CA1265133A - 1,8-dihydroxy 10-phenyl 9-anthrone or 9-anthranol mono, di and tri-esters; process for preparing the same; cosmetic compositions containing these products - Google Patents

Abstract

The invention relates to 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: <IMG> (I) in which : p is 0 or 1 (a) when p = 0, t = 1 and R2 represents a hydrogen gene or -COR3, (b) when p = 1, t = 0 and R1 and R2 independently represent the one of the other 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 -CF3 radical or by a hydroxyl function, and mixtures of said esters. The invention also relates to their preparation process and their application in cosmetics.

Description

i265133 The present invention relates to mono, di and 1,8-dihydroxy-phenyl-10 anthrone-9 or anthranol-9 tri-esters, the process for preparing these esters and their use in cosmetics.
In cosmetics, these esters can be used for improving the appearance of acne prone skin.
Mono, di and tri ~ esters of dihydroxy-1,8 phe-nyl-10 anthrone-9 or anthranol-9, according to the invention, present tent compared to dihydroxy-1,8 phenyl-10 anthrone a-benefits from being more stable and less staining the skin and clothes, especially in basic washing.
Mono, di and tri-esters of 1,8-dihydroxy nyl-10 anthrone-9 or anthranol-9 can be represented ted by the following general formula:

. R2o (RI) pocoR3 (H) t in which:
p is 0 or l (a) when p = 0, t = l and R2 represents an atom hydrogen or -COR3, (b) when p = l, t = O and R and R2 represent inde hanging from each other a hydrogen atom or -COR3, R3 representing an alkyl radical, linear or ra-mified, having from 1 to 17 carbon atoms, a cyclo radical alkyl, or a phenyl radical optionally substituted by lower alkyl, lower alkoxy, halogen atom, ~, 126S ~ 33 - the -a nitro function, a radical -CF3 or by a function hydroxyl, and the melan ~ es of said esters.
By alkyl radical, linear or branched, having 1 to 17 carbon atoms we can hear a methyl radical, ethyl, propyl, isopropyl, _ /
/

~ 6S133 2 -butyl, isobutyl, tertiobutyl, pentyl, isopentyl, heptyle, nonyle, undecyle, pentadécyle et heptadécyle.
By cycloalkyl radical one can understand a radical having from 3 to 6 carbon atoms but preferably the cyclopentyl or cyclohexyl radical.
When the phenyl radical is substituted by an alkyl radical lower, the latter is preferably a methyl, ethyl or tertiobutyl.
When the phenyl radical is substituted by an alkoxy radical lower, this is preferably the methoxy or ethoxy radical.
When the radyl phenyl 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:

