DE3642247A1 - MONO-, DI- AND TRI-ESTERS OF 1,8-DIHYDROXY-10-PHENYL-9-ANTHRONE OR 9-ANTHRANOL, METHODS FOR THE PRODUCTION THEREOF AND THEIR USE IN HUMAN OR VETERINE MEDICINE AND AS A COSMETIC - Google Patents

Description

The present invention relates to mono-, di- and tri-esters of 1,8- Dihydroxy 10-phenyl-9-anthrone or 9-anthranol, production process this ester and its use in human or veterinary medicine and as a cosmetic.

These esters are used in particular in human or veterinary medicine as an anti-proliferation agent, especially in the treatment of Psoriasis and the wart lichen or as an anti-inflammatory agent in the treatment of rheumatism, dermatoses and eczema or as Anti acne remedy.

In cosmetics, these esters are anti-dandruff, seborrhea, against hair loss and they can also affect the skin with a tendency to Acne can be used:

The mono-, di- and tri-esters of 1,8-dihydroxy-10-phenyl-9-anthrone or 9-anthranol according to the invention have the advantage that they are more stable compared to 1,8-dihydroxy-10-phenyl-anthrone and stain both the skin and the clothes less, especially as a basic detergent. The mono-, di- and tri-esters of 1,8-dihydroxy-10-phenyl-9-anthrone or 9-anthranol correspond to the following general formula: in the:
p is 0 or 1,
(a) if p = 0, t = 1 and R _{2 represents} a hydrogen atom or a radical -COR ₃ ,
(b) if p = 1, t = 0 and R ₁ and R ₂ independently of one another represent a hydrogen atom or a radical -COR ₃ ,
R _{3 represents} a branched or linear alkyl radical having 1 to 17 carbon atoms, a cycloalkyl radical, a phenyl radical optionally substituted by a lower alkyl radical, a lower alkoxy radical, a halogen atom, a nitro function, a -CF ₃ radical or a hydroxyl function,
and the mixtures of these esters.

Under a linear or branched alkyl radical with 1 to 17 carbon atoms is a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, heptyl, nonyl, undecyl, pentadecyl and to understand heptadecyl residue.

Under a cycloalkyl radical is a radical with 3 to 6 carbon atoms, preferably to understand a cyclopentyl or a cyclohexyl radical.

When the phenyl group is substituted by a lower alkyl group the latter preferably a methyl, ethyl or tert-butyl radical.

If the phenyl radical is substituted by a lower alkoxy radical, this is preferably a methoxy or an ethoxy radical.

If the phenyl radical is substituted by a halogen atom, this is preferably a chlorine or a fluorine atom.

According to a preferred embodiment of the invention, the compounds according to the invention are the di- or tri-esters which are represented by the following formulas:

Among the esters of the formula I according to the invention, the following can in particular be mentioned:
10-phenyl-1,8,9-triacetoxy-anthracene
10-phenyl-1,8,9-tripropionyloxy-anthracene
10-phenyl-1,8,9-tributyryloxy-anthracene
10-phenyl-1,8,9-triisobutyryloxy-anthracene
10-phenyl-1,8-diisobutyryloxy-9-anthrone
10-phenyl-1,8,9-tricyclohexylcarbonyloxy-anthracene
10-phenyl-1,8-dipivaloyloxy-9-anthrone
10-phenyl-1,8,9-tribenzoyloxy-anthracene
10-phenyl-1,8,9-tricyclopentylcarbonyloxy-anthracene
10-phenyl-1,8,9-trioctanoyloxy-anthracene
10-phenyl-1,8,9-triundecanoyloxy-anthracene
10-phenyl-1,8,9-trioctadecanoyloxy-anthracene
10-phenyl-1,8,9-tritolylcarbonyloxy-anthracene
10-phenyl-1,8,9-tri (p-methoxybenzoyloxy) anthracene
10-phenyl-1,8,9-trim (trifluoromethyl) benzoyloxyanthracene

Another object of the present invention is to provide a method for Preparation of the esters of 1,8-dihydroxy-10-phenyl-9-anthrone or 9-anthranols as defined above.

