JPS6124393B2 - - Google Patents
Info
- Publication number
- JPS6124393B2 JPS6124393B2 JP58033575A JP3357583A JPS6124393B2 JP S6124393 B2 JPS6124393 B2 JP S6124393B2 JP 58033575 A JP58033575 A JP 58033575A JP 3357583 A JP3357583 A JP 3357583A JP S6124393 B2 JPS6124393 B2 JP S6124393B2
- Authority
- JP
- Japan
- Prior art keywords
- vitamin
- water
- solvent
- leaves
- tocopherol
- 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.)
- Expired
Links
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 claims description 89
- 229930003427 Vitamin E Natural products 0.000 claims description 45
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 claims description 45
- 229940046009 vitamin E Drugs 0.000 claims description 45
- 235000019165 vitamin E Nutrition 0.000 claims description 45
- 239000011709 vitamin E Substances 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 12
- 239000012141 concentrate Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 8
- 239000003495 polar organic solvent Substances 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 229930003799 tocopherol Natural products 0.000 claims description 3
- 239000011732 tocopherol Substances 0.000 claims description 3
- 235000019149 tocopherols Nutrition 0.000 claims description 3
- 238000010533 azeotropic distillation Methods 0.000 claims 1
- QUEDXNHFTDJVIY-UHFFFAOYSA-N γ-tocopherol Chemical class OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-UHFFFAOYSA-N 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- GVJHHUAWPYXKBD-IEOSBIPESA-N (R)-alpha-Tocopherol Natural products 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 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 229940087168 alpha tocopherol Drugs 0.000 description 15
- 229960000984 tocofersolan Drugs 0.000 description 15
- 239000002076 α-tocopherol Substances 0.000 description 15
- 235000004835 α-tocopherol Nutrition 0.000 description 15
- AOBORMOPSGHCAX-DGHZZKTQSA-N tocofersolan Chemical compound OCCOC(=O)CCC(=O)OC1=C(C)C(C)=C2O[C@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C AOBORMOPSGHCAX-DGHZZKTQSA-N 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 241000196324 Embryophyta Species 0.000 description 11
- 238000000605 extraction Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical class C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000003957 anion exchange resin Substances 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 235000006708 antioxidants Nutrition 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 241000233788 Arecaceae Species 0.000 description 2
- 240000003133 Elaeis guineensis Species 0.000 description 2
- 235000001950 Elaeis guineensis Nutrition 0.000 description 2
- 239000003674 animal food additive Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000008157 edible vegetable oil Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- -1 for example Substances 0.000 description 2
- 235000013402 health food Nutrition 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 208000000509 infertility Diseases 0.000 description 2
- 230000036512 infertility Effects 0.000 description 2
- 231100000535 infertility Toxicity 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000001766 physiological effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003463 sulfur Chemical class 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 125000002640 tocopherol group Chemical class 0.000 description 2
- 125000001020 α-tocopherol group Chemical group 0.000 description 2
- WGVKWNUPNGFDFJ-DQCZWYHMSA-N β-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C WGVKWNUPNGFDFJ-DQCZWYHMSA-N 0.000 description 2
- GZIFEOYASATJEH-VHFRWLAGSA-N δ-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 GZIFEOYASATJEH-VHFRWLAGSA-N 0.000 description 2
- PZZKGQBMBVYPGR-UHFFFAOYSA-N η-tocopherol Chemical compound OC1=C(C)C=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 PZZKGQBMBVYPGR-UHFFFAOYSA-N 0.000 description 2
- GJJVAFUKOBZPCB-ZGRPYONQSA-N (r)-3,4-dihydro-2-methyl-2-(4,8,12-trimethyl-3,7,11-tridecatrienyl)-2h-1-benzopyran-6-ol Chemical class OC1=CC=C2OC(CC/C=C(C)/CC/C=C(C)/CCC=C(C)C)(C)CCC2=C1 GJJVAFUKOBZPCB-ZGRPYONQSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 206010000234 Abortion spontaneous Diseases 0.000 description 1
- 241001133760 Acoelorraphe Species 0.000 description 1
- 206010003694 Atrophy Diseases 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- GZIFEOYASATJEH-UHFFFAOYSA-N D-delta tocopherol Natural products OC1=CC(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 GZIFEOYASATJEH-UHFFFAOYSA-N 0.000 description 1