~ 3Cl OCOR3 R ~ CO ~ OCOR3 () COR3 ~ '~
C61 ~ 5 C6H5 (~ I ~ (III) Among the esters according to the invention of formula (I), it is possible to especially quote the solvents:
- 10-phenyl-triacetoxy-1,8,9 anthracene, - 10-phenyl-tripropionyloxy-1,8,9 anthracene, - phenyl-lO tributyryloxy-1,8,9 anthrac ~ ne, - 10-phenyl triisobutyryloxy-1,8,9 anthracene, - 1,8-diisobutyryloxyphenyl-10 anthrone-9, - 10-phenyl tricyclohexylcarbonyloxy-1,8,9 anthracene, - 1,8-dipivaloyloxy-phenyl-10 anthrone-9 - phenyl-10 tribenzoyloxy-1,8,9 anthracene, - 18 phenyl-10 erlcyclopentylcarbonyloxy-1,8,9 anthracene, - phenyl-10 trioctanoyloxy-1,8,9 anthracè & e, - 10-phenyl-triundecanoyloxy-1,8,9 anthracene, - 10-phenyl trioctadecanoyloxy-1,8,3 anthracene, - 10-phenyl tritolylcarbonyloxy-1,8,9 anthracene, - 10-phenyl tri (p-methoxybenzoyloxy) -1,8,9 anthracene, - phenyl-10 ~ ri [m- (trlfluoromethyl) benzoyloxy ~ -1,8,9 an ~ hracene, The present invention also relates to the method of preparation of 1,8-dihydroxy-phenyl-10-anthrone-9 or anthranol-9 esters as defined above.
Dihydroxy-1,8 phenyl-10 anthrone-9 is a known compound, the preparation has been described in Arch. der Pharmazie, 298, 273-81 (1965), presenting three possible sites of O-acylation which according to the 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 which is fractionated by chromatography.
The esters according to the invention are obtained by reacting, on the dihydroxy-1,8 phenyl-10 anthrone-9, an activated form of acid such as acid anhydride, (R3CO) 20, or an acid chloride, R3COCl, in the presence a base and preferably an aromatic amine such as pyridine, 18 optionally in an aromatic solvent medium such as in toluene and at a temperature between 20 and 130C.
The formation of mono, di or tri-esters is a function of the proportions molars of the acid anhydride or acid chloride reacted and reaction time.
For the preparation of mono and di-esters preferably used 1.5 to 2.5 equivalents of acid chloride or acid anhydride and we follow the reaction by thin layer chromatography in order to stop it either at mono-ester stage or di-ester stage.
For the preparation of trl-esters a large excess of acid chloride or acid anhydride and in order to complete the reaction the temperature is preferably raised to 80-110C.
~ when a particularly congested acid chloride is used such as for example the plvaloyle ch ~ orure, 11 is particularly easy to access the dl-esters even in the presence of excess without noticing a significant formation of the corresponding tri-ester.
Insofar as one uses easily an chloride of acid eliminable either by evaporation or by washing in basic medium, it is desirable to re-assemble the reaction using the acid chloride at the same time as solvent and as reagent and a ~ outer of 4 to 8 equlvalents of pyrldine.
In this case, we then operate at a temperature between 20 and 60C and the reaction is partially completed.
After the end of the reaction, when it is carried out in a solvent, pour into the reaction medium water and proceed to different washes notam ~ ent with the alde of a solution of sodium bicarbonate.
The organic phase is then dried over magnesium sulfate and then filtered. The 12651 ~ 33 product can be purified either by recrystallization or by chromatography on silica gel using preferably toluene or a toluene / ethyl acetate mixture as eluent.
The present invention also relates to the use of one or more of the es-ters of formula ~ I) in cosmetic, when associated with a cosmetic vehicle acceptable to define a cosmetic composition.
In cosmetics, the compounds according to the invention lQ can be used on skin prone to acne.
The cosmetic compositions can be prepared for example by adding an ester of formula (I), to a concentration between 0.01 and 5 ~, in various inert non-toxic, solid or liquid supports, generally used in compositions for use cosmetic.
Liquid compositions can be presented for example in the form of a sterile solution miscible with the water. The compositions can also contain substances usually used as preservatives, stabilizers, antioxidants, regulators and emulsifiers.
You can also add salts and buffers.
The supports and diluents as listed below above can consist of organic substances or mineral, for example by gelatin, lactose, starch, magnesium stearate, talc, gum arabic, vegetable and mineral oils, fillers, thickeners, dyes, humectants or polyalkylene glycols.
The compositions can be presented in the form ointment, ointment, gel, tincture, cream, solution, lotion, powder micronized, spray, suspension, shampoo or soaked pads.

