DE1492873C3 - - Google Patents

Description

3 4

Marigold flower powder free xanthophyll or xan. Suitable extraction solvents for this are non-

thophyll products with an extraordinarily high level of polar organic liquids, e.g. B. petroleum ether,

Pigmentation activity on simple and elegant hexane, chloroform, ether and acetone.
Way can be obtained by doing this. According to the method of the invention, the

Flower powder with a certain amount of S xanthophylls, also from very dilute solutions

Treated with alkali metal hydroxide and obtained from it or from diluted, stable dispersions,

obtained reaction mixture then with a non- in which the concentration of xanthophyll is less

polar solvent, the xanthophyll or xan is about 0.25 percent by weight. Preferably

thophyll product extracted. * ■ however, xanthophyll concentrations of

The invention relates to a method for io more than 0.25 percent by weight, i.e. H. Concentrations

Extraction of xanthophyll or xanthophyll - from about 0.25 to about 100 percent by weight, a

products made from marigold flower powder, which set thereby. In the presence of dilute solutions or

is characterized in that one dilutes, stable dispersions of xanthophylls

. . , ,,,. .. "with a considerable or substantial alkali

a) eme from the Mangold Flower Powder emer waß- _{15 consumption can it expedient} ß _{ig se} i _n, this ring solution an alkali metal hydroxide with _{solutions or} dispersions initially in konzenemem content of alkali metal hydroxide to convert the the _tri ertere solutions or dispersions. Alkali consumption of the xanthophyll or xanthophyll _{This can, for} . _B. by solvent extraction, phyll product m the flower powder corresponds to at least solvent evaporation and chromatographic, and a short-chain alcohol be _ao process. An example of a suitable standing _ej mixture for about 1 minute to about solvent, wherein the solvent is removed for 24 hours at reflux temperature loading ^^ _{consists of the system} hexane / aqueous

_t acts, _. Methanol.

b) the reaction mixture obtained thereby. _The process of the invention is diluted in the manner of water,., _ ,,. .. a ₅ carried out that that or those to be treated

c) from it with a with the reaction mixture _Xantl f _{ophylle or} . _{ώ6 the} xanthophyll (s) immiscible arctic polar solvent _contain y _en materials with an alkali metal for xanthophyll the xanthophyll or _{xanthohydroxide in the} presence of a short-chain alcohol, extracting the phyl product. _z ' _ß methanol, ethanol and isopropanol, mixed

d) separating the solution obtained and the Losungs- _{30 are} evaporating _A ^ _{carrying out the} process of the medium. Invention suitable alkali metal hydroxide is z. B.

According to a preferred embodiment, sodium hydroxide or potassium hydroxide are used or are

the alkali metal hydroxide is potassium hydroxide. Mixtures of these compounds. It turned out to be

According to a further preferred embodiment, it has been shown to be expedient to use the alkali metal hydroxide in

Ethanol is used as a short-chain alcohol. 35 form of an aqueous solution for use

Bring according to a third preferred embodiment. The amount of alkali metal used

ether is used as a non-polar solvent, hydroxyds corresponds to at least one chemical

Isppropyl ether or chloroform. Equivalent to the amount of potassium hydroxide that results from

According to a fourth preferred embodiment, the alkali consumption value of the xanthophyll or

if the treatment is carried out in the first stage about 4 ° of the xanthophyll products and possibly others

3 hours at reflux temperature. alkali-consuming compounds, the given

The method of the invention is suitable for improving and increasing the pigmentation activity, which can still be present in the starting material. It should be noted that other xanthophylls and xanthophyll products that are used in the concentrates to be processed also contain other erecta L. in the petals of Aztekmarigold (Tagetes 45 alkali-consuming compounds). The method of the invention can, for example, triglyceride oils.
has the advantage over the treatment in the short-chain alcohol in the process known from "Ullmanns Encyklopadie der When the process of the invention takes place die Alkalitechnischen Chemie", vol. 7, p. 103 (1956), that it is the first possible reflux temperature of this liquid .
It is borrowed to obtain the xanthophylls directly from the marigold 50 The treatment time normally depends on obtaining both flower powder in concentrated form, since the treatment temperature as well as the xanthophyll content in the marigold flowers is as high as the desired degree of increase in pigment as in the leaves, so that after the animal activity. Since the treatment temperature of the process of the invention ^{depends on the reflux temperature of the material used in the known process only about 1} Ao of the organic liquid to be processed, the requirement depends, so that with the same expenditure of time, a lot of treatment time also depends on the larger amount of organic material used of xanthophyll with a higher fluidity. For example, obtained with an alkali pigmentation activity. This represents a solution that has been worked out, the sufficient alkali metals represent a considerable technical progress.

