FR2591222A1 - 1,8-DIHYDROXY-1,8-PHENYL-10-ANTHRONE-9 OR ANTHRANOL-9 MONO, DI AND TRI-ESTERS, PROCESS FOR THEIR PREPARATION AND THEIR USE IN HUMAN OR VETERINARY MEDICINE AND IN COSMETICS - Google Patents

Abstract

Mono, di and tri-esters of 1,8-dihydroxy-phenyl-10-anthrone-9 or anthranol-9, characterized in that they correspond to the following formula: (CF DRAWING IN BOPI) in which: p is 0 or 1; (a) when p = 0, t = 1 and R2 represents a hydrogen atom or - COR3; (b) when p = 1, t = 0 and R1 and R2 independently of each other represent a hydrogen atom or -COR3; R3 representing an alkyl radical, linear or branched having from 1 to 17 carbon atoms, a cycloalkyl radical, or a phenyl radical optionally substituted by a lower alkyl, a lower alkoxy, a halogen atom, a nitro function, a radical - CF3 or by a hydroxyl function, and mixtures of said esters. Their preparation and application in human or veterinary medicine and in cosmetics.

Description

The present invention relates to mono-, di- and tri-

  esters of 1,8-dihydroxy-10-phenyl-9-anthrone or anthranol-9, the process for the preparation of these esters and their use in human or veterinary medicine and in cosmetics. In human or veterinary therapy, these esters are particularly suitable for use as anti-proliferative agents, especially in the treatment of psoriasis and warts, or as anti-inflammatory agents in the treatment of rheumatism, dermatitis and of

  eczema or as anti-acne agents.

  In cosmetics, these esters are anti-dandruff, antiseborrhoeic and anti-hair loss agents and can be used

  for acne-prone skin.

  The mono, di and tri-esters of 1,8-dihydroxy-10-phenyl-9-anthrone or 9-anthranol according to the invention have, compared with 1,8-dihydroxy-10-phenylanthron, the advantage of being more stable and less stubborn skin

  and clothes especially in basic washing.

  The mono, di and tri-esters of 1,8-dihydroxy-10-phenyl-9-anthrone or 9-anthranol may be represented by the following general formula: R 2 O (R 1) p OCOR 3 (1)

<(I) -

(11) t C6il5

in which: -

  p is 0 or 1 (a) when p = O, t = 1 and R2 represents a hydrogen atom or -COR3, (b) when p = 1, t = 0 and R1 and R2 independently represent one of the another a hydrogen atom or -COR 3, R 3 representing a linear or branched alkyl radical having 1 to 17 carbon atoms, a cycloalkyl radical, or a phenyl radical optionally substituted by a lower alkyl, a lower alkoxy, an atom of halogen, a r.itro function, a -CF3 radical or by a hydroxyl function,

and mixtures of said esters.

  By linear or branched alkyl radical having from 1 to 17 carbon atoms is meant a methyl, ethyl, propyl or isopropyl radical,

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  butyl, isobutyl, tert-butyl, pentyl, isopentyl, heptyl, nonyl,

  undecyl, pentadecyl and heptadecyl.

  By cycloalkyl radical is meant a radical having from 3 to 6

  carbon atoms, but preferably the cyclopentyl or cyclohexyl radical.

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

  lower, this is preferably the methoxy or ethoxy radical.

  When the phenyl radical is substituted by a halogen atom, this

  the latter is preferably a chlorine or fluorine atom.

