してもよく、また、共役リノール酸エステルを水と混合
して乳化物を調製し、これをソース、ドレッシング、チ
ーズフード、菓子、パン、麺類、飲料、スナック食品等
に添加してもよい。さらに、共役リノール酸エステルを
ゼラチン等を用いてカプセル化し、このカプセルをサプ
リメント食品として用いたり、飲料、菓子、ガム、キャ
ンディー等に添加してもよい。添加量は飲食品中の油脂
含量によって多少変動するが、飲食品の油脂部の５〜80
％となるように添加するとよい。このようにすると常温
乃至冷蔵庫中での脂質成分の酸化を抑制することができ
る。Further, in order to add the conjugated linoleic acid ester of the present invention to foods and drinks to give the effect of inhibiting the oxidation of lipid components, for example, edible oil, margarine, butter and other fats and oils are added to conjugated linoleic acid. An acid ester may be added directly, or a conjugated linoleic acid ester is mixed with water to prepare an emulsion, which is added to sauces, dressings, cheese foods, confections, breads, noodles, beverages, snack foods, etc. May be. Further, the conjugated linoleic acid ester may be encapsulated using gelatin or the like, and the capsule may be used as a supplement food or added to beverages, confectionery, gum, candies, and the like. The amount of addition varies slightly depending on the fat content in the food or drink,
%. By doing so, it is possible to suppress the oxidation of the lipid component at room temperature or in a refrigerator.
【００１８】以下に実施例を挙げて本発明を更に詳しく
説明する。Hereinafter, the present invention will be described in more detail with reference to examples.
【実施例１】水飽和ｎ−ヘキサン１ml中にジパルミトイ
ルホスファチジルコリン５mgと共役リノール酸20mgを溶
解し、Mucor miehei起源のリパーゼを珪藻土に吸着し調
製した固定化リパーゼ (NOVO社製）10mgを加え、反応温
度40℃で48時間、エステル交換反応を行った。反応終了
後、濾過により固定化リパーゼと反応液とを分離し、反
応液をＯＤＳカラムに供給した。そして、クロロホルム
／メタノール／水の混合溶媒を用いて分画し、遊離脂肪
酸画分、ジパルミトイルホスファチジルコリン画分、１
−コンジュケイテッドリノレイル２−パルミトイルホス
ファチジルコリン・１−パルミトイル２−コンジュケイ
テッドリノレイルホスファチジルコリン混合画分、ジコ
ンジュケイテッドリノレイルホスファチジルコリン画分
を得た。なお、反応で生成したエステルの各画分につい
ては、(1) 常法 (３フッ化ホウ素−メタノール法）に従
ってメチルエステル化して、目的成分に結合している脂
肪酸組成をガスクロマトグラフィーにて測定し、また、
(2) ホスホリパーゼＡ２を反応させてリン脂質の２位に
結合している脂肪酸を遊離させ、１位のみに脂肪酸が結
合しているリゾリン脂質を調製し、このリゾリン脂質を
常法に従ってメチルエステル化して、目的成分の１位に
結合している脂肪酸組成をガスクロマトグラフィーにて
測定した。そして、(1) と(2) の測定結果を比較するこ
とで、各画分に含まれるエステルの結合様式を決定し
た。上記で得られたジコンジュケイテッドリノレイルホ
スファチジルコリン画分について、成分に結合している
脂肪酸組成をガスクロマトグラフィーにて測定した結
果、共役リノール酸含量が99％以上であった。Example 1 10 mg of immobilized lipase (manufactured by NOVO) prepared by dissolving 5 mg of dipalmitoylphosphatidylcholine and 20 mg of conjugated linoleic acid in 1 ml of water-saturated n-hexane and adsorbing lipase derived from Mucor miehei onto diatomaceous earth was prepared. The transesterification reaction was performed at a reaction temperature of 40 ° C. for 48 hours. After completion of the reaction, the immobilized lipase and the reaction solution were separated by filtration, and the reaction solution was supplied to an ODS column. Then, fractionation was performed using a mixed solvent of chloroform / methanol / water, and the free fatty acid fraction, dipalmitoylphosphatidylcholine fraction, 1
-A conjugated linoleyl 2-palmitoyl phosphatidylcholine / 1-palmitoyl 2-conjugated linoleyl phosphatidylcholine mixed fraction and a diconjugated linoleyl phosphatidylcholine fraction were obtained. In addition, each fraction of the ester formed by the reaction is (1) methylesterified according to a conventional method (boron trifluoride-methanol method), and the composition of the fatty acid bound to the target component is measured by gas chromatography. And also
(2) Phospholipase A2 is reacted to release a fatty acid bound to the 2-position of the phospholipid to prepare a lysophospholipid having a fatty acid bound only to the 1-position, and the lysophospholipid is methyl-esterified according to a conventional method. Then, the composition of the fatty acid bonded to the first position of the target component was measured by gas chromatography. Then, by comparing the measurement results of (1) and (2), the binding mode of the ester contained in each fraction was determined. The composition of fatty acids bound to the components of the diconjugated linoleyl phosphatidylcholine fraction obtained above was measured by gas chromatography. As a result, the content of conjugated linoleic acid was 99% or more.