- 240000002045 Guettarda speciosa Species 0.000 description 1
- 235000001287 Guettarda speciosa Nutrition 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000699670 Mus sp. Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000037444 atrophy Effects 0.000 description 1
- 229940066595 beta tocopherol Drugs 0.000 description 1
- 230000005779 cell damage Effects 0.000 description 1
- 230000003915 cell function Effects 0.000 description 1
- 208000037887 cell injury Diseases 0.000 description 1
- 230000019522 cellular metabolic process Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000010389 delta-tocopherol Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 210000003754 fetus Anatomy 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 210000002149 gonad Anatomy 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 208000015994 miscarriage Diseases 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012261 resinous substance Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 235000012045 salad Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 208000000995 spontaneous abortion Diseases 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229930003802 tocotrienol Natural products 0.000 description 1
- 239000011731 tocotrienol Substances 0.000 description 1
- 229940068778 tocotrienols Drugs 0.000 description 1
- 235000019148 tocotrienols Nutrition 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 150000003712 vitamin E derivatives Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010497 wheat germ oil Substances 0.000 description 1
- 235000007680 β-tocopherol Nutrition 0.000 description 1
- 239000011590 β-tocopherol Substances 0.000 description 1
- 239000002446 δ-tocopherol Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
- C07D311/70—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with two hydrocarbon radicals attached in position 2 and elements other than carbon and hydrogen in position 6
- C07D311/72—3,4-Dihydro derivatives having in position 2 at least one methyl radical and in position 6 one oxygen atom, e.g. tocopherols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyrane Compounds (AREA)
- Medicines Containing Plant Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明はビタミンE類の濃縮法に関し、さらに
詳しくは、ビタミンE類を含有する禾本科植物や
ヤシ科植物の緑葉より、ビタミンE類特にα−ト
コフエロールを効率よく分離濃縮する方法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for concentrating vitamin E, and more specifically, to a method for efficiently separating vitamin E, especially α-tocopherol, from the green leaves of plants of the Carotid family and palm family, which contain vitamin E. It relates to a method of concentration.
従来、ビタミンE類はその生理作用として、例
えばこのものが欠乏すると、ネズミ雌では不妊症
や胎児吸収流産が、雄では***産生組織の萎縮及
び永久不妊が生じるなど生殖腺に対する作用のみ
が知られていたが、近年その抗酸化力により、動
物体内においても強力な抗酸化力を示して細胞の
過酸化による損傷を防ぎ、細胞の機能と代謝に有
効な役割を果すことが知られるようになつた。し
たがつて、ビタミンE類は最近医薬品、健康食
品、飼料添加剤などの分野において著しく脚光を
浴びており、また、食品包装用プラスチツクフイ
ルムや食用油などの無毒性酸化防止剤としても極
めて注目されている。 Conventionally, the physiological effects of vitamin E are only known to be on the gonads, such as a deficiency in female mice causing infertility and miscarriage of the fetus, and in males causing atrophy of sperm-producing tissue and permanent infertility. However, in recent years, it has become known that its antioxidant power also shows strong antioxidant power in the animal body, preventing cell damage caused by peroxidation and playing an effective role in cell function and metabolism. . Therefore, vitamin E has recently been attracting a lot of attention in the fields of pharmaceuticals, health foods, feed additives, etc., and is also attracting a lot of attention as a non-toxic antioxidant for food packaging plastic films and edible oils. ing.
天然ビタミンE類としては、α,β−トコフエ
ロールのほかにγ,δ,ε,ζ,η−トコフエロ
ールの7種類及びα,β,γ,δ−トコフエロー
ルの分子内から水素原子6個をとつて二重結合を
導入した形の4種類のトコトリエノールが知られ
ている。これらの中で生理活性の最も強いものは
α−トコフエロールであり、したがつてこのα−
トコフエロールを天然物から効率よく抽出する方
法や合成する方法が盛んに研究されている。な
お、天然α−トコフエロールはd一体であるが、
合成α−トコフエロールはd,1−体のラセミ体
である。 In addition to α, β-tocopherol, natural vitamin E includes seven types of γ, δ, ε, ζ, η-tocopherol, and α, β, γ, δ-tocopherol with six hydrogen atoms removed from the molecule. Four types of tocotrienols with double bonds introduced are known. Among these, the one with the strongest physiological activity is α-tocopherol, and therefore this α-
Methods for efficiently extracting and synthesizing tocopherols from natural products are being actively researched. In addition, natural α-tocopherol is d-unit, but
Synthetic α-tocopherol is a racemic d,1-isomer.