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

R3COO OCOR3 R3COO OCOR3 (C 3

OCOR3 OCOR3

  C6115 il (III) Among the esters according to the invention of formula (I), mention may be made in particular of: - 10-phenyl-1,8,8-triacetoxy-anthracene, 10-phenyl-1,8-tripropionyloxy, 9 anthracene, - phenyl-triisobutyryloxy-1,8,9 anthracene, 10-phenyl-tricyclohexylcarbonyloxy-1,8,9 anthracene, - dipivaloyloxy-1,8-phenyl-9-anthrone-9-phenyl-10-tribenzoyloxy-1.8 , 9-anthracene, 8,9-phenyl-tricyclopentylcarbonyloxy-anthracene, 10-phenyl-trioctanoyloxy-1,8,9 anthracene, 10-phenyl-triundecanoyloxy-1,8,9 anthracene, 10-phenyl-trioctadecanoyloxy 1, 8, 9 anthracene, 10-phenyltritolylcarbonyloxy-1,8,9 anthracene, 10-phenyltrimethoxybenzoyloxy -1,8,9 anthracene, 10-phenyltrim (trifluoromethyl) The subject of the present invention is also the process for the preparation of esters of 1,8-dihydroxy-10-phenyl-9-anthrone or 9-anthranol.

as defined above.

  1,8-Dihydroxy-1,8-phenyl-9-anthrone is a known compound, the preparation of which has been described in Arch. der Pharmazie, 298, 273-81 (1965), having three possible sites of O-acylation which following the operating conditions and the nature of the reagent allow access to mono di or tri-esters. These esters can however be obtained in the form of a mixture

  that is fractionated by chromatography.

  The esters according to the invention are obtained by reacting, on 1,8-dihydroxy-9-phenyl-9-anthrone, an activated form of acid such as an acid anhydride, (R 3 CO) 20, or a dichloride. acid, R3COC1, in the presence of a base and preferably an aromatic amine such as pyridine, optionally in an aromatic solvent medium such as in toluene and in a

  temperature between 20 and 130 C.

  The formation of mono, di or tri-esters is a function of the molar proportions of the acid anhydride or acid chloride reacted and the

reaction time.

  1.5 to 2.5 equivalents of acid chloride or acid anhydride are preferably used for the preparation of mono and di-esters, and the reaction is followed by thin-layer chromatography in order to stop it. either at

  stage of the mono-ester either at the di-ester stage.

  For the preparation of the tri-esters a large excess of acid chloride or acid anhydride is used and in order to complete the reaction, the

  -temperature is preferably brought to 80-110 C.

  When a particularly congested acid chloride is used, such as, for example, pivaloyl chloride, it is particularly easy to access the di-esters even in the presence of excess without any evidence of

  important formation of the corresponding tri-ester.

  Inasmuch as an easily removable acid chloride is used either by evaporation or by washing in a basic medium, it is desirable to carry out the reaction using the acid chloride at once.

  as a solvent and as a reagent and add 4 to 8 equivalents of pyridine.

  In this case, a temperature of between 20 and

   C and the reaction is particularly fast.

  After the end of the reaction, when the reaction is carried out in a solvent, water is poured into the reaction medium and the reaction mixture is heated.

  different washes including using a solution of sodium bicarbonate.

  The organic phase is then dried over magnesium sulfate and filtered. The 3 -

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  product can be purified either by recrystallization or by chromatography on silica gel using preferably toluene or a mixture of

  toluene / ethyl acetate as eluent.

  The subject of the present invention is also the use of the esters of formula (1) in human or veterinary medicine and in cosmetics. In human or veterinary therapy, the compounds according to the invention are anti-proliferative agents, in particular in the treatment of psoriasis and warts and useful as anti-inflammatory agents, in particular in the treatment of rheumatism,

  dermatoses and eczema, as well as in the treatment of acne.

  In cosmetics, the compounds according to the invention can be used in the treatment of acne-prone skin, dandruff,

  seborrhea and hair loss.

  The cosmetic or pharmaceutical compositions may be prepared for example by adding an ester of formula (I), at a concentration of between 0.01 and 5%, in various non-toxic, solid or liquid inert carriers generally used in compositions for use cosmetic or therapeutic. The pharmaceutical compositions can be administered enterally, parenterally or topically. For enteral administration, the compositions are in the form of tablets, powders,

  granules, capsules, pills, syrups, suspensions or solutions.