【００１９】[0019]
【実施例２】共役リノール酸に対して塩化チオニルを５
当量添加し、加熱還流した後、減圧濃縮して共役リノー
ル酸クロライドを得た。10％ＤＳＰ及び0.05％トリエチ
ルアミンのエーテル溶液を調製し、氷温下で1/3 当量の
共役リノール酸クロライドを徐々に添加し、次いで減圧
濃縮して、共役リノール酸ＤＳＰエステルを得た。この
共役リノール酸ＤＳＰエステルを市販のRhizopus delem
ar起源リパーゼに対して25当量加え、４℃にて24時間反
応を行った。反応終了後、透析によって未反応物を除去
した後、凍結乾燥して、共役リノール酸修飾リパーゼの
乾燥物を得た。次に、水飽和ｎ−ヘキサン10ml中にコレ
ステロール 100mg及び共役リノール酸100mg を溶解し、
上記で得られた共役リノール酸修飾リパーゼ10mgを加
え、37℃で24時間、エステル合成反応を行った。反応終
了後、反応液をシリカゲルカラムに供給し、クロロホル
ム／メタノール／水の混合溶媒を用いて分画し、コレス
テロール共役リノール酸エステル画分を得た。反応で生
成したエステル画分は、図１に示すように、シリカゲル
薄層プレートを用いたクロマトグラフィー（ＴＬＣ、展
開溶媒：ヘキサン／エーテル／酢酸＝80/30/1 、発色：
5 ％硫酸エタノール) によって、原料である共役リノー
ル酸及びコレステロールとは分離されており、新規なコ
レステロール共役リノール酸エステルであることが確か
められた。上記で得られたコレステロール共役リノール
酸エステル画分について、常法（水酸化カリウム−メタ
ノール法）に従ってメチルエステル化し、成分に結合し
ている脂肪酸組成をガスクロマトグラフィーにて測定し
た結果、共役リノール酸含量が98％以上であった。EXAMPLE 2 Thionyl chloride was added to conjugated linoleic acid in an amount of 5
An equivalent amount was added, and the mixture was heated under reflux and concentrated under reduced pressure to obtain conjugated linoleic acid chloride. An ether solution of 10% DSP and 0.05% triethylamine was prepared, 1 / equivalent of conjugated linoleic acid chloride was gradually added at ice temperature, and then concentrated under reduced pressure to obtain a conjugated linoleic acid DSP ester. This conjugated linoleic acid DSP ester is commercially available from Rhizopus delem.
25 equivalents were added to the ar origin lipase, and the reaction was carried out at 4 ° C for 24 hours. After completion of the reaction, unreacted substances were removed by dialysis, and then lyophilized to obtain a dried conjugated linoleic acid-modified lipase. Next, 100 mg of cholesterol and 100 mg of conjugated linoleic acid were dissolved in 10 ml of water-saturated n-hexane,
10 mg of the conjugated linoleic acid-modified lipase obtained above was added, and an ester synthesis reaction was performed at 37 ° C. for 24 hours. After the completion of the reaction, the reaction solution was supplied to a silica gel column, and fractionated using a mixed solvent of chloroform / methanol / water to obtain a cholesterol-conjugated linoleic acid ester fraction. As shown in FIG. 1, the ester fraction produced by the reaction was subjected to chromatography using a silica gel thin layer plate (TLC, developing solvent: hexane / ether / acetic acid = 80/30/1, color development:
The conjugated linoleic acid and cholesterol as raw materials were separated by 5% ethanol (sulfuric acid, 5%), and it was confirmed that this was a novel cholesterol conjugated linoleate. The cholesterol conjugated linoleic acid ester fraction obtained above was subjected to methyl esterification according to a conventional method (potassium hydroxide-methanol method), and the composition of fatty acids bound to the components was measured by gas chromatography. The content was over 98%.
【００２０】[0020]
【実施例３】0.05M リン酸緩衝液(pH7.0)1mlに、微細に
粉砕した乳糖粉末100mg を分散させ、さらに共役リノー
ル酸100mg を加えた酢酸エチル１mlと混合し、実施例２
で調製した共役リノール酸修飾リパーゼ10mgを加え、37
℃で24時間、反応を行った。反応終了後、反応液をシリ
カゲルカラムに供給し、クロロホルム／メタノール／水
の混合溶媒を用いて分画し、ラクトース共役リノール酸
エステル画分を得た。反応で生成したエステル画分は、
図２に示すように、ＴＬＣ（展開溶媒：クロロホルム／
メタノール／水＝60/35/8 、発色：オルシノール試薬)
によって、原料である共役リノール酸及びラクトースと
は分離されており、新規なラクトース共役リノール酸エ
ステルであることが確かめられた。なお、図２は、ヨウ
素により、共役リノール酸を確認（点線）した後、オル
シノール試薬により発色させたものである。上記で得ら
れたラクトース共役リノール酸エステル画分について、
常法（３フッ化ホウ素−メタノール法）に従ってメチル
エステル化し、成分に結合している脂肪酸組成をガスク
ロマトグラフィーにて測定した結果、共役リノール酸含
量が98％以上であった。Example 3 100 mg of finely ground lactose powder was dispersed in 1 ml of 0.05 M phosphate buffer (pH 7.0), and mixed with 1 ml of ethyl acetate to which 100 mg of conjugated linoleic acid was added.
10 mg of conjugated linoleic acid-modified lipase prepared in
The reaction was performed at 24 ° C. for 24 hours. After the completion of the reaction, the reaction solution was supplied to a silica gel column, and fractionated using a mixed solvent of chloroform / methanol / water to obtain a lactose-conjugated linoleic acid ester fraction. The ester fraction generated in the reaction is
As shown in FIG. 2, TLC (developing solvent: chloroform /
(Methanol / water = 60/35/8, color development: orcinol reagent)
As a result, the raw materials, conjugated linoleic acid and lactose, were separated, and it was confirmed that this was a novel lactose conjugated linoleic acid ester. FIG. 2 shows the result of confirming the conjugated linoleic acid with iodine (dotted line) and then developing the color with an orcinol reagent. About the lactose conjugated linoleic acid ester fraction obtained above,
As a result of methylesterification according to a conventional method (boron trifluoride-methanol method) and the composition of fatty acids bound to the components measured by gas chromatography, the conjugated linoleic acid content was 98% or more.