In the process of the invention can have fresh, 60 mentation activity, so requires a Be-Xanthophylle containing marigold flowers used a treatment temperature of about 90 ° C (reflux, or these can only have a treatment time of about before the temperature of the invention appropriate treatment first dried and through 3 hours. In general, treatment grinds have become be converted into a powder. According to a time from about 1 minute to about 24 hours as the Preferred embodiment of the method of increasing pigmentation activity is suitable for the invention the alkali treatment of the xanthos is carried out. The alkali treatment is preferably carried out phylls in the same way as obtained by known processes until maximum pigmentation is achieved Extracts from the marigold flower powder. activity,

The method of the invention can be carried out in devices that are air-permeable. Preferably, however, the method of the invention is carried out in devices in which a inert atmosphere, for example a nitrogen or carbon dioxide atmosphere, prevails. Further For example, the process of the invention can be carried out at reduced pressures. The implementation of the method of the invention in an inert atmosphere and / or at reduced Can press to avoid a loss of xanthophyll or xanthophylls due to oxidation, be beneficial.

It can optionally be advantageous to add one or more antioxidants to the reaction mixture. The antioxidants can be added before, during and / or after the treatment. Suitable antioxidants are, for example, the known butylated hydroxyanisoles (BHA), butylated hydroxytoluene (BHT), _a o tocopherol, lecithin and 6-ethoxy-1,2-dinydro-2,2,4-trimethylquinoline (hereinafter abbreviated to "ethoxyquin").

After the alkali treatment, the resulting reaction mixture is diluted with water, with extracted a non-polar solvent for xanthophyll which is immiscible with the reaction mixture, the resulting solution separated and evaporated. A partial or complete Neutralization (however, it is advisable not to acidify up to a pH value of substantial below about 6, the preferred pH being about 6.0 to 8), a treatment with Ion exchange resins, chromatographic treatment processes or complex formations carried out will.

The separated xanthophyll can be in various liquids, either through Dissolve or be incorporated by suspending. For example, dispersions in vegetable Oils or other oils can be prepared using suitable surfactants be able. The separated xanthophyll can, optionally in the form of concentrates, also in dry products are incorporated, whereby they are absorbed by the dry products, or they can be prepared by spray drying processes, drum drying processes and the like with solid Feed ingredients are mixed. Products that absorb the xanthophyll include, for example swollen hydrate biotite, calcium silicate and soybean meal. Suitable carriers for through Products obtained by spray cooling are, for example, saturated fats, e.g. B. hydrogenated tallow, hydrogenated Peanut oil, hydrogenated lard, hydrogenated coconut oil, hydrogenated cottonseed oil, hydrogenated Saffron oil and hydrogenated rapeseed oil. Suitable carriers for spray-dried and drum-dried products are, for example, gelatin, natural gums and Strength. Suitable carriers for products made from dispersions are, for example, gellable and non-gellable colloids such as starch, gelatin and najur gums.

. The xanthophylls which can be prepared by the process of the invention can, whether they are in the form of Concentrates, dispersions or solid products are included in all types of poultry feed be to an increased pigmentation of the Skin and / or fat of poultry and the yolk of poultry eggs. The after Process of the invention which can be produced xanthophylls can also be used as dyes for coloring for the human consumption certain foods are used.

The following examples are intended to further illustrate the process of the invention.

In various examples, light absorption values and extinction values are given. From the Light absorption values can be used to draw conclusions about the. Draw xanthophyll concentration. From the absorbance values the yields can be calculated. The absorbance value is equal to the number of Grams of recovered material multiplied by E (1%, 1 cm, chloroform) (wavelength) of recovered Materials, multiplied by 100, divided by the number of grams of the material used, multiplied by E (1%, 1 cm, chloroform) (Wavelength) of the material used.

