CZ86788A3 - Chamomile oils with high content of natural polyines and process for preparing thereof - Google Patents

Abstract

Camomile oil with a content of natural cis- and trans spiro ethers of, in total, at least 1 wt.%, is new. The camomile oil can be prepd. by steam distn. or distn. with water of fresh camomile or extn. residues from camomile extn. Water distn. is pref. carried out at pH 4-8, opt. in the presence of reductants. The extracts pref. contain cis and trans spiro ethers in a total amt. of at least 1.0 mg/100g extract, esp. at least 0.5mg cis and 0.3mg trans spiro ether per 100g extract. The resulting camomile oil pref. contains at least 1 wt.% cis and 0.5 wt.% trans spiro ether, and can be added to any physiologically acceptable solvent to give more camomile extract.

Description

chamomile and chamomile extracts are of importance for the determination of the quality of chamomile and chamomile extracts _, such as, for example, polyis _and such as eis and trans-.alpha.-a-dioycloether (* spiroether).

camomile eajf anti inflammation Xiva and spasaolytic properties · These spiroethers ee but decompose, sown and heat ·

Camomile essential oil can be obtained by distilling it by extracting camomile drugs, that is, dried and dried chamomile flower baskets.

Although distillation allows the tube to be free of other elixions, it is therapeutically attractive. however, the terno-© and labile epiroethers are severed in this process. Therefore, the chamomile contains a typical set of active ingredients for chamomile. However, even by extracting, camomile essential oil cannot be fully recovered, for example, in the production of liquid extracts of 4% ethanol, only about half of the dross, bicabolol and chamene sulphide containing the essential oils and delicate spiroethers pass into the extract.

It has now been unexpectedly assured that in the distillation of the chamomile extracts and the chamomile extracts or the fresh chamomile flowers, the chamomile essential oils, which, despite the thermal «work, are high in polymers, are cut. The names of the thermolab are lazy, preferably trans-en-in-block cyclic ether.

This eis-en-in-bioycloether ("cooking thal" eis-apiroether) and the following are shown below. structure

and tran-R * -ia * blWkloetter (trasRBpitwthBr) at. the following structure h ^ c- ^ c. ·

according to camomile fused · camomile fabric. Such a camomile essential oil is, for example, suitable as an additive to enrich these with an active ingredient a high level of active ingredients having a high level of chamomile;

In addition, it allows the utilization of residues and extraction of chamomile extracts from chamomile extracts, which are contained in the colloidal substances. This has the consequence of the active substances melting to achieve considerable raw material savings for the extract.

bows with

Even the distillation of blooms or εύ with extrnkoe of fresh chamomile flowers does not only require the use of expensive drying sieves, but also eliminates considerable operating costs for the usual pre-treatment of the materials to be distilled. acting substantially dreams Bit.

The addition of chamomile silica, the crushed spasobes according to the invention, which contains a large amount of spiroether, is also achieved in the chamomile network. essential oils obtained by the usual »distillation« action®, in the manufacture of chamomile extracts containing extracts containing © a typical chamomile set

The recovery of the essential oils according to the invention is carried out by steam distillation or water distillation.

In the distillation with water vapor, hot steam is introduced into the distillation vessel at a pressure of at least a pressure of * * or a pressure of up to 0.4 * 0, | "and. The boron vapor of the series may be under pressure and, for example, »0,1 0.1, preferably 0 to 0.0> Wa, the vapor steam having a temperature of, for example, carried 10 až to 140 WW (assis 145 ° C), preferably at least 10 a a Xj © ^@ i, preferably 1 © 5 a

115¾.

The optimizing time is, for example, d to 10 hours, and preferably and up to 4 hours, in the case of aqueous distillation, they do not add to the distilled aateral. The heat may be either xetime or discontinuous.