【００２１】[0021]
【実施例４】0.05M リン酸緩衝液(pH7.0)1mlにアスコル
ビン酸100mg を分散させ、さらに共役リノール酸 100mg
を加えた酢酸エチル1ml と混合し、実施例２で調製した
共役リノール酸修飾リパーゼ10mgを加え、37℃で24時
間、反応を行った。反応終了後、反応液をシリカゲルカ
ラムに供給し、クロロホルム／メタノール／水の混合溶
媒を用いて分画し、アスコルビン酸共役リノール酸エス
テル画分を得た。反応で生成したエステル画分は、図３
に示すように、ＴＬＣ（展開溶媒：クロロホルム／メタ
ノール／水＝60／30／1 、発色: ５％硫酸エタノール)
によって、原料である共役リノール酸及びアスコルビン
酸とは分離されており、新規なアスコルビン酸共役リノ
ール酸エステルであることが確かめられた。上記で得ら
れたアスコルビン酸共役リノール酸エステル画分につい
て、常法（水酸化カリウム−メタノール法）に従ってメ
チルエステル化し、成分に結合している脂肪酸組成をガ
スクロマトグラフィーにて測定した結果、共役リノール
酸含量が95％以上であった。Example 4 100 mg of ascorbic acid was dispersed in 1 ml of 0.05M phosphate buffer (pH 7.0), and 100 mg of conjugated linoleic acid was further dispersed.
The mixture was mixed with 1 ml of ethyl acetate to which was added, 10 mg of the conjugated linoleic acid-modified lipase prepared in Example 2 was added, and the reaction was carried out at 37 ° C. for 24 hours. After completion of the reaction, the reaction solution was supplied to a silica gel column, and fractionated using a mixed solvent of chloroform / methanol / water to obtain an ascorbic acid-conjugated linoleic acid ester fraction. The ester fraction produced by the reaction is shown in FIG.
As shown in the figure, TLC (developing solvent: chloroform / methanol / water = 60/30/1, coloring: 5% ethanol in sulfuric acid)
As a result, the raw materials, conjugated linoleic acid and ascorbic acid, were separated, and it was confirmed that they were novel ascorbic acid conjugated linoleic acid esters. The ascorbic acid-conjugated linoleic acid ester fraction obtained above was subjected to methyl esterification according to a conventional method (potassium hydroxide-methanol method), and the composition of fatty acids bound to the components was measured by gas chromatography. The acid content was more than 95%.
【００２２】[0022]
【実施例５】イソオクタン2ml と水8ml の混合液中にコ
レステロール100mg と共役リノール酸 100mgを溶解し、
Lipase MY （Candida cylindracea 起源、Meito 社製）
25mgを加え、反応温度37℃で６時間攪拌し、エステル交
換反応を行った。反応終了後、濾過によりLipase MY と
反応液とを分離した。そして、反応液をシリカゲルカラ
ムに供給し、ヘキサン／ジエチルエーテル／酢酸の混合
溶媒を用いて分画し、コレステロール共役リノール酸エ
ステル画分65mgを得た。反応で生成したエステル画分
は、実施例２と同様に、ＴＬＣによって、原料である共
役リノール酸及びコレステロールとは分離されており、
新規なコレステロール共役リノール酸エステルであるこ
とが確かめられた。上記で得られたコレステロール共役
リノール酸エステル画分について、常法（水酸化カリウ
ム−メタノール法）に従ってメチルエステル化し、成分
に結合している脂肪酸組成をガスクロマトグラフィーに
て測定した結果、共役リノール酸含量が98％以上であっ
た。Example 5 100 mg of cholesterol and 100 mg of conjugated linoleic acid were dissolved in a mixture of 2 ml of isooctane and 8 ml of water.
Lipase MY (origin of Candida cylindracea, Meito)
25 mg was added, and the mixture was stirred at a reaction temperature of 37 ° C. for 6 hours to perform a transesterification reaction. After the reaction was completed, Lipase MY and the reaction solution were separated by filtration. Then, the reaction solution was supplied to a silica gel column, and fractionated using a mixed solvent of hexane / diethyl ether / acetic acid to obtain 65 mg of a cholesterol-conjugated linoleic acid ester fraction. The ester fraction generated by the reaction was separated from the starting materials, conjugated linoleic acid and cholesterol, by TLC, as in Example 2.
It was confirmed that it was a novel cholesterol conjugated linoleate. The cholesterol conjugated linoleic acid ester fraction obtained above was subjected to methyl esterification according to a conventional method (potassium hydroxide-methanol method), and the composition of fatty acids bound to the components was measured by gas chromatography. The content was over 98%.
【００２３】[0023]
【実施例６】イソオクタン2ml と水8ml の混合液中にβ
−シトステロール100mg と共役リノール酸100mg を溶解
し、Lipase MY (Candida cylindracea起源、Meito 社
製）25mgを加え、反応温度37℃で６時間攪拌し、エステ
ル交換反応を行った。反応終了後、濾過によりLipase M
Y と反応液とを分離した。反応液をシリカゲルカラムに
供給し、ヘキサン／ジエチルエーテル／酢酸の混合溶媒
を用いて分画し、β−シトステロール共役リノール酸エ
ステル画分54mgを得た。反応で生成したエステル画分
は、図４に示すように、ＴＬＣによって、原料である共
役リノール酸及びβ−シトステロールとは分離されてお
り、新規なβ−シトステロール共役リノール酸エステル
であることが確かめられた。上記で得られたβ−シトス
テロール共役リノール酸エステル画分について、常法
（水酸化カリウム−メタノール法）に従ってメチルエス
テル化し、成分に結合している脂肪酸組成をガスクロマ
トグラフィーにて測定した結果、共役リノール酸含量が
98％以上であった。Example 6 β was added to a mixture of 2 ml of isooctane and 8 ml of water.