The examples also contain information on the pigmentation activity of xanthophyll in poultry. This was determined by comparing the effect achieved (the coloring of thighs or the skin or the color of the yolks of egg-laying hens) after feeding a certain one Amount of xanthophyll produced by the process of the invention with the effect obtained by feeding a molecular equivalent of pure lutein (3,3'-dioxy-a-carotene), d. H. one highly active, poultry pigmenting compound.

example 1

50 g of a marigold flower powder with a light absorption value of E (1%, 1 cm, chloroform) (454 Γημ) = 12.3, an alkali consumption value of 250 and xanthophyll with a pigmentation activity of 38% were mixed with 100 ml of 95% ethanol (Remainder water) and 50 ml of a 50% strength aqueous potassium hydroxide solution (50 percent by weight potassium hydroxide and 50 percent by weight water). The mixture obtained. was refluxed for 3 hours. 100 ml of water were then added and the treated, dilute mixture was extracted three times with 100 ml of ether. The ethereal extracts were combined, whereupon the ether was evaporated. In this way a xanthophyll concentrate was obtained. The concentrate yield was 3.2 g. The concentrate had a light absorption value of E (1%, 1 cm, chloroform) (454 m / i) of 187. The absorbance value at a wavelength of 454 ταμ was 97%.

The pigmentation activity of the xanthophyll in the concentrate was about 75% (based on the pigmentation activity of pure lutein = 100%).

Example 2

25 g of marigold flower powder were extracted with isopropyl ether. 1.79 g of an extract were obtained. The extract had a light absorption value of E (1%>, 1 cm, chloroform) (454 ταμ) of 169. The extinction value at 454 τημ was 98%.

0.8 g of the extract were mixed with 2.5 ml of isopropanol and 0.4 ml of a 50% aqueous sodium hydroxide solution mixed. The mixture obtained was then refluxed for 3 hours.

heats. Finally, 10 ml of water were added, and the diluted product was extracted with isopropyl ether. After removal of the solvent, a xanthophyll concentrate was obtained. The yield of concentrate was 0.64 g. It had a light absorption value of E (1%, 1 cm, Chloroform) (454 ταμ) of 194. The extinction value at 454 ταμ was 92%. The pigmentation activity was similar to that in Example 1.

Example 3

0.5 g of the extract from Example 2 were mixed with 2 ml of isopropanol and 0.3 ml of a 50% aqueous sodium hydroxide solution. The resulting mixture was then refluxed for 3 hours and then neutralized to pH 7 with phosphoric acid. The neutralized product had a light absorption value of E (1%, 1 cm, chloroform) (453 ταμ) of 160.

Example 4

425 g of a crude xanthophyll product with a light absorption value of E (1%, 1 cm, chloroform) (452 τημ) of 30 and a xanthophyll with a considerable alkali consumption value, a poultry thigh pigmentation activity of 18% and an egg yolk pigmentation activity of 7% were with 200 ml a 50% aqueous potassium hydroxide solution and 400 ml 95% ethanol mixed. The resulting mixture was then refluxed for 3 hours. The reaction product obtained was then diluted with 600 ml of water and extracted three times with 900 ml of ether. The ether fractions were combined, whereupon the ether was removed by evaporation. 307 g of a xanthophyll concentrate were obtained which had a light absorption value of E (1%, 1 cm, chloroform) (450 τημ) of 42.7. The poultry thigh pigmentation activity of the xanthophyll in the concentrate was 36%. The egg yolk pigmentation activity of the xanthophyll in the concentrate was 17%.

Example5 '

115 g of the crude xanthophyll concentrate described in Example 4 were refluxed in 184 ml of methanol, 32 g of a 50% aqueous sodium hydroxide solution being slowly added to the mixture boiling on the reflux condenser. After a heating time of 1 hour, the mixture obtained was neutralized with 22.8 g of glacial acetic acid in 300 ml of water. An oily phase formed. This oily phase was separated from the aqueous phase and washed with water. The product, namely the xanthophyll concentrate, had a light absorption value of E (1%, 1 cm, chloroform) (450 τημ) of 38.