The compound 1,8-dihydroxy-10-phenyl-9-anthrone is a known compound their production in Arch. der Pharmazie, 298, 273-81 (1965) in which three possible positions for O-acylation are shown are according to the reaction conditions and the nature of the reagent allow access to the mono-, di- or tri-esters.  

These esters can be obtained in the form of a mixture which can be obtained by Chromatography can separate.

The esters according to the invention are obtained by reacting 1,8-dihydroxy-10-phenyl-9-anthrone with an activated acid, such as. B. an acid anhydride, (R ₃ CO) ₂ O, or an acid chloride, R ₃ COCl, in the presence of a base and preferably an aromatic amine, such as. B. pyridine, optionally in an aromatic solvent medium, such as in toluene and at a temperature between 20 and 130 ° C.

The formation of the mono-, di- or tri-esters is a function of the molar Proportions of acid anhydride or acid chloride used was and the response time.

For the preparation of the mono- and di-esters, 1.5 to is preferably used 2.5 equivalents of acid chloride or acid anhydride and followed the reaction by thin layer chromatography to either im them End stage of mono-ester or stage of di-ester.

A large excess of is used to prepare the tri-esters Acid chloride or acid anhydride to complete the reaction and the temperature is preferably increased to 80 to 110 ° C. If you have one Acid chloride used, especially a voluminous, such as. B. pivaloyl chloride, it is particularly easy to present the same di-esters in the present to get an excess of it without getting an essential one Formation of the corresponding tri-ester observed.

Insofar as one uses an acid chloride, either by evaporation or can be easily removed by mixing in a basic environment, it is desirable the reaction using the acid chloride all at once perform both as a solvent and as a reagent and one gives 4 to 8 equivalents of pyridine.  

In this case, the reaction is carried out at a temperature between 20 and 60 ° C through and the reaction is particularly fast.

After completion of the reaction, if you put this in a solvent has carried out, the reaction mixture is poured into water and led various washes, especially using sodium bicarbonate solutions by. The organic phase is then dried over magnesium sulfate and then filters. The product can either be recrystallized or clean by silica gel chromatography and use then preferably toluene or a mixture of toluene / ethyl acetate as Eluent.

The present invention further relates to the use of the esters Formula (I) in human or veterinary medicine and as a cosmetic.

The compounds according to the invention are in human or veterinary therapy Anti-proliferation agents, especially for the treatment of psoriasis and the wart lichen and they are also called anti-inflammatory Agents especially for the treatment of rheumatism, dermatoses and of eczema, but also used to treat acne.

The compounds according to the invention can be used as a cosmetic for treatment the skin with a tendency to acne, dandruff, seborrhea and against hair loss can be used. The cosmetic or pharmaceutical Preparations can be made, for example, by bringing together a Esters of formula (I) in a concentration between 0.01 and 5% various inert, non-toxic, solid liquid carriers, which are usually in the preparations for use in cosmetics or therapy can be used.

The pharmaceutical preparations can be enteral, parenteral or to be administered topically. For enteral administration the preparations are in the form of tablets, powder, granules, capsules, Pills, syrups, suspensions or solutions. The choice depends, of course depending on the administration and the desired activity.  

The pharmaceutical preparations can contain further inert additives. The tablets or granules can, for example, binders, fillers, Contain vehicles or diluents.

The liquid preparations can be in the form of, for example, a sterile, water-miscible solution. In addition to the active ingredient the capsules can contain fillers or thickeners.

The pharmaceutical preparations for oral administration can be found in same way flavor enhancers and substances commonly used, such as. B. preservatives, stabilizers, Antioxidants, regulators and emulsifiers. Salts and buffer substances can also be added. The vehicle and diluents listed below can represent organic or mineral substances, such as. B. gelatin, Lactose, starch, magnesium stearate, talc, gum arbum, vegetable and mineral oils, Fillers, thickeners, colorants, moisturizers or polyalkylene glycols.