-100 mg of sitosterol and 100 mg of conjugated linoleic acid were dissolved, 25 mg of Lipase MY (Candida cylindracea origin, manufactured by Meito) was added, and the mixture was stirred at a reaction temperature of 37 ° C for 6 hours to carry out a transesterification reaction. After the reaction is completed, filter the Lipase M
Y and the reaction solution were separated. The reaction solution was supplied to a silica gel column, and fractionated using a mixed solvent of hexane / diethyl ether / acetic acid to obtain a β-sitosterol conjugated linoleic acid ester fraction (54 mg). As shown in FIG. 4, the ester fraction generated by the reaction was separated from the starting materials, conjugated linoleic acid and β-sitosterol, by TLC, confirming that it was a novel β-sitosterol conjugated linoleic acid ester. Was done. The β-sitosterol conjugated linoleic acid ester fraction obtained above was methylesterified according to a conventional method (potassium hydroxide-methanol method), and the composition of fatty acids bound to the components was measured by gas chromatography. Linoleic acid content
It was over 98%.
【００２４】[0024]
【実施例７】濃硫酸50ml中にアスコルビン酸2.8gと共役
リノール酸5.6gを混合し、30℃で１時間攪拌した。25℃
で24時間放置した後、反応液を300gの氷中に混合し、す
ばやく攪拌した。この反応液をジエチルエーテル500ml
で抽出し、ジエチルエーテル抽出液を飽和食塩水で洗浄
した。ジエチルエーテル抽出液を蒸発させ、得られた固
形物をヘキサン 400mlで３回抽出し、残った不溶性物を
乾燥後、石油エーテルで抽出し、石油エーテルを蒸発さ
せてアスコルビン酸共役リノール酸エステル画分を得
た。反応で生成したエステル画分は、実施例４と同様
に、ＴＬＣによって、原料である共役リノール酸及びア
スコルビン酸とは分離されており、新規なアスコルビン
酸共役リノール酸エステルであることが確かめられた。
上記で得られたアスコルビン酸共役リノール酸エステル
画分について、常法（水酸化カリウム−メタノール法）
に従ってメチルエステル化し、成分に結合している脂肪
酸組成をガスクロマトグラフィーにて測定した結果、共
役リノール酸含量が95％以上であった。Example 7 2.8 g of ascorbic acid and 5.6 g of conjugated linoleic acid were mixed in 50 ml of concentrated sulfuric acid, and the mixture was stirred at 30 ° C. for 1 hour. 25 ℃
For 24 hours, the reaction solution was mixed in 300 g of ice, and rapidly stirred. 500 ml of this reaction solution in diethyl ether
And the diethyl ether extract was washed with saturated saline. The diethyl ether extract was evaporated, the resulting solid was extracted three times with 400 ml of hexane, the remaining insolubles were dried, extracted with petroleum ether, and the petroleum ether was evaporated to remove the ascorbic acid conjugated linoleate ester fraction. I got The ester fraction produced by the reaction was separated from the starting materials, conjugated linoleic acid and ascorbic acid, by TLC in the same manner as in Example 4, confirming that it was a novel ascorbic acid conjugated linoleic acid ester. .
The ascorbic acid-conjugated linoleic acid ester fraction obtained above is subjected to a conventional method (potassium hydroxide-methanol method).
As a result of measuring the composition of fatty acids bound to the components by gas chromatography, the content of conjugated linoleic acid was 95% or more.
【００２５】[0025]
【実施例８】ｎ−ヘキサン／ジエチルエーテル(1/1) 混
合液10ml中にジパルミトイルホスファチジルエタノール
アミン50mgと共役リノール酸20mgを溶解し、１規定ナト
リウムメトキシド水溶液20mlを加え、攪拌しながら50℃
で２時間、エステル交換反応を行った。反応終了後、反
応液を室温に冷却し、遠心操作によりn-ヘキサン／ジエ
チルエーテル混合液を回収した。この溶液からn-ヘキサ
ン／ジエチルエーテルを減圧蒸留により除去した後、ク
ロロホルム／メタノールの混合溶媒に溶解し、ＯＤＳカ
ラムに供給した。これをクロロホルム／メタノール／水
の混合溶媒を用いて分画し、遊離脂肪酸画分、ジパルミ
トイルホスファチジルエタノールアミン画分、1-コンジ
ュケイテッドリノレイル 2- パルミトイルホスファチジ
ルエタノールアミン・1-パルミトイル 2- コンジュケイ
テッドリノレイルホスファチジルエタノールアミン混合
画分、ジコンジュケイテッドリノレイルホスファチジル
エタノールアミン画分を得た。なお、反応で生成したエ
ステルの各画分については、(1) 常法 (３フッ化ホウ素
−メタノール法）に従ってメチルエステル化して、目的
成分に結合している脂肪酸組成をガスクロマトグラフィ
ーにて測定し、また、(2) ホスホリパーゼＡ２を反応さ
せてリン脂質の２位に結合している脂肪酸を遊離させ、
１位のみに脂肪酸が結合しているリゾリン脂質を調製
し、このリゾリン脂質を常法に従ってメチルエステル化
して、目的成分の１位に結合している脂肪酸組成をガス
クロマトグラフィーにて測定した。そして、(1) と(2)
の測定結果を比較することで、各画分に含まれるエステ
ルの結合様式を決定した。上記で得られたジコンジュケ
イテッドリノレイルホスファチジルエタノールアミン画
分について、成分に結合している脂肪酸組成をガスクロ
マトグラフィーにて測定した結果、共役リノール酸含量
が99％以上であった。Example 8 Dipalmitoyl phosphatidylethanolamine (50 mg) and conjugated linoleic acid (20 mg) were dissolved in n-hexane / diethyl ether (1/1) mixture (10 ml), and 1N sodium methoxide aqueous solution (20 ml) was added. ° C
For 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and an n-hexane / diethyl ether mixture was recovered by centrifugation. After n-hexane / diethyl ether was removed from this solution by distillation under reduced pressure, it was dissolved in a mixed solvent of chloroform / methanol and supplied to an ODS column. This was fractionated using a mixed solvent of chloroform / methanol / water, and the free fatty acid fraction, dipalmitoyl phosphatidylethanolamine fraction, 1-conjugated linoleyl 2-palmitoylphosphatidylethanolamine / 1-palmitoyl 2-conjugate A mixed linoleyl phosphatidylethanolamine fraction and a diconjugated linoleyl phosphatidylethanolamine fraction were obtained. In addition, each fraction of the ester formed by the reaction is subjected to (1) methyl esterification according to a conventional method (boron trifluoride-methanol method), and the composition of the fatty acid bound to the target component is measured by gas chromatography. And (2) reacting phospholipase A2 to release the fatty acid bound to the 2-position of the phospholipid,