これらのビタミンE類は、植物の葉、茎、種子
などに含まれており、ビタミンE類全体としての
含有量は、種子の部分が多いため、従来は主とし
て小麦胚芽油、綿実油、サラダ油などの種子油か
ら抽出されていた。しかし、本発明者らの研究の
結果、種子中に存在するビタミンE類では、最も
活性の高いα−トコフエロールの比率が低く、α
−トコフエロールの比率はむしろ葉や茎、特に葉
の部分の方が大きいことが分つた。 These vitamin E types are found in plant leaves, stems, seeds, etc., and since the overall content of vitamin E is higher in seeds, it has traditionally been found mainly in wheat germ oil, cottonseed oil, salad oil, etc. It was extracted from seed oil. However, as a result of research by the present inventors, the proportion of α-tocopherol, which has the highest activity, is low among the vitamin E species present in seeds, and
- It was found that the ratio of tocopherols was rather large in leaves and stems, especially in the leaf parts.
したがつて、α−トコフエロールに富むビタミ
ンE類を得るための原料としては、植物の葉や茎
を用いるのが有利であるが、葉や茎に含まれてい
るビタミンE類の含量は微量であるため、その組
織体よりビタミンE類を選択的に濃縮することは
かなり困難である。この葉や茎などよりビタミン
E類を濃縮する方法として、一般的にはまず葉や
茎などを強制乾燥又は天日乾燥して水分を除去し
たのち、有機溶媒を用いて抽出、濃縮するか、あ
るいは低級アルコールやケトン類などの水に可溶
性の有機溶媒を用いて水を除去しながら、該溶媒
中にビタミンE類を溶出させて濃縮するなどの方
法がとられている。 Therefore, it is advantageous to use plant leaves and stems as raw materials for obtaining vitamin E rich in α-tocopherol, but the content of vitamin E contained in leaves and stems is very small. Therefore, it is quite difficult to selectively concentrate vitamin E from the tissue. To concentrate vitamin E from leaves and stems, generally, the leaves and stems are first force-dried or sun-dried to remove moisture, and then extracted and concentrated using an organic solvent. Alternatively, a method is used in which water is removed using a water-soluble organic solvent such as a lower alcohol or ketone, and vitamin E is eluted into the solvent and concentrated.
しかしながら、前者の強制乾燥又は天日乾燥法
では、乾燥工程におけるビタミンE類の損失を伴
なう欠点があり、また後者の水に可溶性の有機溶
媒を用いる方法では、溶媒中に水分が多く含まれ
るため、溶媒の回収が困難となつて経済性に乏し
いという欠点がある。 However, the former method of forced drying or sun drying has the disadvantage of loss of vitamin E in the drying process, and the latter method of using a water-soluble organic solvent contains a large amount of water in the solvent. This has the disadvantage that it is difficult to recover the solvent, making it uneconomical.
本発明者らは、このような欠点を克服し、新鮮
緑葉よりビタミンE類、特にα−トコフエロール
を損失することなく、効率よく分離濃縮する方法
について鋭意研究を重ねた結果、特定の溶媒によ
る抽出と、イオン交換体による処理とを組み合わ
せることにより、その目的を達成しうることを見
出し、本発明をなすに至つた。 The present inventors overcame these drawbacks and conducted intensive research on a method for efficiently separating and concentrating vitamin E, especially α-tocopherol, from fresh green leaves without losing them. The present inventors have discovered that the object can be achieved by combining the treatment with an ion exchanger and the treatment with an ion exchanger, leading to the present invention.