When the pharmaceutical preparations are intended for topical application they are in the form of an ointment, a pomade, a gel, a tincture, a cream, a solution, a lotion, a micronized Powder, a spray, a suspension, a shampoo or of a soaked tampon. The ointments or pomades are preferred and they are obtained by mixing an ester according to the invention with non- toxic inert carriers suitable for topical treatment are manufactured.

The invention is illustrated below using several examples for the preparation of the esters according to the invention and on the basis of several examples of preparations explained in more detail about the use of therapy and cosmetics, without being limited to these examples.  

1,8-dihydroxy-10-phenyl-9-anthrone a) Preparation of 10-phenyl-1,8,10-trihydroxy-9-anthrone

In a 2 liter reaction vessel, which is equipped with a mechanical stirrer, an argon feed, a cooling device and a feed device equipped, 30 g of 1,8-dihydroxyanthraquinone are added and 2 liters of anhydrous tetrahydrofuran. Then you cool the Solution to -70 ° C.

The anthraquinone crystallizes at this temperature. Subsequently a solution, the 4 equivalents, is added with stirring for 30 minutes Contains phenyllithium, too.

The temperature is maintained between -60 ° C and -70 ° C during the entire period of addition. When the addition is complete, a sample is used to check whether the total amount of the 1,8-dihydroxyanthraquinone has been transferred. At this temperature, the reaction mixture is acidified by adding 400 cm ^{3 of} acetic acid, and then the mixture is allowed to cool to room temperature.

The solvent is evaporated to dryness under reduced pressure. The product obtained, which is in the form of an oily mass, is crystallized out by stirring in water. The crystals obtained are separated off, washed in dichloromethane and then dried. 32 g of yellow crystals are obtained, which are recrystallized from methanol. The product has a melting point of 260 ° C.

b) Preparation of 1,8-dihydroxy-10-phenyl-9-anthrone

In a 2 liter reaction vessel equipped with a mechanical Stirrer and an argon supply line bring 50 g of 10-phenyl-1,8,10-trihydroxy 9-anthrone, then 200 g of finely ground tin chloride and 2 liters of acetic acid.

Into this mixture, which is stirred at room temperature, 200 cm ^{3 of} concentrated HCl are then added dropwise over 30 minutes. The disappearance of 10-phenyl-1,8,10-trihydroxy-9-anthrone is followed by thin layer chromatography. The reduction reaction is complete after about 2 hours. The 1,8-dihydroxy-10-phenyl-9-anthrone precipitated in the mixture is separated off, washed with water and dried. 42 g of light yellow crystals are then obtained. The filtrate is poured into a mixture of 1 liter of water and 1 kg of crushed ice. The remaining precipitated product is separated, washed in water and dried. An additional 4 g of the desired product is then isolated.

The 1,8-dihydroxy-10-phenyl-9-anthrone obtained is pure.

It has a melting point of 193 to 194 ° C.

The structure of the 1,8-dihydroxy-10-phenyl-9-anthrone is shown by  Mass spectrography confirmed, with the starting peak on the spectrum at 3 m / e: 302 by direct ionization and at m / e: 303 by chemical Ionization in isobutane corresponding to M + H⁺ observed. These Results are in line with the molecular weight of 302 of the product match.

The NMR spectrum confirms this structure in the same way.  

A singlet is particularly observed at 5.30 p. p .m., whose integration corresponds to a proton. It is the proton that is positioned on the carbon atom in position 10 of the anthrone nucleus. The signal of the 11 aromatic protons is a multiplet whose δ is from 6.60 to 7.50 ppm (11).

The spectrum also shows another singlet at 12.40 p. p. m. that disappears through exchange in heavy water and its integration the two protons of the hydroxyl groups in positions 1 and 8 corresponds.