A lysophospholipid having a fatty acid bonded only to the first position was prepared, and the lysophospholipid was methylesterified according to a conventional method, and the composition of the fatty acid bonded to the first position of the target component was measured by gas chromatography. And (1) and (2)
By comparing the measurement results, the binding mode of the ester contained in each fraction was determined. The composition of fatty acids bound to the components of the diconjugated linoleyl phosphatidylethanolamine fraction obtained above was measured by gas chromatography. As a result, the content of conjugated linoleic acid was 99% or more.
【００２６】[0026]
【試験例１】実施例１〜４で得られた共役リノール酸エ
ステルの抗酸化活性を、大澤らの方法（J.Agric.Food C
hem. Vol.35,No.5, p.809-812,1987）により測定した。
すなわち、ウサギ保存血液と等張液(10mM リン酸緩衝液
/152mM NaCl,pH7.4)とを等量混和し、４℃、1500×g(35
00rpm)で20分間遠心分離した（計３回）。洗浄した血球
に低張液 (10mMリン酸緩衝液、pH7.4)をよく混和し、４
℃、20000 ×g(11000rpm) で40分間遠心分離した（計４
回）。ここで得た緩い沈殿部分（ゴースト）を用いて共
役リノール酸エステルの抗酸化活性について検討した。
実施例１〜４で得られた共役リノール酸エステルを10mM
の濃度に調製し、前述の赤血球膜ゴーストと混合し、こ
れに酸化剤としてｔ- ブチルヒドロペルオキシドを1mM
の濃度で加えて酸化反応を行った。次いでＴＢＡ反応を
行い、532nm で吸光度を測定して、酸化生成物を定量し
た。抗酸化活性は、共役リノール酸又は共役リノール酸
エステル無添加のサンプルにおける吸光度を酸化抑制率
０％とし、共役リノール酸又は共役リノール酸エステル
を添加したサンプルにおける吸光度から次式により算出
した。Test Example 1 The antioxidant activity of the conjugated linoleic acid esters obtained in Examples 1 to 4 was measured by the method of Osawa et al. (J. Agric. Food C.
hem. Vol. 35, No. 5, p. 809-812, 1987).
That is, isotonic solution (10 mM phosphate buffer)
/ 152 mM NaCl, pH 7.4), and mix at 4 ° C, 1500 xg (35
(00 rpm) for 20 minutes (3 times in total). Hypotonic solution (10 mM phosphate buffer, pH 7.4) is mixed well with the washed blood cells.
And centrifuged at 20,000 xg (11000 rpm) for 40 minutes.
Times). The antioxidant activity of the conjugated linoleate was examined using the loose precipitate (ghost) obtained here.
10 mM of the conjugated linoleic acid ester obtained in Examples 1 to 4
, And mixed with the above-mentioned erythrocyte membrane ghost, and t-butyl hydroperoxide was added thereto as an oxidizing agent at 1 mM.
At a concentration of 1% to effect an oxidation reaction. Next, a TBA reaction was performed, and the absorbance was measured at 532 nm to quantify the oxidation product. The antioxidant activity was calculated from the absorbance of the sample to which no conjugated linoleic acid or conjugated linoleic acid ester was added and the absorbance of the sample to which conjugated linoleic acid or conjugated linoleic acid ester was added, according to the following formula.
【００２７】[0027]
【数１】酸化抑制率（％）＝[1- (添加サンプルの吸光
度／無添加サンプルの吸光度)]×100 （但し、式中、添加サンプルとは、共役リノール酸又は
共役リノール酸エステルを添加したサンプルを、また、
無添加サンプルとは、共役リノール酸又は共役リノール
酸無添加のサンプルをそれぞれ意味する。）## EQU1 ## Oxidation inhibition rate (%) = [1- (absorbance of added sample / absorbance of non-added sample)] × 100 (where the added sample is conjugated linoleic acid or conjugated linoleic acid ester) Sample,
The non-added sample means a conjugated linoleic acid or a sample without conjugated linoleic acid, respectively. )
【００２８】結果を図５に示した。実施例１〜４で得ら
れたいずれの共役リノール酸エステルにおいても、共役
リノール酸に比べて高い酸化抑制率が得られており、共
役リノール酸の抗酸化活性がエステル化することにより
大きく向上していることがわかった。ジコンジュケイテ
ッドリノレイルホスファチジルコリン、アスコルビン酸
共役リノール酸エステルでは、特に顕著な抗酸化活性の
向上が見られた。以上の試験結果から、共役リノール酸
エステルは生体内における脂質成分の酸化を抑制する作
用を有することがわかった。The results are shown in FIG. In any of the conjugated linoleic acid esters obtained in Examples 1 to 4, a higher oxidation inhibition rate was obtained as compared to conjugated linoleic acid, and the antioxidant activity of conjugated linoleic acid was greatly improved by esterification. I understood that. In the case of diconjugated linoleyl phosphatidylcholine and ascorbic acid-conjugated linoleate, particularly remarkable improvement in antioxidant activity was observed. From the above test results, it was found that the conjugated linoleic acid ester has an action of suppressing oxidation of lipid components in a living body.