すなわち、本発明に従えば、植物の緑葉を粉砕
し、その際生じる水分を除去したのち、非水溶性
でありかつ水と共沸混合物を形成する非極性有機
溶媒を用いて、該緑葉中に残存する水分を前記溶
媒とともに共沸留去させながら、該緑葉に含まれ
るビタミンE類を該溶媒中に溶出させ、次いでこ
の溶出液から該溶媒を留去したのち、その残液を
イオン交換体で処理することによつて、α−トコ
フエロールを主体とするビタミンE類の濃縮物を
得ることができる。 That is, according to the present invention, after pulverizing the green leaves of a plant and removing the water produced at the time, the green leaves are treated with a non-polar organic solvent that is insoluble in water and forms an azeotrope with water. The vitamin E contained in the green leaves is eluted into the solvent while the remaining moisture is azeotropically distilled off with the solvent, and then the solvent is distilled off from the eluate, and the remaining liquid is treated with an ion exchanger. By processing with , it is possible to obtain a concentrate of vitamin E containing α-tocopherol as a main component.
本発明方法で用いる原料としては、例えば稲、
麦、とうもろこしなどの穀類や原野に自生するひ
げしばなどの禾本科植物、あるいはヤシ科植物な
どの葉が好適である。 The raw materials used in the method of the present invention include, for example, rice,
Suitable are grains such as wheat and corn, leaves of plants of the family Heliaceae such as Hijiba, which grow wild in the wilderness, or plants of the palm family.
これらの葉は、その果実に比べてビタミンE類
の含有量は少ないが、ビタミンE類中のα−トコ
フエロールの含有割合が極めて高いという特徴を
有している。 These leaves have a lower content of vitamin E than the fruit, but are characterized by an extremely high content of α-tocopherol in the vitamin E.
また、本発明に用いる非極性有機溶媒は、非水
溶性であり、かつ水と共沸混合物を形成するもの
であつて、このようなものとしては、例えばn−
ヘキサン、n−ヘプタン、ベンゼン、トルエンな
どの炭化水素系溶媒、トリクレン四塩化炭素など
のハロゲン系溶媒を挙げることができる。 Furthermore, the non-polar organic solvent used in the present invention is water-insoluble and forms an azeotrope with water, such as n-
Examples include hydrocarbon solvents such as hexane, n-heptane, benzene and toluene, and halogen solvents such as trichlene carbon tetrachloride.
次に、本発明に用いるイオン交換体としては、
塩基性アニオン交換体が好適であり、このものは
膜状、繊維状、粒状など任意の形状で用いること
ができる。特に好適なのは、オルガノ製アンバー
ライトIRA 401CL型アニオン交換樹脂、オルガ
ノ製アンバーリストA−26非水溶液用アニオン交
換樹脂である。 Next, as the ion exchanger used in the present invention,
A basic anion exchanger is suitable, and this can be used in any form such as film, fiber, or granule. Particularly suitable are Organo's Amberlyte IRA 401CL type anion exchange resin and Organo's Amberlyte A-26 anion exchange resin for non-aqueous solutions.
次に本発明の実施態様の1例を示すと、まず原
料として、新鮮な禾本科植物やヤシ科植物などの
葉を用い、これを十分に粉砕したのち、その際生
じる水分を圧縮ろ過などによつて除去する。次い
で前記の非極性有機溶媒を加えて共沸温度下で加
熱し、原料に残存する水分を該溶媒とともに共沸
留去させながら、植物組織体に含有するビタミン
E類を該溶媒中に溶出せしめる。次にろ過などに
よつて繊維質とビタミンE類含有溶液を分離した
のち、溶液中の溶媒を留去して濃縮物を得る。 Next, an example of an embodiment of the present invention will be described. First, fresh leaves of a plant of the Coconutaceae family or a Coconut family plant are used as a raw material, and after the leaves are thoroughly crushed, the water produced at that time is filtered through compression etc. Twist and remove. Next, the above-mentioned non-polar organic solvent is added and heated at an azeotropic temperature, and while water remaining in the raw material is azeotropically distilled off with the solvent, vitamin E contained in the plant tissue is eluted into the solvent. . Next, the fibers and the vitamin E-containing solution are separated by filtration or the like, and then the solvent in the solution is distilled off to obtain a concentrate.
