JPS58144382A - Separation of tocopherol and tocotrienol - Google Patents

Abstract

PURPOSE:To separate the titled substance having vitamin E activity and useful as a antisterility agent for animal and antioxidant for food, etc., easily, by extracting the leaves of balm, banana, pineapplie, or sugar cane with an organic solvent. CONSTITUTION:Leaves of balm, banana, pineapple, and sugar cane are crushed or chopped, optionally dried, and extracted with an organic solvent such as an alcohol (e.g. methanol), ether (e.g. ethyl ether), ketone (e.g. acetone), carboxylic acid ester (e.g. methyl formate), hydrocarbon (e.g. hexane), etc. or their mixture to obtain an extract containing tocopherols and tocotrienols. The extract is subjected to the low temperature fractionation in the presence of an organic solvent to concentrate the tocopherols and tocotrienols in the soluble fraction.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for separating tocopherols and tocotrienols contained in leaves of noseem, banana, pineapple, sugarcane, etc.

Tocopherols have vitamin E activity and have been used as active anti-infertility drugs, but recently it has been revealed that they have the ability to prevent the oxidation of fats and oils, prevent adult diseases, and prevent aging. Demand for products, pharmaceuticals, nutritional foods, cosmetics, etc. is rapidly increasing.

The inventors have discovered that the leaves of palm, Bana N, pineapple, sugarcane, etc. are crushed or shredded and then dried or not.
Extraction is performed using organic solvents such as alcohol, ether, ketone, etc. alone or in combination, but by extraction using a mixed solvent of these organic solvents and a hand-soluble organic solvent,
It has been found that tocopherols and tocotrienols can be separated. Furthermore, it has been discovered that tocopherols and tocotrienols can be concentrated in this extract by low-temperature fractionation, adsorption treatment using silica, argus, ion exchange resin, etc., and molecular distillation alone or in combination, The invention has been completed.

In the present invention? Copherols are α-tocopherol,
Al such as β-tocopherol, γ-tocopherol and human δ-tocopherol. '77' (Tocotrienols α-tocotrienol, β-tocotrienol, γ-
These eight components may include tocotrienol and δ-tocotrienol, δ-tocopherol, α
-1β- and H-J-tocotrienol are minor components,
α-tocopherol and γ- have the strongest vitamin E activity.
Contains tocopherol as the main ingredient.

The starting materials of the present invention are palm, banana, pineapple and sugarcane leaves, including both growing and harvested leaves, such as leaves cut when harvesting fruit and leaves cut when harvesting sugarcane. You can also give

According to the present invention, alcohols such as methanol, ethanol, and impropanol; ethers such as ethyl ether and impropyl ether; ketones such as acetone and methyl ethyl ketone; and carboxylic acid esters such as methyl formate, ethyl formate, methyl acetate, and ethyl acetate. Extract the leaves using organic solvents such as hydrocarbons such as , petroleum ether, hexane, heptane, benzene, toluene, and xylene, and halogenated hydrocarbons such as dichloroform, methylene chloride, and ethylene chloride, alone or in combination, as extraction solvents. The treatment yields an extract containing tocopherols and tocotrienols.

The extract in the present invention is subjected to low-temperature fractionation in the presence of an organic solvent, and a concentrate of tocopherols and tocotrienols is obtained in the soluble portion.

In addition, the extract in the present invention is dissolved in a nonpolar organic solvent and passed through a column packed with alumina or silica, and then alcohol, ether, ketone, ester, aromatic compound, organic chloride, etc. are added as a single or mixed solution. The solvent can be removed from the latter effluent section to obtain tocopherol and tocotrienol concentrates in the residue. Instead of alumina or silica in the above method, an ion exchanger is packed in a column, and an organic solvent solution of the extract is poured into the column, followed by an acidic organic solvent.The resulting section is washed with water, and after distillation, the residue is Concentrates of tocopherols and tocotrienols can be obtained therein.

Furthermore, the extract in the present invention layer is 10-2 to 1O-3-
Molecular distillation is carried out at a vacuum degree of U or below, and the temperature is 190℃ to 230℃.
The fraction distilled in can be collected to obtain a concentrate of tocopherols and tocotrienols.

The present invention will be explained in detail below with reference to Examples.

Example 1 Two kilograms of palm leaves (water content 42%) were shredded and extracted at room temperature of 22 to 24°C using a mixed solution of hexane and ethanol (V/V, 1:1). 102 g of extract was obtained. Ethanol 8001111 was added to this extract, and after shaking well, it was cooled to -20°C and the soluble portion was separated.

Ethanol was distilled off from the soluble portion to obtain residue 251.

This residue (1) contains 81,000 g of α-tocopherol.
g/g, p-) Copherol 350μ979, γ-tocopherol 4,240μ9/9, γ-tocoto1 noenol 200μg/g, total 85,790μ,! It contained iI/g.

Example 2 1 kg of sugarcane leaves (water content: 73%) were shredded and extracted at room temperature of 20-22°C using a mixed solution of hexa/ethanol (V/V, 1:1). 15g extract
I got it. Add 200ml of ethanol to this extract,
After stirring thoroughly, the mixture was cooled to -20°C and the soluble portion was separated. Ethanol was distilled off from the soluble portion to obtain 3 g of residue. This residue contains 12,000 tt of α-tocopherol.
l/11 and r-): 7 fer o-le 4,500μ, 9/
g, a total of 16,500 μ9/9.