【００２９】[0029]
【試験例２】実施例１〜４で得られた共役リノール酸エ
ステルの抗酸化活性を、食用油脂に添加してランシマッ
ト法により測定した。すなわち、精製大豆油と精製カツ
オ油を重量比で１／１になるように混合し、この混合食
用油脂に対して共役リノール酸エステルをそれぞれ50pp
m の濃度で添加した。なお、対照サンプルとして共役リ
ノール酸エステル無添加の混合食用油脂と、実施例１〜
４で出発物質として用いた共役リノール酸を添加した混
合食用油脂を調製した。これらの混合食用油脂3gをラン
シマット試験に供した。ランシマット測定はアメリカ油
化学協会公定法(Cd12b-92)に準じ、測定温度は80℃に設
定した。試験結果を図６に示す。Test Example 2 The antioxidant activity of the conjugated linoleic esters obtained in Examples 1 to 4 was added to edible oils and fats and measured by the Rancimat method. That is, refined soybean oil and refined skipjack oil are mixed at a weight ratio of 1/1, and 50 parts each of the conjugated linoleic acid ester is added to the mixed edible fat and oil.
m. As a control sample, a mixed edible oil and fat without conjugated linoleic acid ester, and Examples 1 to
In 4, an edible mixed fat or oil was added to which the conjugated linoleic acid used as a starting material was added. 3 g of these mixed edible fats and oils were subjected to the Rancimat test. Rancimat measurement was performed according to the official method of the American Oil Chemistry Association (Cd12b-92), and the measurement temperature was set to 80 ° C. The test results are shown in FIG.
【００３０】実施例１〜４で得られた共役リノール酸エ
ステルを添加した混合食用油脂は、共役リノール酸添加
混合食用油脂及び無添加混合食用油脂に比較していずれ
も酸化誘導期が伸長しており、共役リノール酸添加混合
食用油脂及び無添加混合食用油脂に比較して高い酸化安
定性を示した。すなわち、この試験結果により、共役リ
ノール酸の抗酸化活性がエステル化することにより大き
く向上していることがわかった。ジコンジュケイテッド
リノレイルホスファチジルコリン、アスコルビン酸共役
リノール酸エステルでは、特に顕著な抗酸化活性の向上
が見られた。The mixed edible oils and fats to which the conjugated linoleic acid esters obtained in Examples 1 to 4 were added exhibited an extended oxidation induction period as compared with the mixed edible oils and fats with and without conjugated linoleic acid. It showed higher oxidative stability compared to the mixed edible fats and oils with and without conjugated linoleic acid. That is, from the test results, it was found that the antioxidant activity of the conjugated linoleic acid was greatly improved by esterification. In the case of diconjugated linoleyl phosphatidylcholine and ascorbic acid-conjugated linoleate, particularly remarkable improvement in antioxidant activity was observed.
【００３１】[0031]
【試験例３】試験例２で用いた各食用混合油脂を使用し
て揚げパン（クルトン）を調製し、揚げパンの酸化安定
性をランシマット法により測定した。すなわち、市販の
トースト用食パンの周辺を除去した後、一辺約 8mmの立
方体になるように食パンをカットした。このカットした
食パン5gを、180 ℃に加熱した各混合食用油脂50g 中で
５分間揚げ、揚げパンを調製した。この揚げパン3gを試
験例２と同様にしてランシマット試験に供した。ランシ
マット測定はアメリカ油化学協会公定法(Cd 12b-92) に
準じ、測定温度は60℃に設定した。試験結果を図７に示
す。Test Example 3 Fried bread (cruton) was prepared using each of the edible mixed fats and oils used in Test Example 2, and the oxidation stability of the fried bread was measured by the Rancimat method. That is, after removing the periphery of a commercially available bread for toast, the bread was cut into a cube having a side of about 8 mm. 5 g of the cut bread was fried for 5 minutes in 50 g of each mixed edible oil and fat heated to 180 ° C. to prepare a fried bread. 3 g of the fried bread was subjected to the Rancimat test in the same manner as in Test Example 2. Rancimat measurement was performed according to the official method of the American Oil Chemistry Association (Cd 12b-92), and the measurement temperature was set at 60 ° C. The test results are shown in FIG.
【００３２】実施例１〜４で得られた共役リノール酸エ
ステルを添加した混合食用油脂を用いた揚げパンは、共
役リノール酸添加混合食用油脂及び無添加混合食用油脂
を用いた揚げパンに比較していずれも酸化誘導期が伸長
しており、共役リノール酸添加混合食用油脂及び無添加
混合食用油脂を用いた揚げパンに比較して高い酸化安定
性を示した。すなわち、この試験結果により、共役リノ
ール酸の抗酸化活性がエステル化することにより大きく
向上していることがわかった。ジコンジュケイテッドリ
ノレイルホスファチジルコリン、アスコルビン酸共役リ
ノール酸エステルでは、特に顕著な抗酸化活性の向上が
見られた。The fried bread using the mixed edible oil and fat to which the conjugated linoleic acid ester obtained in Examples 1 to 4 was added was compared with the fried bread using the mixed edible oil and fat with the conjugated linoleic acid and the non-added mixed edible oil and fat. In each case, the oxidation induction period was prolonged, and higher oxidative stability was exhibited as compared with fried bread using mixed edible fats and oils with and without conjugated linoleic acid. That is, from the test results, it was found that the antioxidant activity of the conjugated linoleic acid was greatly improved by esterification. In the case of diconjugated linoleyl phosphatidylcholine and ascorbic acid-conjugated linoleate, particularly remarkable improvement in antioxidant activity was observed.