  The dosage is of course dependent on the route of administration

and the activity sought.

  The pharmaceutical compositions may further contain inert additives. The tablets or granules may contain, for example,

  binders, fillers, carriers or diluents.

  The liquid compositions may be present for example in the form of a sterile solution miscible with water. In addition to the active compound, the capsules may contain a filler or thickener. Oral pharmaceutical compositions may also contain flavor enhancers and substances commonly used as preservatives, stabilizers, antioxidants, regulators and emulsifiers. We

  can also add salts and buffers.

  The carriers and diluents as enumerated above may consist of organic or inorganic substances, for example by gelatin, lactose, starch, magnesium stearate, talc, gum arabic, oils and the like. plants and minerals, loads,

  thickeners, dyes, humectants or polyalkylene glycols.

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  When the pharmaceutical compositions are intended for topical application, they are in the form of an ointment, an ointment, a gel, a tincture, a cream, a solution, lotion, micronized powder, spray, suspension, shampoo or soaked pads. Ointments or ointments are preferred and are prepared by mixing an ester according to the invention with non-toxic inert carriers

  appropriate for topical treatment.

  Several examples of the preparation of the esters according to the invention as well as several examples of compositions for therapeutic use will now be given by way of illustration and without any limiting nature.

and cosmetic.

  Preparation of 1,8-dihydroxy-10-phenyl-9-anthrone a) Preparation of 10-phenyltrihydroxy-1, 8, 10, 9-anthrone In a 2-liter reactor equipped with mechanical agitation, an inlet of argon, a coolant and an introducer

  g of 1,8-dihydroxyanthraquinone and 2 liters of anhydrous tetrahydrofuran.

  The solution obtained is then cooled to -70 C.

  At this temperature, the anthraquinone is crystallized. A solution containing 4 equivalents is then added with stirring in 30 minutes.

of phenyllithium.

  The temperature is maintained throughout the time of the addition between 60 ° C. and -70 ° C. At the end of the addition, it is checked on a sample taken that all the dihydroxy-1,8-anthraquinone is converted. At this temperature, the reaction medium is acidified by adding 400 cm3 of acetic acid, and then the mixture is allowed to return to ambient temperature. The solvent is evaporated to dryness under reduced pressure. The product obtained, in the form

  of an oily mass, crystallizes by stirring in water.

  The crystals obtained are drained, washed with dichloromethane and then dried. 32 g of yellow crystals are thus obtained which are recrystallized in the

  methanol. The product has a melting point of 216 C.

  Analysis C20H 1404 Caleulated: C: 75.46 H: 4.43 0: 20.10 Found: 75.48 4.35 19. 95 b) Preparation of the 1,8-dihydroxy-1,8-phenyl-9-anthrone In a 2-liter reactor equipped with mechanical stirring and of an argon inlet, 50 g of 10-phenyl-1,8,10-trihydroxy-9-anthrone are introduced,

  then 200g of ground stannous chloride and 2 liters of acetic acid.

  To this mixture, stirred at room temperature, 200 cm3 of concentrated hydrochloric acid are then added dropwise in the course of 30 minutes. The

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  disappearance of phenyl-10 trihydroxy -], 8,10 anthrone-9 is followed by thin layer chromatography. After about two hours, the reduction reaction is complete. The 1,8-dihydroxy-phenyl-10-anthrone-9 precipitated in the medium is drained, washed with water and dried. 42 g of light yellow crystals are thus obtained. The filtrate is poured onto a mixture of 1 liter of water and 1 kg of crushed ice. The rest of the product precipitates, is drained, washed with water and dried. An additional quantity of 4 g of the expected product is thus isolated.

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

  It has a melting point of 193-194 C.

  Analysis C20H1403 Calc .: C: 79.45 H: 4.66 0: 15.87 Found: 79.25 4.71 16.00 The structure of 1,1-dihydroxy-10-phenyl-9-anthrone is confirmed by mass spectrography where the parent peak is observed on the spectrum at m / e: 302 by direct ionization and at m / e: 303 by chemical ionization with isobutane corresponding to M + H +. These results are consistent with the mass

molar of 302g of the product.