この濃縮物中にはビタミンE類以外の成分が含
まれているため、メタノールやエタノールなどの
低級アルコールを加えて加熱し、アルコールに不
溶性の樹脂状物を除いたのち、アルコール溶液を
イオン交換体と接触させて、その中のビタミンE
類を吸着させ、次いで溶離剤として、例えば酢酸
を含むエタノール溶液を用い、イオン交換体に吸
着しているビタミンE類を溶離させる。次にこの
ビタミンE類含有溶液に、n−ヘキサンなどの非
水溶性溶媒を加えたのち、飽和食塩水などを用い
て十分水洗し、次いで無水ボウ硝などで乾燥後、
溶媒を留去して目的のビタミンE類含有濃縮物を
得る。 This concentrate contains components other than vitamin E, so lower alcohols such as methanol and ethanol are added and heated to remove resinous substances insoluble in alcohol, and the alcohol solution is converted into an ion exchanger. The vitamin E in it comes into contact with
Then, using an ethanol solution containing acetic acid as an eluent, for example, vitamin E adsorbed on the ion exchanger is eluted. Next, a non-aqueous solvent such as n-hexane is added to this vitamin E-containing solution, followed by thorough washing with saturated saline, followed by drying with anhydrous salt water, etc.
The solvent is distilled off to obtain the desired vitamin E-containing concentrate.
このようにして得られた濃縮物中には、α−ト
コフエロールを主とするビタミンE類が約70%以
上含まれている。 The concentrate thus obtained contains about 70% or more of vitamin E, mainly α-tocopherol.
本発明のビタミンE類の濃縮法によると、植物
の緑葉より、ビタミンE類特にα−トコフエロー
ルを極めて効率よく分離濃縮することができる。 According to the method for concentrating vitamin E of the present invention, vitamin E, especially α-tocopherol, can be separated and concentrated from green leaves of plants very efficiently.
また得られた濃縮物は、α−トコフエロールを
主とするビタミンE類を約70%以上含有してお
り、そのままで医薬品、健康食品、飼料添加剤と
して、あるいは食用油や食品包装用フイルムなど
の無毒性酸化防止剤として利用することができ
る。 In addition, the obtained concentrate contains approximately 70% or more of vitamin E, mainly α-tocopherol, and can be used as it is as a pharmaceutical, health food, or feed additive, or as edible oil, food packaging film, etc. It can be used as a non-toxic antioxidant.
次に実施例によつて本発明をさらに詳細に説明
するが、本発明はこの実施例によつて限定される
ものではない。 Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.
実施例 1
原野に自生する禾本科植物のひげしばの新鮮な
葉1Kgを粉砕し、その際生じる水分を圧縮ろ過に
より除いたのち、粉砕した繊維質を3の二ツ口
フラスコ(上部に還流冷却器を取り付け、この冷
却器の下部に水分分離用分液漏斗を取り付ける)
内に入れ、さらにベンゼン700mlを加えて70℃付
近で2時間加熱し、留出する水分とベンゼンを冷
却器下部に取付けた分液漏斗に導いて、水分は系
外に取り出し、ベンゼンはフラスコ内に還流さ
せ、繊維質中のベンゼン可溶部を抽出した。Example 1 1 kg of fresh leaves of Hijishiba, a herbaceous plant that grows naturally in the wilderness, was crushed, and the water produced at that time was removed by compression filtration. Attach a cooler and attach a separatory funnel for moisture separation at the bottom of this cooler)
Add 700ml of benzene and heat at around 70℃ for 2 hours.The distilled water and benzene are introduced into a separating funnel attached to the bottom of the condenser.The water is taken out of the system, and the benzene is removed from the flask. The mixture was refluxed to extract the benzene-soluble portion in the fibers.