【００３３】[0033]
【発明の効果】本発明の共役リノール酸エステルは、飲
食品用の抗酸化剤として幅広い分野の飲食品に利用でき
る。本発明の共役リノール酸エステルを飲食品に添加す
ることにより、飲食品の保存中の酸化が抑制でき、ま
た、飲食品摂取後の生体内酸化をも抑制することがで
き、有用なものである。The conjugated linoleic acid ester of the present invention can be used in a wide variety of foods and drinks as an antioxidant for foods and drinks. By adding the conjugated linoleic acid ester of the present invention to foods and drinks, oxidation during storage of foods and drinks can be suppressed, and in vivo oxidation after ingestion of foods and drinks can also be suppressed, which is useful. .
【図１】実施例２のコレステロール共役リノール酸エス
テル生成反応における反応液の反応開始前と反応開始後
６時間のＴＬＣの結果を示す。FIG. 1 shows the results of TLC before and after 6 hours from the start of the reaction of the reaction solution in the cholesterol-conjugated linoleic acid ester formation reaction of Example 2.
【図２】実施例３のラクトース共役リノール酸エステル
生成反応における反応液の反応開始前と反応終了後のＴ
ＬＣの結果を示す。FIG. 2 shows T before and after the reaction of the reaction solution in the lactose-conjugated linoleic acid ester formation reaction of Example 3.
The result of LC is shown.
【図３】実施例４のアスコルビン酸共役リノール酸エス
テル生成反応における反応液の反応開始前と反応終了後
のＴＬＣの結果を示す。FIG. 3 shows the results of TLC before and after the reaction of the reaction solution in the ascorbic acid-conjugated linoleic acid ester formation reaction of Example 4.
【図４】実施例６のβ−シトステロール共役リノール酸
エステル生成反応における反応液の反応開始前と反応終
了後のＴＬＣの結果を示す。FIG. 4 shows TLC results before and after the reaction of the reaction solution in the β-sitosterol conjugated linoleic acid ester formation reaction of Example 6.
【図５】試験例１における各共役リノール酸エステルの
酸化抑制率を示す。FIG. 5 shows the rate of inhibition of oxidation of each conjugated linoleic acid ester in Test Example 1.
【図６】試験例２における各共役リノール酸エステル添
加混合食用油脂の抗酸化活性を示す。6 shows the antioxidant activity of the mixed edible fats and oils added with each conjugated linoleic acid ester in Test Example 2. FIG.
【図７】試験例３における各共役リノール酸エステル添
加混合食用油脂を配合した揚げパンの酸化安定性を示
す。FIG. 7 shows the oxidative stability of a fried bread blended with each edible oil and fat added with each conjugated linoleic acid ester in Test Example 3.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ａ６１Ｋ 31/685 ６０２ Ａ６１Ｋ 31/685 ６０２ ４Ｃ０５７ 31/70 ６０６ 31/70 ６０６ ４Ｃ０８６ Ｃ０７Ｃ 69/58 Ｃ０７Ｃ 69/58 ４Ｃ０９１ Ｃ０７Ｆ 9/10 Ｃ０７Ｆ 9/10 Ｂ ４Ｈ００６ Ｃ０７Ｈ 13/06 Ｃ０７Ｈ 13/06 ４Ｈ０２５ Ｃ０７Ｊ 9/00 Ｃ０７Ｊ 9/00 ４Ｈ０５０ Ｃ０９Ｋ 15/06 Ｃ０９Ｋ 15/06 15/32 15/32 Ｃ Ｃ１２Ｎ 9/20 Ｃ１２Ｎ 9/20 11/14 11/14 Ｃ１２Ｐ 7/64 Ｃ１２Ｐ 7/64 Ｆターム(参考） 4B021 LW01 LW05 LW06 LW07 LW08 MC03 MK21 MP01 4B033 NA01 NA27 NB12 NB24 NB62 NB66 NC04 ND02 ND20 4B050 CC10 DD03 GG01 GG10 LL02 4B064 AD68 AD72 AD73 CA21 CA22 CA33 CA37 CA38 CB26 CB30 CD05 CD06 CD12 CE10 DA10 4C037 LA02 LA03 4C057 AA17 BB01 BB03 HH03 4C086 AA01 AA03 AA04 BA18 DA40 EA03 EA19 MA01 MA11 MA52 NA05 4C091 AA01 BB06 CC01 DD01 EE05 FF01 GG01 HH01 JJ03 KK01 LL01 MM03 NN01 PA02 PA05 PB05 QQ01 4H006 AA01 AA02 AA03 AB83 AC48 KA03 KA06 4H025 AA14 AA63 AA81 4H050 AA01 AB83 AC40 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI theme coat ゛ (Reference) A61K 31/685 602 A61K 31/685 602 4C057 31/70 606 31/70 606 4C086 C07C 69/58 C07C 69 / 58 4C091 C07F 9/10 C07F 9/10 B 4H006 C07H 13/06 C07H 13/06 4H025 C07J 9/00 C07J 9/00 4H050 C09K 15/06 C09K 15/06 15/32 15/32 C C12N 9/20 C12N 9/20 11/14 11/14 C12P 7/64 C12P 7/64 F-term (reference) 4B021 LW01 LW05 LW06 LW07 LW08 MC03 MK21 MP01 4B033 NA01 NA27 NB12 NB24 NB62 NB66 NC04 ND02 ND20 4B050 CC10 DD03 GG01 GG10 AD02 AD73 CA21 CA22 CA33 CA37 CA38 CB26 CB30 CD05 CD06 CD12 CE10 DA10 4C037 LA02 LA03 4C057 AA17 BB01 BB 03 HH03 4C086 AA01 AA03 AA04 BA18 DA40 EA03 EA19 MA01 MA11 MA52 NA05 4C091 AA01 BB06 CC01 DD01 EE05 FF01 GG01 HH01 JJ03 KK01 LL01 MM03 NN01 PA02 PA05 PB05 QQ01 4H006 AA01 AA48A03A03A03A03A03A03
Claims (7)
酸エステル。 【化１】R1-COO-R2 [I] （但し、R1はC17H32で表され共役二重結合１個を有する
脂肪族炭化水素基であり、R2は水酸基又はエステル結合
を１個以上有する有機化合物残基である。）1. A conjugated linoleic acid ester represented by the following general formula [I]. R 1 -COO-R 2 [I] (where R 1 is an aliphatic hydrocarbon group represented by C 17 H 32 and having one conjugated double bond, and R 2 is a hydroxyl group or an ester bond) Is an organic compound residue having at least one