  The spectrum of R.M.N also confirms this structure. We observe in particular a singlet at 5.30p.p.m whose integration corresponds to a

  proton. It is the one that is linked to the carbon in position 10 of the anthrone nucleus.

  The signal of the eleven aromatic protons is a multiplet whose i

is 6.60 to 7.50 p.p.m (11).

  Finally, the spectrum shows another singlet at 12.40 p.p.m, which disappears by exchange with heavy water and whose integration corresponds well to

  two protons of the hydroxyl groups in positions 1 and 8.

EXAMPLE I

  Preparation of 10-phenyltriacetoxy-1,8,9 anthracene

  A mixture of 40 g of 1,1-dihydroxy-phenyl-10 anthrone and 0.5 cm 3 of pyridine in 400 cm 3 of acetic anhydride is stirred under an inert atmosphere and gradually brought to a temperature between 60 and 70 ° C. The starting material is quantitatively converted to the corresponding triacetate after three hours. After cooling with an ice bath, the product crystallizes. It is drained, washed with ethyl ether and dried. 45 g of greenish-yellow solid are thus obtained which are dissolved in a mixture of 200 cm 3 of acetic acid and 200 cm 3 of dichloro-1,2-ethane brought to a temperature of approximately 80 ° C. The solution is then filtered, at this temperature and by cooling the filtrate, the product crystallizes. It is

  drained, washed with ethyl ether and dried.

  35 g of 10-phenyl-1,8,9-triacetoxy-anthracene are obtained in the form of

  4th light yellow crystals of melting point: 279 C.

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  Elemental Analysis: C26H2006 Calcd: C: 72.88 H: 4.70 0: 22.40 Found: 72. 87 4.73 22.15

EXAMPLE II

  Preparation of 10-phenyl-1,8,9-tripropionyloxy anthracene To a mixture stirred under argon of 2.5 g of 1,8-dihydroxy-phenyl-10 anthrone in 25 cm3 of propionic anhydride is added 0.100 cm3 of anhydrous pyridine. The reaction mixture is then heated for one hour at C, after which time all of the starting material is converted. The excess reagent is then removed by evaporation under vacuum. The solid obtained is solubilized in the minimum of toluene, deposited on a column of silica gel and then eluted with toluene. After evaporation of the eluent, 1.3 g of a

  solid which is recrystallized from a toluene / hexane mixture.

  1.1 g of white crystals of melting point 216 C. are thus isolated.

Elemental analysis: C 29H2606

2926 6

  Calculated: C: 74.02 H: 5.56 0: 20.40 Found: 74.14 5.59 20.19

EXAMPLE III

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

  A mixture, stirred under an inert atmosphere, of 3 g of 1,8-dihydroxy phenyl anthrone, of 3,16 cm 3 of pyridine (4 equivalents) and of 4.26 cm 3 of isobutyryl chloride (4 equivalents) in 100 ° C. of anhydrous toluene is brought at reflux of the solvent for 10 hours. The reaction medium is then washed several times with water. The organic phase is then decanted, dried over magnesium sulfate and concentrated. The product obtained in the form of a viscous liquid is dissolved in the minimum of toluene and deposited on a column of silica gel. The expected tri-ester is eluted with toluene-methylene chloride (3/1). After concentration of the eluent 2.3 g of solid is obtained which is recrystallized in toluene. 1.4 g of 10-phenyltrisobutyryloxy-1,8,9 anthracene are isolated in the form of yellow crystals

Melting point: 2240C.