The distillation and the water are carried out in a sufficiently large shaking vessel filled with water (for example, the temperature is mixed with one part by weight of the material to be distilled with at least one part by weight of water, preferably 10 and 100 parts by weight). preferably with 10 to 6 parts by weight of water, which may contain conventional additives such as reactants (for example sodium ascorbate, ascorbic acid) or inorganic acids (for example hydrochloric acid, sulfuric acid) and alkali metal hydroxides (for example dilute BaOl) Distillation can be carried out at ph mel values of 4 and S. 8, however, it is advantageous not to adjust the p® so that the distillation is carried out in a neutral environment. The amount of editorial agent added is, for example, 0.1 to 1 part by weight per 1 part by weight of plant material.

The distilled material may be crushed before the process. The moisture content of the material used for distillation is, for example, an average of 6 > (water-alcohol) for the chamomile extraction residue and an average of 8 > for the fresh chamomile. The distillation may be carried out in conventional mobile or stationary distillation vessels.

The distillate condensed by cooling is collected, for example, in a scoop (container), vsbAmM

- 6 camomile essential oils and oxen based on different specific gravity (for example, the bottle of La Clarita, but also in other conventional separators as well as separators with spinning devices).

The chamomile oil of the top phase may, for example, be used after separation of the aqueous phase and without further steps to produce chamomile extract preparations. for example, phase differences can be quenched by the addition of salts such as sodium chloride (salting out).

In the distillation, optionally, the distillation of the apparatus may be flushed with a low boiling lipefilament solvent, for example, a liquid saturated aliphatic carbon - by ¹ ε> to? carbon atoms (e.g. n-pentaamide, petroleum ether) once or more (two times and three times) to remove the last residual oil from the distilled bridge. For flushing with 1, for example, 1 to 2 wt. Ml of hydrocarbon is used per 1 part by weight of the dry residue of the extraction residue used. The hydrocarbon removal (see below) is combined with the residue of aqueous distillate.

when the hydrocarbon is combined with the distillate distillate, the active substances of the distillate pass into the hydrocarbon. Separation of the hydrocarbon phase from the aqueous phase is then effected, for example, by a mixed method by adding sotefto chloride followed by repeated shaking (for example twice) of the aqueous phase with a hydrocarbon. After drying the hydrocarbon oil, the chamomile oil will remove the hydrocarbon, conveniently at temperatures between 4G and 60 ° C. Last hydrocarbon residues may be removed, for example, current © »hot air (temperature 40 to 6U ^G C).

The term "fresh chamomile flowers" means chamomile flowers that distil or freeze within 24 hours of being picked.

The process according to the invention is quite generally applicable, that is to say, it is suitable for all existing compounds which contain spiroethers. in particular, the following Heiwana (or drugs prepared therefrom) are used, for example; Diploid chamomile variety Oegumill (protected in ZB under the Law on Variety Protection, German patent 24 02 302, Italian patent 1 Qj> *> 0> 'b), tstraploid chamomile variety Menšena (German published application M 2J 207), tetraploid chamomile according to German Published Document 35 42 756 *

Further suitable are, for example, the following diploid starting camomiles; ^w Argentine origin * (see L. Padala, Mondina et al., S. G.ussio, Quantitative determination of essential oil, Total content of azalenes and chamazu-flax in German camomile, Matrlcaria ehamomilla, grown in Argentina, Planta med. Jig, pages 27J to 280, Xifb)

Jakeš i. All of you that contain bisabolol in iodine at measurable concentrations («rules over» $ 5) in essential oil. For example, the chamomiles described in the following literature may be described in the following literature: &quot; Sohillher, H. &quot; felklová, V. Lukeš and K. Jaslcová «I by gas analysis <ctoroaatgrate> and on the halo-type types of oil» Arch, Bhara. 210-215 .mu.l of J. 08X.alpha. And A. Wael rhodkshad aorfoxic and chemical char actor for the isolation of certain populations and varieties of Matríoarla ehwmill h.% Acta Bert. lop to 114 (! $ »)

The following chamomile tetraploidies also come into consideration, for example: chamomile varieties hedegold teti * erythroi (dad, Ooty Lea (mako), M-2 (Mažarskc) · These varieties are described in the following literature: M, Chládek, V. Kosová, M, «Ruby, pharaohia 7X2 to '71 'O-Wh (* Ca & bajeka, Mss. PosnaúdýóJ)» <»· feetkkc and P, Wlia * rhara, žHalle lg |, 81 j to S2J tlf # j, X * Sárkáay, Berlu Beagar ,