類残基、有機酸残基のいずれかである請求項１記載の共
役リノール酸エステル。2. The conjugated linoleate according to claim 1, wherein R 2 is any of a phospholipid residue, a sterol residue, a saccharide residue, and an organic acid residue.
結合を１個以上有する有機化合物とエステル化又はエス
テル交換することを特徴とする請求項１又は２に記載の
共役リノール酸エステルの製造法。3. The method for producing a conjugated linoleic acid ester according to claim 1, wherein the conjugated linoleic acid is esterified or transesterified with an organic compound having one or more hydroxyl groups or ester bonds.
ル交換する請求項３記載の製造法。4. The method according to claim 3, wherein the esterification or transesterification is carried out using a lipase.
化学的に脂肪酸修飾されたリパーゼである請求項４記載
の製造法。5. The method according to claim 4, wherein the lipase is an immobilized lipase or a lipase chemically modified with a fatty acid.
エステルを有効成分とする抗酸化剤。6. An antioxidant comprising the conjugated linoleic acid ester according to claim 1 as an active ingredient.
エステルを添加して脂質成分の酸化抑制作用を賦与した
飲食品。7. A food or drink having the conjugated linoleic acid ester according to claim 1 or 2 added to impart an effect of inhibiting the oxidation of lipid components.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001079241A1 (en) * | 2000-04-18 | 2001-10-25 | Henkel Kommanditgesellschaft Auf Aktien | Glycoside esters, the production and the use thereof in cosmetics, pharmaceutical products and foodstuff or animal feed |
| WO2001029060A3 (en) * | 1999-10-21 | 2001-11-01 | Univ Oklahoma State | Sterol esters of conjugated linoleic acids and process for their production |
| JP2004248671A (en) * | 2003-01-31 | 2004-09-09 | Rinoru Oil Mills Co Ltd | Method for purification of conjugated linoleic acid isomer and application of the same |
| JP2007175067A (en) * | 2003-01-31 | 2007-07-12 | Nisshin Oillio Group Ltd | Method for purification of conjugated linoleic acid isomer and application of the same |
| KR100914213B1 (en) | 2008-05-16 | 2009-08-26 | 충남대학교산학협력단 | Composition with the inhibition activities of hyperlipidemia and obesity |
| CN103849660A (en) * | 2014-03-28 | 2014-06-11 | 大连医诺生物有限公司 | Method for preparing conjugated linoleic acid through coupling method using immobilized lipase as catalyst |
-
1999
- 1999-03-01 JP JP05263899A patent/JP3483197B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001029060A3 (en) * | 1999-10-21 | 2001-11-01 | Univ Oklahoma State | Sterol esters of conjugated linoleic acids and process for their production |
| WO2001079241A1 (en) * | 2000-04-18 | 2001-10-25 | Henkel Kommanditgesellschaft Auf Aktien | Glycoside esters, the production and the use thereof in cosmetics, pharmaceutical products and foodstuff or animal feed |
| JP2004248671A (en) * | 2003-01-31 | 2004-09-09 | Rinoru Oil Mills Co Ltd | Method for purification of conjugated linoleic acid isomer and application of the same |
| JP2007175067A (en) * | 2003-01-31 | 2007-07-12 | Nisshin Oillio Group Ltd | Method for purification of conjugated linoleic acid isomer and application of the same |
| JP4510045B2 (en) * | 2003-01-31 | 2010-07-21 | 日清オイリオグループ株式会社 | Method for purifying conjugated linoleic acid isomers and uses thereof |
| KR100914213B1 (en) | 2008-05-16 | 2009-08-26 | 충남대학교산학협력단 | Composition with the inhibition activities of hyperlipidemia and obesity |
| CN103849660A (en) * | 2014-03-28 | 2014-06-11 | 大连医诺生物有限公司 | Method for preparing conjugated linoleic acid through coupling method using immobilized lipase as catalyst |
| CN103849660B (en) * | 2014-03-28 | 2016-01-06 | 大连医诺生物有限公司 | A kind of with immobilized lipase be catalyzer be coupled the method for legal system for conjugated linolic acid |
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| Publication number | Publication date |
|---|---|
| JP3483197B2 (en) | 2004-01-06 |
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