EXAMPLE I Preparation of 10-phenyl-1,8,9-triacetoxy-anthracene

A mixture of 40 g of 1,8-dihydroxy-10-phenylanthrone and 0.5 cm ^{3 of} pyridine in 400 cm ^{3 of} acetic anhydride is stirred under an inert atmosphere and the temperature is gradually increased to between 60 and 70 ° C. The starting product was converted quantitatively into the corresponding triacetate after 3 hours. After cooling with an ice bath, the product crystallizes. This is separated off, washed in ethyl ether and then dried. 45 g of a solid with a green-yellowish color are obtained, which is dissolved in a mixture of 200 cm ^{3 of} acetic acid and 200 cm ^{3 of} 1,2-dichloroethane, which has been brought to a temperature of 80 ° C. The solution is then filtered at this temperature and the product is crystallized by cooling the filtrate. This is separated off, washed in ethyl ether and dried.

35 g of 10-phenyl-1,8,9-triacetoxy-anthracene are obtained in the form of light yellow crystals with a melting point of 279 ° C.

EXAMPLE II Preparation of 10-phenyl-1,8,9-tripropionyloxy-anthracene

0.100 cm ^{3 of} anhydrous pyridine is added to a mixture of 2.5 g of 1,8-dihydroxy-10-phenylanthrone in 25 cm ^{3 of} propionic anhydride, which is stirred under an argon atmosphere. The mixture is then brought to a temperature of 70 ° C. over an hour, at the end of which the entire starting product is transferred. The excess reagent is then removed by evaporation under reduced pressure. The solid obtained is dissolved in the minimum amount of toluene required, applied to a silica gel and then eluted with toluene. After evaporation of the eluent, 1.3 g of a solid are obtained, which is recrystallized in a mixture of toluene / hexane. Then 1.1 g of white crystals with a melting point of 216 ° C. are isolated.

EXAMPLE III Preparation of 10-phenyl-1,8,9-triisobutyryloxy-anthracene

A mixture, stirred under an inert atmosphere, from 3 g of 1,8-dihydroxy-10-phenylanthrone, 3.16 g of pyridine (4 equivalents) and 4.26 cm ^{3 of} isobutyryl chloride (4 equivalents) in 100 cm ^{3 of} anhydrous toluene brought to reflux of the solvent over 10 hours. The reaction mixture is then washed several times with water. The organic phase is decanted off, dried over magnesium sulfate and concentrated. The product obtained in the form of a viscous liquid is dissolved in a minimal amount of toluene and applied to a column of silica gel. The expected triester is eluted with a mixture of toluene-methylene chloride (3/1).

After concentration of the solvent, 2.3 g of the solid is obtained, which is recrystallized from toluene. 1.4 g of 10-phenyl-1,8,9-triisobutyryloxy-anthracene are isolated in the form of yellow crystals with a melting point of 224 ° C.

EXAMPLE IV Preparation of 10-phenyl-1,8,9-tri (cyclohexylcarbonyloxy) anthracene

15 cm ^{2 of} cyclohexanecarboxylic acid chloride are slowly added to a mixture of 3 g of 1,8-dihydroxy-10-phenylanthrone with 3.2 cm ^{3 of} pyridine with stirring. The reaction mixture is then brought to a temperature of 100 ° C. over 3 hours. It is then diluted at room temperature with the addition of 200 cm ^{3 of} methylene chloride, then washed in bicarbonate saturated water and then with water. The organic phase is dried over sodium sulfate. After evaporation of the methylene chloride, 4.2 g of yellow solid are obtained, which is recrystallized in a mixture of toluene / ethyl ether. After filtration and drying, 3.75 g of 10-phenyl-1,8,9-tri- (cyclohexylcarbonyloxy) -anthracene are obtained in the form of yellow crystals with a melting point of 235 ° C.

EXAMPLE V Preparation of 1,8-dipivaloyloxy-10-phenyl-anthrone

A mixture of 3 g of 1,8-dihydroxy-10-phenylanthrone, 3.16 cm ^{3 of} pyridine, 4.8 cm ^{3 of} pivyloyl chloride in 100 cm ^{3 of} anhydrous toluene is stirred under an argon atmosphere for 10 hours at the boiling point of the solvent. After cooling to room temperature, the reaction mixture is washed several times in water. The organic phase is decanted off, dried over magnesium sulfate and concentrated. The residue is applied to a silica gel column and then eluted with toluene. After concentration of the elution phase, 2.38 g of a solid is obtained, which is recrystallized in a mixture of toluene / hexane. Then 1.4 g of 1,8-dipivaloyloxy-10-phenyl-anthrone are isolated in the form of white crystals with a melting point of 160 ° C.