6o example 6

100 g of marigold flower powder [E (1%, 1 cm, chloroform) (454 τημ) = 20.4; Alkali consumption value = 230] were heated under reflux with stirring for 2 hours with 500 ml of denatured ethyl alcohol containing 31 g of NaOH and 20 ml of water. The mixture was then cooled to room temperature and neutralized to pH 8.0 using a 50% aqueous solution of phosphoric acid. Then 0.3 g of "ethoxyquine" was added. A further 300 ml of water were added, after which the alcohol was removed by distillation. The aqueous slurry was then dried by spray drying in a laboratory dryer at an injection temperature of 204 ° C. Fine-grain granules were obtained. The product had a light absorption value of E (1%, 1 cm, chloroform) (454 πΐμ) = 14.8. The yield determined by absorbance was about 95%. The poultry thigh pigmentation activity was about 75%.

Example7

200 g of marigold flower powder [E (1%, 1 cm, chloroform) (454 τημ) = 18.6; Alkali consumption value = 230] were heated with 100 ml of denatured ethyl alcohol containing 50 g of sodium hydroxide and 35 ml of water in a reflux condenser with stirring. The heating time was IV2 hours. The reaction mixture was then cooled to room temperature and neutralized to a pH of 8.0 by adding a 50% strength aqueous solution of phosphoric acid. The residue was then filtered and washed with 500 ml of denatured ethyl alcohol and added to the filtrate. Then 30.8 g of hydrated lime and 0.4 g of "ethoxyquine" were added and the alcohol was removed by distillation. The oily phase obtained was then mixed with an aqueous solution of starch (116 g of a modified starch and 240 ml of water). The emulsion obtained was then dried by spray drying.

The obtained fine-grain solid product had a light absorption value of E (1%, 1 cm, chloroform) (454 πΐμ) = 11.7. The poultry thigh pigmentation activity was 95%. After storage for 75 days at room temperature (20 to 25 ° C.), the product obtained was still 92% pure Activity.

Example 8

The procedure described in Example 7 was repeated. The oily phase, however, was with a Emulsified starch product from feed purity. (A starch product was used that was obtained by pyroconversion made from starch pretreated with diastase with a small amount of an acid as a buffer and a viscosity of 15 to 50 cP [measured with a Brookfield viscometer at 22 ° C and a solids content of 20%].) One such modified starch product is commercially available available. The resulting emulsion was then drum dried, followed by the dried Product has been ground.

The obtained fine granulated product had a light absorption value of E (1%, 1 cm, chloroform) (454 ηΐμ) = 24.8. The poultry thigh pigmentation activity was 99%. The product obtained had after storage for 60 days at room temperature (20 to 25 ° C) still has an activity of 98.4%.

Example 9

The procedure described in Example 8 was repeated, but the starch oil product through

209 681/144

Spray drying was used instead of drum drying.

The obtained fine-grained solid product had a light absorption value of E (1 ⁰ Io, 1 cm, chloroform) (454 τημ) of 27.8. The poultry thigh pigmentation activity was 81 ^° Io. After storage for 60 days at room temperature (20 to 25 ° C.), the product still had an activity of 95.6%.

Example 10

100 g of marigold flower powder [E (1%>, 1 cm, chloroform) (454 ταμ) = 20.4; Alkali consumption value = 230] were refluxed with stirring for IV2 hours together with 500 ml of denatured ethanol containing 31 g of sodium hydroxide and 31 ml of water. The mixture was then neutralized to pH 8.0 with a 50% aqueous solution of phosphoric acid. Then 0.3 g of "ethoxyquine" were added. Then 500 ml of denatured ethanol was added and the mixture was filtered. Finally, 5 g of wheat oil and 12 g of fine-grain swollen hydrate biotite were added, whereupon the solvent was distilled off with stirring and heating.

The obtained fine-grained product had a light absorption value of E (1%, 1 cm, chloroform) (454 τημ) = 25.6. The poultry thigh pigmentation activity was about 75 ⁰ Io. After storage for 60 days at 20 to 25 ° C., the product still showed an activity of 98.2%.