  Elemental analysis: C32H3206 Calc .: C: 74.98 H: 6; 29 0: 18.72 Found: 74. 78 6.27 18.57

EXAMPLE IV

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

  To a mixture of 3 g of 1,8-dihydroxy-phenyl-10-anthrone in 15 cm3 of cyclohexane carboxylic acid chloride, 3.2 cm3 of pyridine are added slowly with stirring. The reaction medium is then heated for 3 hours at 1000C. It is then diluted to room temperature, by the addition of 200 cm3 of

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  methylene chloride, then washed with bicarbonate water and then with water. The organic phasc is dried over sodium sulfate. After evaporation of the methylene chloride, gold obtains 4.2 g of yellow solid which is recrystallized in a toluene / ethyl ether mixture. After filtration and drying, 3.75 g of 10-phenyltri (cyclohexylcarbonyloxy) -1,8,9 anthracene are obtained.

  form of yellow crystals with a melting point of 235 C.

  Elemental analysis: C41H4406 Calc'd: C: 77.82 H: 7.00 0: 15.17 Found: 77. 97 7.00 15.01

EXAMPLE V

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

  A mixture of 3 g of 1,8-dihydroxy-10-phenylanthrone, 3.16 cm 3 of pyridine, 4.8 cm 3 of pivaloyl chloride in 100 cm 3 of anhydrous toluene is stirred under an argon atmosphere for 10 hours at room temperature. boiling of the solvent. After cooling to room temperature, the reaction medium is washed several times with water. The organic phase is decanted, dried over magnesium sulfate and concentrated. The residue deposited on a column of silica gel is then eluted with toluene. After concentration of the elution phases, 2.38 g of a solid which is

  recrystallized from a toluene / hexane mixture.

  1.4 g of 1,8-dipivaloyloxy-phenyl-10-anthrone are thus isolated

  white crystals of melting point: 160 C.

  Elemental analysis: C30H3005 Calc'd: C: 76.57 H: 6.42 0: 16.99 Found: 76. 40 6.40 16.92

EXAMPLE VI

  Preparation of phenyl-10-tribenzoyloxy-1,8,9-anthracene To a stirred mixture at room temperature and under an inert atmosphere of 1 g of 1,8-dihydroxy-10-phenyl-9-anthrone in 15 cm 3 of sodium chloride.

  benzoyl is added dropwise 1.2 cm3 of pyridine.

  After stirring for one hour, all of the starting anthrone is converted to the corresponding triester. The reaction medium is concentrated under reduced pressure, dissolved in 100 cm3 of methylene chloride, washed

  several times with water and finally dried over sodium sulphate.

  The organic phase is then deposited on a column of silica gel and eluted with toluene / methylene chloride, progressively

  enriched with methylene chloride.

  After concentration of the elution phases, 1.55 g of triester are obtained, which is recrystallized from toluene. The crystals are

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  dried and dried. One thus isolated lg of phenyl-10 tribenzoyloxy-1,8,9

  anthracene in the form of yellow crystals with a melting point of 255 ° C.

  Elemental Analysis: C1E2606 Calcd: C: 80.12 H: 4.26 0: 15.62 Found: 80. 08 4.32 15.79

  EXAMPLES OF PHARACEUTICAL AND COSMETIC COMPOSITIONS

  Example 1 - Non-Soluble O.5g Tablet - Phenyl-10-triacetoxy-1,8,9 anthracene ........, 100g - Lactose ................ ...................... 0, 082g - Stearic acid ...................... ........ 0.003g - Purified talc ................................. O, 015g - Sweetener...............

  .................. qs - Colorant ............................. ........ qs - QSP rice starch ............................ O, 500g This tablet is prepared by direct dry compression of the mixture of DTD: different constituents.

  Example 2 - Insoluble 0.8g Tablet - Phenyl-10-triisobutyryloxy-1,8,9 anthracene .. 0,200g - Lactose ...................... ................ 0, 200g - 20% gum arabic in water ............... 0.080g - Liquid paraffin .. .......................... 0.004g - Purified talc .................

  .............. 0.016g - QSP Starch ............................... This tablet is obtained by granulating, wet, the mixture of phenyl-10-triisobutyryloxy-1,8,9 anthracene, starch, lactose and DTD: gum arabic 20%. in water.