抽出終了後のベンゼン溶液を室温まで冷却した
のち、吸引ろ過して繊維質とベンゼン溶液を分離
し、次いでベンゼン溶液を300mlになるまで濃縮
後、室温に冷却して析出するゲル状物質を7000r.
p.mの遠心分離機を用いて沈降除去したのち、ベ
ンゼンを留去して緑褐色のベンゼン抽出物80gを
得た。この抽出物にメタノール100mlを加えてか
きまぜながら加熱したのち、0℃付近まで冷却し
析出する樹脂状化合物を吸引ろ過して分別した。
メタノール溶液は室温(25℃)付近まで加温した
のち、300mlの塩基性陰イオン交換樹脂(オルガ
ノ製アンバーライトI・R・A401CL型アニオン
交換樹脂)を充てんしたガラスカラム層を通過さ
せてビタミンE類を吸着させた。次いでこのイオ
ン交換樹脂を300mlのエタノールで洗浄したの
ち、10%酢酸を含むエタノール溶液300mlでビタ
ミンE類をイオン交換樹脂より脱着し、この溶液
にn−ヘキサン300mlを加えたのち、飽和食塩水
で洗浄して酢酸及びエタノールを除き、次いでn
−ヘキサン溶液に無水ボウ硝を加えて乾燥後、n
−ヘキサンを留去して粘ちよう性液体2.5gを得
た。この粘稠性液体中のビタミンE類の含有量を
高速液体クロマトグラフイーによつて求めたとこ
ろ、約70%であり、α−トコフエロールを主とし
ていた。 After the extraction, the benzene solution was cooled to room temperature, filtered under suction to separate the fibers and the benzene solution, and then the benzene solution was concentrated to 300 ml, cooled to room temperature, and the precipitated gel-like substance was filtered for 7000 r.
After sedimentation and removal using a PM centrifuge, benzene was distilled off to obtain 80 g of a greenish-brown benzene extract. 100 ml of methanol was added to this extract, heated while stirring, cooled to around 0°C, and precipitated resinous compounds were separated by suction filtration.
After warming the methanol solution to around room temperature (25°C), it is passed through a glass column layer filled with 300 ml of basic anion exchange resin (Amberlite I/R/A401CL type anion exchange resin manufactured by Organo) to extract vitamin E. were adsorbed. Next, this ion exchange resin was washed with 300 ml of ethanol, and then vitamin E was desorbed from the ion exchange resin with 300 ml of an ethanol solution containing 10% acetic acid. After adding 300 ml of n-hexane to this solution, it was desorbed with saturated saline. Wash to remove acetic acid and ethanol, then n
- After adding anhydrous sulfur salt to a hexane solution and drying it, n
- Hexane was distilled off to obtain 2.5 g of a viscous liquid. The content of vitamin E in this viscous liquid was determined by high performance liquid chromatography and was found to be approximately 70%, consisting mainly of α-tocopherol.
実施例 2
熱帯産ヤシ科植物のアブラヤシの新鮮な葉1Kg
を十分に粉砕し、その際生じる水分を圧縮ろ過し
て除去したのち、実施例1で用いたものと同じ抽
出用フラスコ内に入れ、さらにn−ヘプタン700
mlを加えて80℃付近で2時間加熱し、n−ヘプタ
ンと共沸してくる水分を系外に取り出しながらビ
タミンE類の抽出を行つた。Example 2 1 kg of fresh leaves of oil palm, a tropical palm tree
After sufficiently pulverizing the water produced at that time and removing it by compression filtration, it was placed in the same extraction flask as used in Example 1, and further added with 700 g of n-heptane.
ml was added and heated at around 80°C for 2 hours, and vitamin E was extracted while removing water that azeotroped with n-heptane from the system.