Example 11

12.2 kg of marigold flower powder [E (1 ⁰ Io, 1 cm, chloroform) (454 ΐημ) = 20.4; Alkali consumption value = 230] were extracted with 215 Γ hexane at a temperature of 20 to 25 ° C while stirring for 6 hours. The mixture was then filtered and the filtered cake was washed with 90 liters of hexane. The hexane was then removed from the filtrate by distillation. An oily extract weighing 1.18 kg remained. The oil had a light absorption value of E (1%>, 1 cm, chloroform) (454 ηΐμ) = 210. The extinction value of the oily extract was 99.5%. The alkali consumption value of the extract was 90,

25 g of the degassed oil [E (1 ⁰ Io, 1 cm, chloroform) (454 ταμ) = 254; Alkali consumption value = 85] were treated under reflux with stirring for 2 hours with 100 ml of denatured ethyl alcohol containing 10 g of sodium hydroxide and 10 ml of water. The mixture was then neutralized to a pH of 8.0 by adding a 50% strength aqueous solution of phosphoric acid. The alcohol was then removed by heating in vacuo. Then 1.0 g of "ethoxyquine" and 12 parts by weight of wheat oil were added to the oil and the mixture was ball milled until the xanthophyll crystals were substantially below 2.0 microns in size.

The product obtained consisted of an oily suspension of solid xanthophyll particles and had a light absorption value of E (1 ⁰ Io, 1 cm, chloroform) (454 νημ) = 15.0. The poultry thigh pigmentation activity was 105 ⁰ Io. After storage for 21 days at room temperature, the product obtained still had 100% activity.

Example 1-2 '. .

1 part by weight of the oily suspension; -geniäß, Example 11 became 1.5 parts by weight '; fine-grain swollen hydrate biotite added, whereupon it would be thoroughly mixed under; heating and stirring> ^ .._ .. _:

The obtained fine-grained solid product had a light absorption value of E (1 ⁰ Io, 1 cm, chloroform) (454 ταμ) = 6.8. The poultry thigh pigmentation activity was 66.0%.

Example 13

300 g of the oily extract from Example 11 and 900 ml of denatured ethanol containing 90.7 g of sodium hydroxide and 40 ml of water were refluxed for IV2 hours. 1.01 of water and 8.4 g of "ethoxyquine" were added to the resulting reaction mixture, which was then extracted with chloroform until all of the xanthophyll had been separated off. The chloroform solution containing the extracted xanthophyll was then washed thoroughly with water, after which the chloroform was separated by distillation. A crystalline material remained which consisted essentially of xanthophyll. The crystalline material had a light absorption value of E '(1 ⁰ Io, 1 cm, chloroform) (454 τημ) = 334.

15 g of the crystalline material and 75 g "Polysorbate 80" (97% mixture of esters of oleic acids with sorbitol and their mono- and dianhydride with an acid number <7.5 and a water content <0.2 ⁰ Io, condensed with about 20 moles of ethylene oxide per mole of sorbitol) were ground together in a ball mill until the particle size of the xanthophyll crystals was essentially less than 2.0 microns. 21 g of the mixture ground in the ball mill were then mixed with 30 g of finely divided swollen hydrate biotite, whereupon the mixture was heated on a steam bath with stirring until the oily phase had been completely absorbed by the swollen hydrate biotite. The product obtained had a light absorption value of E (1 ⁰ Io, 1 cm, chloroform) (454 τημ) '= 20.1. The poultry thigh pigmentation activity of this product was 87%.

Were 69 g of the mixture of Example 13 treated in the ball mill at 75 ° C. with an aqueous Solution of 105 g of the modified starch product described in Example 10 and 210 ml When water was mixed and the emulsion obtained was dried by spray drying, it became a fine-grained emulsion solid product obtained.

This product had a light absorption value of E ^(0: 1 Io 1 cm, chloroform) (454 τημ) = 11.6 and a Geflügelschenkelpigmentierungsaktivität of 81%. ■ ■

Claims (5)