  The granules are then dried and sieved. These

  The latter are then mixed with paraffin and talc.

  Example 3 - Granules in sachets of 3g - Phenyl-10-tripropionyloxy-1,8,9 anthracene .............................. ..... 0.150g -Sucharose ..........

....................... 2,220g Methylcellulose ...................... .... DTD: .. 0,030g - Purified water ................................. 0,600g The dough obtained by mixing the four constituents is granulated by DTD: wet and dried.

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  Example 4 - Capsules containing 0.05 g of active compound - Phenyl- (tri (cyclo) hexylcarbonyloxy) -1.8.9 anthracene ................... ................ 0, 050g - Hui] e cod liver QSP ................... 0,500g L The capsule shell is made by molding and drying a suitable mixture of gelatin, glycerin, water and preservative. The suspension containing the active compound is introduced into the capsule which is

then sealed.

  Example 5 - Capsule containing 0.3 g of powder composition of the powder: Dipivaloyloxy-l, 8 phenyl-10 anthrone ......... 0.080 g - corn starch .....

  ........................ 0.060g - Lactose QSP ..................... ........ DTD: ..... 0.300g The powder is packaged in a capsule composed of gelatin, DTD: titanium dioxide and a preservative.

  Example 6 - Hydrophobic ointment - Dipivaloyloxy-1,8-phenyl-10 anthrone .....

  .. 1,00g - Vaseline ..................................... 49,00g Ceresin .. ................................... 15,00g - Salicylic acid .... DTD: ... ...................... 0,30g - Vaseline oil ..................... ..DTD: ..... 34.70g Example 7 - Nonionic emulsion for topical application - Phenyl-10-triacetoxy-1,8,9 anthracene ........ 0,70g - Eucerine anhydrous .. ........................... 70.00g - Vaseline oil ............. DTD:. ......... 10,00g Preservative QS - Butylhydroxytoluene QS - Demineralized sterile water QSP ................ 100,00g For a good conservation, this emulsion should be stored at..DTD: protected from heat and light.

  Example 8 - Anhydrous gel - Dipivaloyloxy-1,8-phenyl-10 anthrone ......... 1, 50g - "Aerosil 200" (silica) from DEGUSSA. 7.00g - Isopropyl myristate QSP 100.00g EXAMPLE 9 - Two-part milk to emulsify extemporaneously First part - Phenyl-10-tripropionyloxy-1,8 anthracene ..... 2,00g - "MIGLYOL 812" (triglycerides capric / caprylic acid) from DYNAMIT NOBEL QSP ......................

............ 20,00g..DTD: - 11 -

  Second part - "Tween 80" (polyoxyethylenated sorbitan meno-oleate with 20 moles of ethylene oxide) of the ATLAS Company ...................... .... 10,00g - Preservatives QS - QSP Sterile Demineralized Water ................ .80,00g The first part is shaken in order to put the active compound in

  suspension and mix the two parts before applying the milk.

  Example 10 - Stick - Phenyl-10-triisobutyryloxy-1,8,9 anthracene .. 5,00g Cocoa butter .......................... 12.50g - ozokerite wax ..

  ......................... 18,50g - Refined white paraffin ............. DTD: ... ... 6.25g - Vaseline oil ........................... 12.75g - Isopropyl myristate QSP .... 100 mg Example 11 - Anti-hair loss and anti-dandruff capillary composition - Dipivaloyloxy-1, 8 phenyl-10 anthrone ......... 0 , 50g - Stannous chloride ..................... DTD: ....... 0,30g - Isopropyl myristate QSP ...... ........ O ..... 100,00g..DTD: - 12- 2591222

Claims (13)