抽出終了後のn−ヘプタン溶液を室温まで冷却
したのち、吸引ろ過して繊維質とn−ヘプタン溶
液を分離し、次いでn−ヘプタン溶液を濃縮して
暗緑褐色粘ちよう性残留分95gを得た。この粘ち
よう性残留分にメタノール400mlを加えてかきま
ぜながら加熱したのち、0℃近辺まで冷却して析
出する固体を遠心分離機を用いて分離した。エタ
ノール溶液は実施例1と同様のイオン交換樹脂
300ml層を通過させてビタミンE類を吸着させ
た。次いでこのイオン交換樹脂を500mlのメタノ
ールで洗浄したのち、10%の酢酸を含むエタノー
ル溶液300mlでビタミンE類をイオン交換樹脂よ
り溶離し、この溶液にn−ヘキサン300mlを加え
たのち、飽和食塩水で洗液が中性となるまで洗浄
し、次いでn−ヘキサン溶液に無水ボウ硝を加え
て乾燥後、活性白土3gを加えて十分かきまぜて
緑色系色素を吸着させたのち、分別ろ過する。ろ
別した活性白土は100mlのn−ヘキサンで洗浄
し、洗液とろ液を合併してn−ヘキサンを留去し
た。粘ちよう性淡緑色の液体2.5gを得た。この
ものを高速液体クロマトグラフイーにより分析し
たところ、α−トコフエロールを主成分とするビ
タミンE類の含有量が約70%であつた。 After the extraction, the n-heptane solution was cooled to room temperature, filtered under suction to separate the fibrous material from the n-heptane solution, and the n-heptane solution was then concentrated to obtain 95 g of a dark greenish-brown sticky residue. Obtained. 400 ml of methanol was added to this sticky residue, heated while stirring, cooled to around 0°C, and the precipitated solid was separated using a centrifuge. The ethanol solution is the same ion exchange resin as in Example 1.
It passed through a 300ml layer to adsorb vitamin E. Next, this ion exchange resin was washed with 500 ml of methanol, and then vitamin E was eluted from the ion exchange resin with 300 ml of an ethanol solution containing 10% acetic acid. After adding 300 ml of n-hexane to this solution, saturated saline was added. The solution is washed with water until the washing liquid becomes neutral, and then anhydrous sulfur salt is added to the n-hexane solution, and after drying, 3 g of activated clay is added and stirred thoroughly to adsorb the green pigment, followed by fractional filtration. The filtered activated clay was washed with 100 ml of n-hexane, the washing liquid and the filtrate were combined, and the n-hexane was distilled off. 2.5 g of a viscous pale green liquid was obtained. When this product was analyzed by high performance liquid chromatography, the content of vitamin E whose main component is α-tocopherol was about 70%.
実施例 3
アシタバ(Angelica utilis)の葉1Kgを用い、
実施例1と同じ処理を行うことにより、イソシト
ール20%、α−トコフエロール12%を含む粘ちよ
うな暗かつ色液体を得た。Example 3 Using 1 kg of Angelica utilis leaves,
By carrying out the same treatment as in Example 1, a viscous dark and colored liquid containing 20% isositol and 12% α-tocopherol was obtained.
参考例
約1cm平方に裁断し、水分を除去したアブラヤ
シの葉1Kgとトルエン5Kgを、水分分離管を備え
た10容−フラスコ内に装入し、84℃に加熱し
て、葉部中の水分を共沸除去しながら、3時間抽
出を行つた。次いで抽出液をろ過して葉その他の
固形分を除いたのち、溶媒を留去させた。このよ
うにしてビタミンE類の濃縮物を得た。この際の
ビタミンE類全量の抽出率は1.92%であつた。Reference example: 1 kg of oil palm leaves, cut into approximately 1 cm square pieces and from which water has been removed, and 5 kg of toluene are placed in a 10-volume flask equipped with a water separation tube, heated to 84°C, and the water in the leaves is removed. Extraction was carried out for 3 hours while azeotropically removing. The extract was then filtered to remove leaves and other solids, and the solvent was distilled off. In this way, a concentrate of vitamin E was obtained. At this time, the extraction rate of the total amount of vitamin E was 1.92%.
次に比較のために、同じ原料1Kgとトルエン5
Kgを10容−フラスコに装入し、共沸を行うこと
なく50℃で3時間かきまぜることによつて抽出を
行つた。この抽出液から溶媒を除去して得られる
濃縮物について、ビタミンE類全量の抽出率を求
めたところ0.54%であつた。また、溶媒をトルエ
ンからn−ヘキサンに変え、他は全く同じ条件下
で抽出したときの抽出率は0.46%であつた。 Next, for comparison, 1 kg of the same raw material and 5 toluene
Kg was charged into a 10 volume flask and the extraction was carried out by stirring at 50° C. for 3 hours without azeotroping. Regarding the concentrate obtained by removing the solvent from this extract, the extraction rate of the total amount of vitamin E was determined to be 0.54%. Furthermore, when extraction was performed under the same conditions except that the solvent was changed from toluene to n-hexane, the extraction rate was 0.46%.