The residues and extracts of hashama used for the action of the invention include those residues which are normally obtained in the traction of the chamomile drug or fresh chamomile with alcohols or alcohol and water. The alkali metal used for such extraction is, for example, the following alkali and their non-water-soluble or branched aliphatic alcohols having from 1 to 6 carbon atoms such as carbon monoxide. solketal (2,2 * dl-ethyl-4-hydroxy-3-hydroxy-X) -dioxane, such as ethoxylate, ethanol, 1-propuaeX, 2-propaaol, butanol etc. it is also possible to use mixtures of these oil and mixtures with water. In the case of aqueous aqueous mixtures, the water content is, for example, 0 to preferably 10 to 10, preferably> 0 to 55, percent by volume.

the extracts from the chamomile extraction are immediately, still in wet condition, subjected to distillation according to Vywalds. It is possible to settle these residues (up to 60 ° e, Z to 5 hours) and to store them if necessary. (15 to 25 [deg.] C., relative to a flow rate of 40 [deg.] &lt; 0 &gt;) and transported for a longer time according to the chamomile oil obtained according to the invention contains at least 1% by weight, preferably not name 1.5; most preferably, 2 weight percent of the polyin (sonnet is a polythe with one natural pelyisy), the polythe (sum of all polyes) is, for example, al. 20, preferably 4 and 18, in particular 10 to 10 percent by weight. The content of the eis-ether is, for example, at least even a percentage of heoth, preferably 2 to 1, with the names 5 to 1p of the weight percent. For example, victims of Sina trana-spiroether, for example, hejme 0, $, with 0, &gt; ad 15, with the names 1 mazuleau of Sina, for example 0.9 t &lt;

up to 32 haetnosto prooent. The content of bisololoxide A is, for example, 1 to 10% by weight, preferably 2 to 4% by weight. The content of bis-bololoxide * is, for example, 0.8 to 1% by weight, preferably g to 4

The chamomile oil obtained according to the invention is added, for example, in pure form or as a solution in a phospho-acceptable organic solvent (e.g. ethanol), to water-alcoholic chamomile extracts which have a known &quot; effect &quot; stirring. The aqueous-alcoholic extracts are, for example, those extracts produced by germany using ethanol or isopropanol. Content. The alcohol content of the extract should not exceed 20% by weight. Generally, it will contain 20 to > 0 weight percent, and preferably 1 percent alcohol. Addition of camomile

With respect to such extracts, it could be calculated so that it finally contained 100 to 250 and &lt;

180 to 200 µl of an alcoholic extract. The content of bisabolol is then, for example. when using camomile rich in bisabolol 20 to

100 mg, preferably 40 to 80 mg per 100 g of extract. Extract mg then contains, for example, 1.5 cis- and trans-spiroether per

100 g.

chamomile extracts or chamomile extract preparations which are obtained with the addition of chamomile essential oil according to the invention contain, for example, at least 1.0 mg per 100 g, preferably 1 to 10, in particular 2 to 5 mg, of polyins. The cis-spiroether content is at least 0.5 mg per 100 g, preferably 0.7 to 4.0, in particular 1.0 to 5.0 mg. The content of the trans-spiroether is at least 0.5, preferably 0.7 to 5.0, in particular 0.7 to 1.4 mg per 100 g. The chamazulene content is, for example, 5 to 25 mg per 100 g, preferably 5 to 20 mg. The content of bis-bisabolol is, for example, 50 to 100 mg per 100 g, preferably 50 to 80 mg, in particular 40 to 60 mg per 100 g. The content of bisabololoxide A is, for example, 5 to 50 mg per 100 g. 100 g, preferably 5 to 25, in particular 5 to 20 mg per 100 g. The content of bisabololoxide B is, for example, 5 to 20 mg per 100 g, preferably 5 to 18, in particular 5 to 15 mg per 100 g.

