DE1152221B - Process for obtaining triterpenic acids - Google Patents

Description

Process for the production of triterpene acids Addition to patent 1101697 It is known that triterpenic acids, besides in hawthorn, in numerous other plants, in particular plants of the family of the Labiats, Rosaceae and Ericaceae occur. In contrast to Crataegus oxyacantha, which in leaves, berries and flowers besides Oleanolic and ursolic acid also contains crataegolic acid, occurs in other plants, as far as could be ascertained, crataegolic acid rarely occurs, so that it is preferred only contain other triterpenic acids.

In the German patent specification 1101697 is a method for extraction the water-insoluble ingredients, especially the triterpenic acids from Crataegus described. It has now been found to be the same from the other Plant the triterpenic acids with the help of trichlorethylene, which also contains other halogenated hydrocarbons can be added or mixtures of these solvents with at most 30% lower aliphatic alcohols with 1 to 5 carbon atoms, in good yield can be won. The same goes for extracts made from such drugs, for example with the help of alcohols, and those in addition to the triterpenic acids Contain water-soluble ingredients of the plant.

From those obtained with the aid of the solvents or their mixtures Extracts you get a raw mixture of triterpene acids, just like in the main patent described by a subsequent treatment with aliphatic or cycloaliphatic Hydrocarbons such as ligroin, gasoline and the like, with fatty substances and fat-soluble Dyes in solution walk. Even if the starting drug was already defatted, it is such treatment is consistently required as it is always present in the extract obtained there are still small residues of fats and, above all, large amounts of colorants.

Yields of crude triterpenic acid mixture from different plants are shown in the table below: Raw booty Amount of drug,% yield Drug triterpenic acid color dried per drug G Folia althaeae. 3000 7.0 0.233 green Herba cichorii. 3000 4, 5 0, 150 green Cortex 50000, 50, 010 Bright Cortex phaseoli (fructus). 2200 2, 0 0, 092 light Folia farfarae 4500 11, 50 0, 25 dark green Herba salvia prat. (German goods) 3400 23, 0 0, 67 dark green Pirus malus et comunis (marc). 3200 64, 0 2, 0 light yellow Herba origan .. 3500 19, 0 0, 54 dark green Herba hederae helicis. 2000 6, 0 0, 30 dark green Herba hederae terestris. 2500 32, 0 1, 28 dark green Herba serpylli c. fl. 3000 45, 0 1, 50 dark wort Flores ericae ..... 3500 189.0 5, 40 light yellow Cortex salicis frag ... 5700 70, 0 1, 22 light green Herba tanaceti c. fl .. 3500 3, 0 0, 08 dark green Folia sennae Tinnevelly ... 3000 18, 0 0, 60 Dark green Raw booty Amount of drug,% yield Drug triterpenic acid color dried per drug G Folia rosmarini. 3200 145.0 4.53 red brown Folia uvae ursi ..... 5470 150, 0 2, 72 green Folia castaneae vescae .. 1650 6, 0 0, 36 green Folia betulae .. 3600 248, 0 6, 88 Dark green Folia saponariae .. 3000 5, 0 0, 16 Dark green Folia quercus ... 3000 12, 0 0, 40 green Radix taraxaci .. 24005, 00, 20 Light yellow Radixliquiritiae ... 2500 3, 0 0, 12 Light yellow Flores caryophylli 1700 105, 0 6, 17 Light yellow Herba myrtilli ....... 3000 30.0 1, 0 green Apple pomace .. 3000 62 2, 06 light Folia rosmarini repeat 3000 148 4, 60 red-brown Flores ericae .. 3000 165 5, 30 light Herba geum .. 3000 20 0.66 Dark green Herba bistortae. 2200 12 0.54 dark green Herba matricariae .. 3000 3 0.00 dark green Flores pruni spinosae. 3000 40 1.30 light green Herba ericae c.flor. 3000 160 5.30 light green Herba agrimoniae .. 3000 9 0.30 light green Herba alchemillae .. 3000 40 1, 30 dark green Herba anserinae ... 3000 20 0.66 light Fructus pruni spinosae ... 3000 6 0, 20 Hell In this case too, the use of trichlorethylene as an extractant for the plants proved to be particularly suitable. Even better yields are obtained with mixtures of trichlorethylene and aliphatic alcohols with 1 to 5 carbon atoms, but the trichlorethylene content should be at least 700%, since with a higher alcohol content water-soluble parts go into the extract and thus make further processing unnecessary.