1 2 that such a material does not have sufficiently high claims: pigmentation activity. It was found that the pigmentation 1. A process for the extraction of xanthophyll activity of the xanthophylls and Xanthophyllprodukte _s or Xanthophyllprodukten from Marigoldblüten- 5 strongly on their origin and the process for their powder, characterized in that depend on insulation. In particular, it was found one that the pigmentation activity of xanthophylls a) a maximum from the Marigoldblütenpulver, one ^{of the} Marigoldblüten is significantly less than the aqueous solution eiies AlkalLetallhydro- Pigmenüerungsaktiyitat of Xanthoxyds having a content of alkali metal ¹⁰ pills. It was also found that xanthophyll hydroxide, which at least corresponds to the alkali consumption of the xanthophylls or xanthophyll product, in particular the xanthophylls of chard flowers, to the flower powder, have a considerable alkali consumption value, and a short-chain alcohol with one existing during xanthophylls Maximum pigment mixture for about 1 minute to about 24 hours of disruptive activity only rarely or none at all when treated at the reflux temperature and exhibiting alkali consumption value b) the reaction mixture obtained in this way with the expression "alkali consumption water diluted worth" used in der ^{me, f represents the number of milligrams of potash} c) thereof with a with the reaction mixture hydroxide is need ^ao the yernicht by chemical reaction of immiscible non-polar solvent, when 1 g of the material under investigation for xanthophyll the xanthophyll or ^m | extracted · Kahumhydroxyd ui 95% ethanol mixed Xanthophyllprodukt and ^and _ \ Is heated to boiling temperature for an hour, d) the solution obtained is separated off and the amount of potassium hydroxide in g ^ / oigem Solvent evaporates. Ethanol is determined so that with back titration with . as 0.5 η hydrochloric acid and phenolphthalein as 2. The method according to claim 1, characterized in the volume of acid 45 consumed indicates that the alkali metal hydroxide is up to 55% of the volume of the acid required for Potassium hydroxide used. Titration of the amount of potassium hydroxide in 95% 3. The method according to claims 1 and 2, ethanol in the absence of the examined material characterized in that it is consumed as short-30. chain alcohol used ethanol. From the German patent specification 846 882 is already 4. The method according to claims 1 to 3, a method for isolating vegetable dyes, characterized in that one as not - in particular of xanthophyll from fresh or polar solvent ether, isopropyl ether or blanched vegetable raw material known, Used chloroform. 35 in which the plant material with calcium oxide, gypsum, 5. Process according to claims 1 to 4, sodium sulfate, aluminum oxide, silica gel or characterized in that the heating period mixed calcium carbide and then from the in the first stage is 3 hours. so pre-treated plant material the desired Dye is extracted in a fractionated manner. In this 40 patent the teaching is given that calcined Soda is a suitable means to the plant material for a fractional extraction of the coloring matter prepare. However, it has been shown that Xanthophylls are yellow-coloring plant substances which the xanthophyll, which can be produced by this process, essentially from one or more oxidized substances, has only a low pigmentation activity.
Carotenoid compounds exist. Under Xantho- Aus »Ullmanns Encyklopädie der Technische Therefore, in the following, phylles are not just pure chemical compounds ", Vol. 7, p. 103 (1956), and" Beilstein's hand bindings, but also mixtures of one or the book of organic chemistry «, 4th edition, vol. 30 understand multiple connections. (1938), pages 94 and 95, are also already Known by the feeding of xanthophylls or extraction processes. In it, however, is single-xanthophylls containing feedstuffs to poultry borrowed quite generally indicated that a xanthophylllassen Animals with particularly yellow skin, containing yellow acetone extract from plant meal, deal with Obtain fat and eggs with deep yellow yolks. Ge caustic soda is treated and that this takes off with yellow skin is due to the appealing keeping product for the poultry farming as well as for the Color particularly desirable. Eggs with dark yolk 55 can be used to enhance the egg yolk color however, they are particularly fond of making can. According to this known method, a Egg noodles, egg biscuits and the like are used. Xanthophyll ester by saponification of an extract Those often used today, especially calorie- obtained from leaves. To achieve a sufficient Food is very poor in xanthophylls. In order to have sufficient pigmentation activity after this However, enough xanthophylls are available to the poultry. So far, poultry feed has also been required to feed because of the xanthophyll content already added substances that have a high xanthophyll - the leaves are extremely low. The result is there exhibit. From the French patent specification of is that this known method is very by-1 305 716, for example, it is already known to be understandable and time consuming and to xanthophyll Wingfed dried, ground petals of 65 leads, which has only a low pigmentation activity add yellow flowers of marigold plants. A 'has. such material is hereinafter referred to as "Marigold". It has now been found that, if adhered to flower powder «. It has been shown, however, very specific procedural measures from the