Example 1

In a 1000-liter round-bottom flask, mix 41 g of heimane extraction residue (corresponding to 10 g of dry matter) with 500 ml of water * adjust the mixture to> 1x 6 *> with a dilute sodium hydroxide solution & distil for approximately 5 hours, For example, a 1000 ml shaking funnel is used as the collecting screen. When 400 [mu] l of distillate is obtained * 2 more shifts are continued in the distillation without reporting * after which the distillation head and the condenser are rinsed with SC and pentane. the rentane is combined with the distillate and after. Add 5 g of sodium chloride shake. Repeat the shaking for a further s times with «1 pentaam. The combined organic phases are dried over δ g of anhydrous seventh sulphate and filtered. Container and filter. The pentane phase is then carefully concentrated to approximately ml volume (water bath &gt; 6 ° C), washed with a stream of hot air (temperature:

up to 60 ° C * hair dryer) · Heiitone silic® is obtained.

ohasazulen % (-) - α-bisabolol 20 * 5 bisabololoxide A 2 * 7 f bisabololoxide B 4 * 1 $ cis-spiroetner 10 * 2 fi trans-spir etnei » . i>?

* 1> *

This is a chamomile residue from the extraction of chamomile> driven by dry ethanol with water (47: $ | v / v), Poillteu be a drug rich in flip-flops> 4 Ga SGg,

Comparative example (anaaý procedure)

10 g of camomile flowers are distilled (the drug is identical to the camomile drug prior to the extraction used in Example 1) as described in Example 1.

Distilled oil has the following composition:

eham & zalen 7 »6 M (-) - oL-bleabolol> 4 * 4 eats bieafeololoxide and 1.6 f feisabololoxide B 1.7 eats-splroether and> eats tri- na-spiroether. not proven.

Example 2

In a two-necked flask of 1000 al, add> 7.8 g of fresh chamomile of the Seguaill variety, rich in bisabolol (corresponding to 10 g of the drug, this enamored succulent chamomile flowers). ps fits into the flask and the nozzle with the ball! »ehlsdídea is fed to the flask by the sides and the nozzle and the steam generates steam. BsstiXses ss ends after 4 hours.

The distillate essential oil of the upper lash was separated using a Florentine bottle and the essential oil was analyzed. Its composition is as follows:

ohaaasulsn 12,5 f -bisabolol 22.1 IS bisabolaloxide A *, TJE bisabololoxide B ois-spiroether 11, 8 IS traas-epiroether 7,5 *.

A comparative example (saaa procedure) is bestized with 10 g of dried chamomile turtles (the drug is identical to gently dried worms used in Example 2) as described in the example of the upper lash spaced camomile stltes and having the following composition:

ehaa & eulea 9.6 t (-) - Bisafeolol 21.2) i hisabololoxid A J.O Č Msa & olGloxld. (B) M t ois-eplroetker 1,1 t trsaa-spiroetfcer 0,5 6.

v ··

Claims (7)

1, Camomile oil containing natural cis- and trans-spiroethers in a total amount of at least 1 weight percent. 2. Revaluate the camomile oil containing at least 1% by weight of natural cis-spireotheres and at least 0,5% by weight of natural trans-spiroethers. J. A process for producing a camomile oil with a high content of natural spiroethers, which scalds by subjecting fresh camomile or chamomile extract residues to a steam distillation or water distillation. 4. The process according to claim 1, wherein the distillation is carried out at a pH of 4 and 5, optionally with the addition of reducing substances. 5. Use of camomile oil according to one or more of the preceding points as an additive in the manufacture of camomile extracts or camomile surveillance preparations. 6. Chamomile extracts or preparations with chamomile extract containing eis * and tr * spirethers in a total amount of at least 1.0 mg / 100 g. He, camomile extracts or preparations with chamomile extract containing an eis-spiroether of at least,, / / 100 g and a trans-spiroether of at least 0.1 mg, mg / 100 g. A process for the preparation of chamomile extracts having a high content of eis- and trans-spiroethers is characterized in that the chamomile silage is prevented according to one or more of the scales, optionally in a physiologically acceptable rosette, with the chamomile extracts. < 9 »Camomile siliee, obtained according to one or several previous points. 10th chamomile extract sky preparations with chamomile extract / from one or more skenébodle before eháaejíeíoh stings *, ^A *