EXAMPLE VI Preparation of 10-phenyl-1,8,9-tribenzoyloxy-anthracene

1.2 cm ^{3 of} pyridine are added dropwise to a mixture of 1 g of 1,8-dihydroxy-10-phenyl-9-anthrone in 15 cm ^{3 of} benzoyl chloride, which is stirred at room temperature and under an inert atmosphere.

After stirring for one hour, the entire starting anthrone is transferred to the corresponding triester. The reaction mixture is concentrated under reduced pressure, dissolved in 100 cm ^{3 of} methylene chloride, washed several times in water and finally dried over magnesium sulfate.

The organic phase is then applied to a silica gel column and with a mixture of toluene / methylene chloride with increasing Methylene chloride concentration eluted.

After concentration of the elution phase, 1.55 g of the expected is obtained Tri-esters, which are recrystallized from toluene. The crystals are separated and dried.

1 g of 10-phenyl-1,8,9-tribenzoyloxy-anthracene is isolated in the form of yellow crystals with a melting point of 255 ° C.

EXAMPLE VII Preparation of 1,8-diisobutyryloxy-10-phenyl-anthrone

A mixture of 18 g of 1,8-dihydroxy-10-phenylanthrone, 19 cm ^{3 of} pyridine and 25 cm ^{3 of} isobutyryl chloride in 500 cm ^{3 of} anhydrous toluene is stirred under protection from light and under an inert atmosphere and brought to reflux of the solvent for 5 hours .

After cooling, the reaction mixture is washed three times in water and dries over magnesium sulfate.

The residue obtained is evaporated under reduced pressure applied a silica gel column. The column is eluted with toluene, then with a mixture of toluene / methylene chloride, increasing Methylene chloride concentration used. At the beginning of the chromatography phase 5 g of 10-phenyl-1,8,9- are isolated after evaporation of the solvent triisobutyryloxy anthracene, described in Example III.  

The later fractions, which are rich in di-esters, are concentrated and the product obtained is recrystallized from a mixture of toluene / pentane.

1.5 g of 1,8-diisobutyryloxy-10-phenylanthrone are obtained in the form of beige crystals with a melting point of 136 ° C.

EXAMPLE VIII Preparation of 10-phenyl-1,8,9-tributyryloxy-anthracene

19 cm ^{3 of} pyridine and 24.5 cm ^{3 of} butyryl chloride are added to a solution of 18 g of 1,8-dihydroxy-10-phenylanthrone in 500 cm ^{3 of} anhydrous toluene, which is stirred under the exclusion of light and an inert atmosphere. The mixture is then held under reflux of the toluene for 3 hours, at the end of which time all of the starting product has reacted.

After cooling, the mixture is washed three times in water and the toluene phase is dried over sodium sulfate. After concentration you wear it Residue on a silica gel column. The expected product is eluted with a mixture of hexane / toluene.

After concentration of the eluent, 23 g of product are obtained, which are recrystallized in a mixture of toluene / pentane, which gives 16 g of 10-phenyl-1,8,9-tributyryloxy-anthracene in the form of light yellow crystals with a melting point of 150 ° C receives.

Examples of pharmaceutical and cosmetic preparations EXAMPLE 1 Insoluble 0.5 g tablet

10-phenyl-1,8,9-triacetoxy-anthracene 0.100 g Lactose 0.082 g Stearic acid 0.003 g Purified talc 0.015 g Rice starch QSP 0.500 g

This tablet is pressed directly to dryness the mixture of different ingredients.