  ]. Moro, di and tri-esters of 1,8-dihydroxy-10-phenyl-9-anthrone or 9-anthranol, characterized in that they correspond to the following formula: R2 0 (R1) p OCOR3 4 (I) (11) where: p is 0 or 1 (a) when p = O, t = 1 and R2 represents a hydrogen atom or -COR3, (b) when p = 1, t = 0 and R1 and R 2 represent, independently of one another, a hydrogen atom or -COR 3, R 3 representing a linear or branched alkyl radical having from 1 to 17 carbon atoms, a cycloalkyl radical, or a phenyl radical optionally substituted by an alkyl radical; lower, a lower alkoxy, a halogen atom, a nitro function, a -CF3 radical or by a hydroxyl function, and mixtures of said esters.   2. Compounds according to claim 1, characterized in that the alkyl radical having 1 to 17 carbon atoms is a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl,   isopentyl, heptyl, nonyl, undecyl, pentadecyl or heptadecyl.   3. Compounds according to claim 1, characterized in that   the cycloalkyl radical is the cyclopentyl or cyclohexyl radical.   4. Compounds according to claim 1, characterized in that the phenyl radical is substituted by at least one methyl, ethyl, tert-butyl, methoxy, ethoxy, fluorine or chlorine atom, a functional group.   nitro, the -CF3 radical or a hydroxyl function.   5. Compounds according to any one of claims 1 to 4,   characterized in that they are di-esters of the following formula: - 13 2591222 R3 00 OCOR3 C6115 c610   R3 having the same meanings as those given to the 1.   6. Compounds according to any one of claims 1 to 4,   characterized in that they are tri-esters of the following formula: R CO OCOR R OCOR3 C6Il5   R3 having the same meanings as those given to the claim 1.   Compounds according to any one of the preceding claims,   characterized in that they are selected from the group consisting of: 10-phenyl-1,8,8-triacetoxy-anthracene, 10-phenyl-tripropionyloxyl, 8,9-anthracene, 10-phenyl-1,8-triisobutyryloxy , 9-anthracene, 10-phenyltricyclohexylcarbonyloxy-l1,8,9 anthracene, - dipivaloyloxyl, 8-phenyl-10-anthrone-9-phenyl-10-tribenzoyloxy-1,8,9 anthracene, 10-phenyl-tricyclopentylcarbonyloxy-1 , 8,9-anthracene, 10-phenyltroctanoyloxy-1,8,9-anthracene, 10-phenyl-triundecanoyloxy-1,8,9-anthracene, 10-phenyl-trioctadecanoyloxy-1,8,9-anthracene, 10-phenyl tritolylcarbonyloxy-1,8,9 anthracene, phenyl-10-tri (pmethoxybenzoyloxy) -1,8,9 anthracene, 10-phenyltrim (trifluoromethyl) benzoyloxy-1,8,9 anthracene, 8. Process for the preparation of mono, di and tri-esters according to one   any of claims 1 to 7, characterized in that it consists of - 14 - 2591222   reacting, with or without a solvent, the 1-8-dihydroxy-10-phenyl-9-anthrone an activated form of acid such as an acid anhydride, (R3CO) 20 or an acid chloride RCOC1, R. with the same meanings as those given in claim 1, in the presence of a base such as pyridine and at a temperature between 20 and 130 C. 9. Method according to claim 8, characterized in that the   reaction is conducted in toluene.   10. A pharmaceutical or cosmetic composition, characterized in that it contains as active ingredient in a vehicle suitable for   least a compound according to any one of claims 1 to 7 or obtained   according to any one of claims 8 and 9.   11. Composition according to claim 10, characterized in that it contains the active ingredient at a concentration between 0.01 and% relative to the total weight of the composition. 12. Use of a compound according to any of   Claims 1 to 7 for the preparation of a therapeutic composition   intended for the treatment of psoriasis, warts, rheumatism,   dermatoses, eczema and acne.   13. Use of a compound according to any one of   Claims 1 to 7 for the preparation of a cosmetic composition for   the treatment of acne-prone skin, dandruff, seborrhea and hair loss.