The so obtained, freed from fat and some of the colorants crude triterpenic acid mixture is still colored throughout and can be adsorptive Treatment clean. It is best to use solutions of the triterpenic acid mixture for this purpose in a mixture of halogenated hydrocarbons, for example trichlorethylene or chloroform, and a lower aliphatic alcohol, preferably with 1 to 3 carbon atoms.

A solution in a mixture of equal parts is particularly favorable halogenated hydrocarbon and alcohol. Activated carbon, active alumina, bentonite and the like can be used. Depending on the amount of used adsorbent and the plants from which the triterpenic acid mixture was isolated, the purified mixture falls after distilling off the solvent practically colorless to pale yellow or light green in color.

The purification of the crude triterpenic acid mixture by selective adsorption is usually not necessary if the individual triterpenic acids are isolated should ; but it still proved to be advantageous because the separation was easier going on.

The triterpenic acid mixture can also be purified by treatment with an ester with a maximum of 3 carbons, i.e. methyl formate, methyl acetate and ethyl formate, but especially methyl formate, possible in the cold. Here the dyes are largely dissolved out, along with possibly existing Sitosterols and small amounts of low-melting triterpenic acids are still unknown Constitution. But it is also possible to use both methods for purifying the triterpenic acid mixture to apply one after the other.

A separation into the individual triterpenic acids is just like described in the main patent, possible.

As has been found, however, with fractional concentration, or with fractional precipitation, not very pure individuals, but the individual Acids are still contaminated with other acids.

Better separation can, as has been found, through treatment with esters that have a maximum of 3 carbons, especially methyl formate, can be achieved in the heat. Here the ursolic acid remains practically undissolved, while oleanolic acid and lower melting triterpenic acids, along with possibly any remaining amounts of dye, go into solution. Crataegolic acid, if present only partially goes into solution, the main amount mostly remains with the undissolved Ursolic acid. If there is no crataegolic acid in the plant in question, then there is the residue from treatment with hot methyl formate from almost pure ursolic acid.

For further cleaning, especially to remove crataegolic acid, the portion insoluble in hot methyl formate can be obtained from a treatment with methylene chloride subdue in the heat. Here the ursolic acid remains undissolved, while crataegolic acid and any other impurities that may be present go into solution. To achieve an ursolic acid of the highest purity, the product obtained can still be obtained from a Recrystallize alcohol and possibly the hot alcohol solution of an adsorptive Subject to treatment with an adsorbent.

The oleanolic acid can be obtained in a similar manner from the isolate the above solution, from which the lower ester is distilled off. By treatment with methylene chloride in the heat, the oleanolic acid also remains undissolved, while the crataegolic acid, lower-melting triterpenic acids and possibly existing dyes go into solution. The oleanolic acid can be used as well as with the ursolic acid described, can be obtained completely pure by recrystallization from alcohol.

From the alcoholic mother liquors, after evaporation of the Solvent still win more Ursol and oleanolic acid, which is expediently the combined alcoholic solutions again the treatment with low estei and methylene chloride, possibly in reverse order. That the Oleanolic acid and ursolic acid can be obtained in this way by treatment with methylene chloride Can be cleaned is surprising in itself, since it can be cleaned by extraction with methylene chloride or, better yet, methylene chloride-alcohol mixtures from the drugs.

Probably the other ingredients of the drug favor it Solubility of the acids in the solvent.

Claims (3)

PATENT CLAIMS: 1. Process for the production of triterpenic acids according to patent 1101697, characterized in that drugs other than Crataegus, the as well as crataegus contain triterpenic acids, or extracts of these drugs that contain water-soluble substances in addition to the triterpenic acids as starting material be used. 2. The method according to claim 1, characterized in that mixtures of an aliphatic alcohol with a maximum of 5 carbon atoms with trichlorethylene be used for extraction, the trichlorethylene content at least 70% amounts to. 3. The method according to claim 1 or 2, characterized in that the extracts evaporated to dryness with an aliphatic ester, especially pre-cleaned with methyl formate, with the same solvent in the heat in two Separate fractions, bring each fraction to dryness for itself and each fraction treated by itself in the heat with methylene chloride.