EXAMPLE 2 0.8 g insoluble tablet

10-phenyl-1,8,9-triisobutyryloxy-anthracene 0.200 g Lactose 0.200 g Gum arabic, 20% in water 0.080 g Liquid paraffin 0.004 g Purified talc 0.016 g Rice starch 0.800 g

This tablet is in the form of granules over the moist Processing the mixture of 10-phenyl-1,8,9-triisobutyryloxy anthracene, starch, lactose and gum arabic, in 20% water.

You then dry and then sieve the granules. The Granules are then mixed with the paraffin and talc.  

EXAMPLE 3 Granules in 3 g sachets

10-phenyl-1,8,9-tripropionyloxy-anthracene 0.150 g Sucrose 2.220 g Methyl cellulose 0.030 g Purified water 0.600 g

The paste obtained by mixing the four ingredients is wet granulated and then dried.

EXAMPLE 4 capsules containing 0.05 g of the active ingredient

10-phenyl-1,8,9-tri- (cyclohexylcarbonyloxy) - anthracene 0.050 g Cod liver oil QSP 0.500 g

The encapsulation of the capsule is molded until it dries a suitable mixture consisting of gelatin, glycerin, Water and preservatives. The suspension containing the active ingredient is in inserted the capsule, which is then closed.

EXAMPLE 5 capsules containing 0.3 g powder

Powder composition:
1,8-Dipivaloyloxy-10-phenyl-anthrone 0.080 g corn starch 0.060 g lactose QSP 0.300 g

The powder is conditioned into a capsule that is made up of Gelatin, titanium dioxide and a preservative.  

EXAMPLE 6 Hydrophobic ointment

1,8-dipivaloyloxy-10-phenyl-anthrone 1.00 g Vaseline 49.00 g Ceresin wax 15.00 g Salicylic acid 0.30 g Vaseline oil 34.70 g

EXAMPLE 7 Nonionic emulsion for topical application

10-phenyl-1,8,9-triacetoxy-anthracene 0.70 g Eucerin, anhydrous 70.00 g petroleum jelly oil 10.00 g preservative QS
Butylated hydroxytoluene QS
Water, demineralized, sterile, QSP100.00 g

For adequate preservation, the emulsion should stored away from light and heat.

EXAMPLE 8 Anhydrous Gel

1,8-dipivaloyloxy-10-phenyl-anthrone 1.50 g "Aerosil 200" ® (silica gel) from DEGUSSA 7.00 g Isopropyl myristate, QSP100.00 g

EXAMPLE 9 Milk in two parts for emulsion if desired

First part:
10-phenyl-1,8,9-tripropionyloxy-anthracene 2.00 g "MIGLYOL 812" ® (triglycerides of capric / caprylic acid) from DYNAMIT NOBEL, QSP 20.00 g second part
"Tween 80" ® (polyoxyethylene sorbitan monooleate, polyoxethylated with 20 moles of ethylene oxide)
from the company ATLAS 10.00 g preservative, QS
Demineralized water, sterile, QSP 80.00 g

The first part is in suspension around the active ingredient to bring stirred, then both parts before Applying the milk mixed.

EXAMPLE 10 Stick

10-phenyl-1,8,9-triisobutyryloxy-anthracene 5.00 g Cocoa butter 12.50 g Ozokerite wax 18.50 g White refined paraffin 6.25 g Vaseline oil 12.75 g Isopropyl myristate, QSP100.00 g

EXAMPLE 11 Hair Loss and Dandruff Preparation

1,8-dipivaloyloxy-10-phenyl-anthrone 0.50 g Tin chloride 0.30 g Isopropyl myristate, QSP100.00 g

EXAMPLE 12 Ointment

1,8-diiobutyryloxy-10-phenylanthrone 1.00 g "MIGLYOL 812" ® (triglycerides of capric / caprylic acid) from DYNAMIT NOBEL 49.25 g White Vaseline 49.25 g Salicylic acid 0.50 g

Claims (13)