このように、共沸操作を行わない場合は、ビタ
ミンE類の抽出率が著しく低下する。 As described above, when the azeotropic operation is not performed, the extraction rate of vitamin E is significantly reduced.
Claims (1)
去したのち、非水溶性でありかつ水と共沸混合物
を形成する非極性有機溶媒を用いて、該緑葉中に
残存する水分を前記溶媒とともに共沸留去させな
がら、該緑葉に含まれるビタミンE類を該溶媒中
に溶出させ、次いでこの溶出液から該溶媒を留去
したのち、その残液をイオン交換体で処理し、α
−トコフエロールを主体とするビタミンE類の濃
縮物を得ることを特徴とするビタミンE類の濃縮
法。1. After pulverizing the green leaves of a plant and removing the water generated during the process, the water remaining in the green leaves is removed together with the solvent using a non-polar organic solvent that is insoluble in water and forms an azeotrope with water. While performing azeotropic distillation, vitamin E contained in the green leaves is eluted into the solvent, and then the solvent is distilled off from this eluate, and the remaining liquid is treated with an ion exchanger to obtain α
- A method for concentrating vitamin E, which is characterized by obtaining a concentrate of vitamin E mainly consisting of tocopherols.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58033575A JPS59161372A (en) | 1983-03-01 | 1983-03-01 | Concentration of vitamin e |
GB08323370A GB2135672B (en) | 1983-03-01 | 1983-08-31 | Method for the preparation of vitamin e concentrate |
MY8700479A MY8700479A (en) | 1983-03-01 | 1987-12-30 | Method for the preparation of vitamin e concentrate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58033575A JPS59161372A (en) | 1983-03-01 | 1983-03-01 | Concentration of vitamin e |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59161372A JPS59161372A (en) | 1984-09-12 |
JPS6124393B2 true JPS6124393B2 (en) | 1986-06-10 |
Family
ID=12390326
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP58033575A Granted JPS59161372A (en) | 1983-03-01 | 1983-03-01 | Concentration of vitamin e |
Country Status (3)
Country | Link |
---|---|
JP (1) | JPS59161372A (en) |
GB (1) | GB2135672B (en) |
MY (1) | MY8700479A (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
HUT63158A (en) * | 1990-05-23 | 1993-07-28 | Lipogenics Inc | Process for obtaining tokotrienols, tokoferols and tokotrienol-like compounds and pahrmaceutical compositions comprising same as active ingredient |
FR2669032B1 (en) * | 1990-11-14 | 1993-04-23 | Cecchi Georges | PROCESS FOR THE MANUFACTURE OF A PREPARATION OF D-ALPHA-TOCOPHEROL. |
ATE165383T1 (en) * | 1992-12-16 | 1998-05-15 | Shell Int Research | COMPOSITION BASED ON REFINED PETROLEUM WAX |
US5582692A (en) * | 1994-10-07 | 1996-12-10 | Artisan Industries, Inc. | Method for the purification of vitamin E |
US5985344A (en) * | 1997-09-02 | 1999-11-16 | The Ricex Company | Process for obtaining micronutrient enriched rice bran oil |
WO2007129136A1 (en) * | 2006-05-08 | 2007-11-15 | Achidi Valentin Agon | Antimalarial properties of extracts of elaeis guineensis (oil palm) leaves |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58180480A (en) * | 1982-04-14 | 1983-10-21 | Agency Of Ind Science & Technol | Separation of tocopherol |
-
1983
- 1983-03-01 JP JP58033575A patent/JPS59161372A/en active Granted
- 1983-08-31 GB GB08323370A patent/GB2135672B/en not_active Expired
-
1987
- 1987-12-30 MY MY8700479A patent/MY8700479A/en unknown
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58180480A (en) * | 1982-04-14 | 1983-10-21 | Agency Of Ind Science & Technol | Separation of tocopherol |
Also Published As
Publication number | Publication date |
---|---|
GB2135672A (en) | 1984-09-05 |
MY8700479A (en) | 1987-12-31 |
JPS59161372A (en) | 1984-09-12 |
GB8323370D0 (en) | 1983-10-05 |
GB2135672B (en) | 1986-05-29 |
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