Example 3゜Residue obtained in Example 3 (1) 10g 'k 50
ml of ethanol, and add the OH type basic anion exchange resin Amberlite IRA401 to a diameter of 5crIL.
The mixture was poured into a layer packed in a glass chromatography tube with a length of 100 ann to a height of 50 cm to adsorb tocopherols and tocotrienols, and then 3QQml of hexane was poured to wash away neutral substances. Next, 5% acetic acid ethanol 2
0011 was poured, and the solvent gold was distilled off from the effluent to obtain a tocopherol concentrate (O, syc purity 65%).

Example 4: After shredding 1 kg of pineapple leaves (45% moisture),
Extraction was performed using acetone at room temperature of 23-24°C.

Extract 45.2. I got an F. This extract was added to ethanol 4
After dissolving in 00ml, it was cooled at -20°C and the soluble portion was separated. Ethanol was distilled off from the soluble portion to obtain 8.6 g of a residue. This residue is α-tocopherol.

48.000 ttl//l! , r -) ko7 engineering a-
12,800all/g1 α-tocotrienol 6
50 μg/El, γ-tocotriol/-1. i oot
t9/9, containing a total of 62.5 s o tti/1.

Example 5 After 2 kg of 50 ゜ Wasp leaves (water content: 65 g) were shredded, they were extracted at room temperature of 24 to 25°C using a mixed solution of hexane and ethanol (V/V, 1:1). This extract contains α-tocopherol 22,000μm179, γ-tocopherol 1,060μg, Q, total 23,060ggZI
It contained.

:'7. −1〜・′−2゛.

! j ” l', ' I ' + , - Procedural amendment (spontaneous) 5 Decoy Giken No. 357 March 8, 1980 Commissioner of the Patent Office Kazuo Wakasugi 1, Indication of case Patent application No. 25519 of 1988
Patent applicant address related to case No. 1, 1-3-1 Kasumigaseki, Chiyoda-ku, Tokyo Name (11) Makoto Ishizaka, Director of the Agency of Industrial Science and Technology -4, Designated Agent 6, Number of inventions increased by amendment O8 , Contents of the amendment The following amendments will be made in the specification of the present application.

(1) Correct "excitation" to "animal" in lines 5 and 4 from the bottom of page 1.

(2) Correct “insoluble organic solvent” in line 5 of page 2 to “water-insoluble organic solvent”.

(3) "Aromatic compounds and" in line 7 of page 4 will be corrected to "aromatic compounds, non-polar organic solvents and".

(4) Correct [25,1 on page 5, line 1O] to r15.9J.

(5) Example 5 on page 7, lines 7 to 13 is corrected as follows.

``Example 5'' After cutting 20 kg of Banana leaves (65 g water) into pieces, they were extracted using a hexane-ethanol (V/V, [1) mixed solution at room temperature of 24-25°C. α-tocopherol 22,000 μy, γ-tocopherol 1,06
It contained 0 μg, a total of 23,060 gg.

(6) Add Example 6 and Example 7 next to page 5, line 1 O.

Power Example 6 Palm leaves (9C moisture 48%) were crushed using a roller and then shredded, and hexane-ethanol (V/V, 1
:1), add 12J of mixed solution, -night room temperature 22-24℃
After being left to stand, the extract was separated. 186 g of extract was obtained.

Methanol 11 was added to this extract, and after shaking well, it was cooled to 0° C. and the soluble portion was separated. Methanol was distilled off from the soluble portion to obtain 48 g of residue.

Refined palm oil 20.9 was added to the residue 20.9, molecular distillation was carried out, and the first fraction (~19
0°C), 2nd distillate 190-200°C, 3rd distillate 200°C
It was divided into 4 categories of ~220°C 1 residue. The tocopherol content in each category was 23.5% in the first category, 8.1% in the second category, 2.5% in the third category, and 0.6% in the residual content.

Example 7 2.3 kg of palm leaves (water content: 42 g) were shredded and
22-24°C), hexane-ethanol (1:
1. When extraction is performed with a mixed solvent (V/V), the extract 116
g was obtained. Add 51 hexane-ethanol (1:1, V/V) mixed solvent or 51 hexane to this extract and stir well. The mixture is then washed with plenty of warm water to remove water-soluble substances. After drying thoroughly,
It was cooled to -20°C, and the hexane soluble portion was separated. This hexane-soluble part was collected in a silica column (810,811 people, 10
0-200 mesh) and subsequent elution with hexane, the hydrocarbons were eluted first, followed by the alpha-tocopherol. The α-tocopherol fraction obtained was 25 g, containing α-tocopherol concentration ihalos, 4
The recovery rate of α-tocopherol was 83.3%. ”

Claims (1)

[Claims] (1) In a method for separating tocopherols and tocotrienols in balm leaves, banana leaves, pineapple leaves, and sugarcane leaves, the leaves of the plants are subjected to extraction treatment using an organic solvent alone or in a mixture. A method for separating tocopherols and tocotrienols, characterized by