1. mono-, di- and tri-esters of 10-phenyl-1,8-dihydroxy-9-anthrone or 9-anthranol, characterized in that they correspond to the following formula: in the
p is 0 or 1, and
(a) when p is 0, t = 1 and R _{2 represents} a hydrogen atom or a radical -COR ₃ ,
(b) when p is 1, t = 0 and R ₁ and R ₂ independently represent a hydrogen atom or -COR ₃ ,
R _{3 is} a linear or branched alkyl radical having 1 to 17 carbon atoms, a cycloalkyl radical, a phenyl radical which is optionally substituted by a lower alkyl radical, a lower alkoxy radical, a halogen atom, a nitro function, a -CF ₃ radical or a hydroxyl function,
and mixtures of these esters. 2. Compounds according to claim 1, characterized in that the alkyl radical with 1 to 17 carbon atoms is a methyl, Ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, Pentyl, isopentyl, heptyl, nonyl, undecyl, pentadecyl or Is heptadecyl residue.   3. Compounds according to claim 1, characterized in that the cycloalkyl radical is a cyclopentyl or a cyclohexyl Rest is. 4. Compounds according to claim 1, characterized in that the phenyl radical at least by a methyl, ethyl, tert-butyl, methoxy, ethoxy radical, a fluorine atom or a chlorine atom, a nitrofunction, a -CF ₃ radical or one Hydroxyl function is substituted. 5. Compounds according to any one of claims 1 to 4, characterized in that the esters have the following formula: wherein R _{3 has} the meaning given in claim 1. 6. Compounds according to any one of claims 1 to 4, characterized in that they are tri-esters of the following formula: wherein R _{3 has} the meaning given in claim 1. 7. Compounds according to one of claims 1 to 6, characterized in that they are selected from the following group:
10-phenyl-1,8,9-triacetoxy-anthracene
10-phenyl-1,8,9-tripropionyloxyanthracene
10-phenyl-1,8,9-tributyryloxy-anthracene
10-phenyl-1,8,9-triisobutyryloxy-anthracene
10-phenyl-1,8,9-diisobutyryloxy-9-anthrone
10-phenyl-1,8,9-tricyclohexylcarbonyloxy-anthracene
10-phenyl-1,8-dipivaloyloxy-9-anthrone
10-phenyl-1,8,9-tribenzoyloxy-anthracene
10-phenyl-1,8,9-tricyclopentylcarbonyloxy-anthracene
10-phenyl-1,8,9-trioctanoyloxy-anthracene
10-phenyl-1,8,9-triundecanoyloxy-anthracene
10-phenyl-1,8,9-trioctadecanoyloxy-anthracene
10-phenyl-1,8,9-tritolylcarbonyloxy-anthracene
10-phenyl-1,8,9-tri (p-methoxybenzoyloxy) anthracene
10-phenyl-1,8,9-tri [m- (trifluoromethyl) benzoyloxy] anthracene 8. A process for the preparation of the mono-, di- and tri-esters according to one of claims 1 to 7, characterized in that 1,8-dihydroxy-10-phenyl-9-anthrone with an activated acid in or with no solvent Form of the acid anhydride, (R ₃ CO) ₂ O, or an acid chloride, R ₃ COCl, where R _{3 has} the meaning given in claim 1, in the presence of a base, for. B. pyridine, and at a temperature between 20 and 130 ° C. 9. The method according to claim 8, characterized in that one carries out the reaction in toluene. 10. Pharmaceutical or cosmetic preparation, characterized in that that they are an active ingredient in one suitable carrier material at least one compound according to one of the Claims 1 to 7 or a compound obtained according to one of the claims 8 and 9.   11. Preparation according to claim 10, characterized in that that they have the active ingredient in a concentration between 0.01 and 5 wt .-% based on the total weight of the Preparation contains. 12. Use of a compound according to any one of claims 1 to 7 for the manufacture a therapeutic preparation for treatment psoriasis, wart lichen, rheumatism, dermatoses, is determined by eczema and acne. 13. Use of a compound according to any one of claims 1 to 7 for the manufacture a cosmetic preparation for the treatment of the for Acne-prone skin, dandruff, seborrhea and hair loss is determined.