- 4a -Ointments or ointments are preferred and are prepared by mixing an ester according to the invention with inert non-toxic supports.
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// _ ~ 265,133 We will now give by way of illustration and without any limiting character several examples of preparation of esters according to the inversion as well as several examples of compositions for cosmetic use.
tick.
Preparation of 1,8-dihydroxy-phenyl-10 anthrone-9 a) repair of phenyl-10 trihydroxy-1,8,10 anthrone-5 In a 2 liter reactor fitted with mechanical agitation, a arrival of argon, a refrigerant and an introduction bulb, we place 30g of 1,8-dihydroxy anthraquinone and 2 liters of anhydrous tetrahydrofuran.
The solution obtained is then cooled to -70C.
At this temperature, the anthraqulnone is crystallized. We add then with stirring, in 30 minutes, a solution which contains 4 equivalents of phenyllithium.
The temperature is maintained throughout the addition 1 ~ between -60C and -70C. At the end of the addition, a sample is checked taken that all 1,8-dihydroxy anthraquinone is transformed. At this temperature, the reaction medium is added by adding 400 cc of acid acetic, then the mixture is allowed to return to room temperature. The solvent is evaporated to dryness under reduced pressure. The product obtained, in the form of an oily mass, crystallized by stirring in water.
The crystals obtained are drained, washed with dichloromethane and then dried. We thus obtain 32g of yellow crystals which we recrystallize in the methanol. The product has a melting point of 216C.
Analysis C20H144 Calculated: C: 75.46 H: 4.43 0: 20.10 Irouvé: 75.48 4.35 19.95 b ~ Preparation of 1,8-dihydroxy-phenyl-10 anthrone-9 In a 2 liter reactor fitted with a mechanical stirrer and ur.e arrival of argon, 5Gg of 10-phenyl-trihydroxy-1,8,10 anthrone-9 are introduced, then 200g of ground stannous chloride and 2 liters of acetic acid.
To this mixture, stirred at the ambient temperature, then added drop by drop, in 30 mlnutes, 200cm3 of concentrated hydrochloric acid. The ~ 26S133 disappearance of phenyl-10 trihydroxy-1,8,10 anthrone-9 is followed by thin layer chromatograph. After about two hours, the reaction of reductlon is complete. Dihydroxy-1,8 phenyl-10 anthrone-9 precipitated in the medium is drained, washed with water and dried. We get ain ~ i 42g of S light yellow crystals. The filtrate is poured onto a mixture of 1 liter of water and 1 kg of crushed ice. The rest of the product precipitates, it is drained, washed with water and dried. We also isolate an additional 4g of the product expected.
The 1,8-dihydroxy-phenyl-10 anthrone-9 thus obtained is pure.
It has a melting point of 193-194C.
Analysis C20H14 3 Calculated: C: 79.45 H: 4.66 0: 15.87 Found: 79.25 4.71 16.00 The structure of 1,8-dihydroxy-phenyl-10 anthrone-9 is confirmed by mass spectrography where we observe on the spectrum the parent peak at m / e: 302 by direct ionization and at m / e: 303 by chemical ionization at isobutane corresponding to M ~ H. These results are in agreement with the mass molar of 302g of the product.
The NMR spectrum also confirms this structure. We observe in particular a singlet at 5.30 p.pm whose integration corresponds to a proton. It is the one which is linked to carbon in position 10 of the anthrone nucleus.
The signal of the eleven aromatic protons is a multiplet whose o is from 6.60 to 7.50 p.pm (11).
Finally, the spectrum shows another singlet at 12.40 ppm, 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-phenyl-triacetoxy-1,8,9 anthracene.
A mixture of 40g of 1,8-dihydroxy-phenyl-10 anthrone and 0.5cm3 of pyridine in 400 cm 3 of acetic anhydride is stirred under an inert atmosphere and gradually brought to a temperature between 60 and 70C. The starting material is quantitatively transformed into the corresponding triacetate after three hours. After cooling with an ice bath, the product crystallizes. It is drained, washed with ethyl ether and then dried. We thus obtains 45g of solid greenish yellow color which is dissolved in a mixture of 200 cm 3 of acetic acid and 200 cm 3 of 1,2-dichloroethane brought to a temperature of around 80C. The solution is then filtered, at cetee temperature and by cooling the filtrate, the product crystallizes. It is wrung, washed with ethyl ether and dried.
35 g of phenyl-10 triacetoxy-1,8,9 anthracene are obtained, in the form light yellow crystals with melting point: 279C.

~ 65,133 7 -Elementary analysis: C26H20O6 Calculated: C: 72.88 H: 4.70 0: 22.40 Found: 72.87 4.73 22.15 EXAMPLE II
Preparation of 10-phenyl-tripropionyloxy-1,8,9 anthracene.
To a stirred mixture under an argon atmosphere of 2.5 g of dihydroxy-1,8 phenyl-10 anthrone in 25cm3 of propionic anhydride, 0.100cm3 of anhydrous pyridine. The reaction mixture is then brought for one hour to 70C, time after which all the starting material is transformed. Excess of reagent is then removed by evaporation under vacuum. The solid obtained is solubilizes in the minimum amount of toluene, deposited on a column of silica gel then eluted with toluene. After evaporation of the eluent, 1.3 g of a solid which is recrystallized from a toluene / hexane mixture.
Is thus isolated 1, lg of white crystals with melting point: 216C
Elemental analysis: C29H26O6 Calculated: C: 74.02 H: 5.56 0: 20.40 Found: 74.14 5.59 20.19 EXAMPLE III
Preparation of 10-phenyl-triisobutyryloxy-1,8,9 anthracene.
A mixture, stirred under an inert atmosphere, of 3 g of 1,8-dihydroxy phenyl-10 anthrone, 3.16 cm3 of pyridine (4 equivalents) and 4.26 cm3 of isobutyryl chloride (4 equivalents) in 100cm3 of anhydrous toluene is brought to 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 amount of toluene and deposited on a silica gel column. The expected tri-ester is eluted with the mixture toluene-methylene chloride (3/1). After concentration of the eluent, 2.3g of solid are obtained which is recrystallized from toluene. We isolate 1.4g 30 of phenyl-10 triisobutyryloxy-1,8,9 anthracene in the form of crystals ~ aunes melting point: 224C.
Ana] elementary: C32H3206 Calculated: C: 74.98 H: 6.29 0: 18.72 Found: 74.78 6.2718.57 EXEMP ~ E IV
Preparation of phenyl-10 tri (cyclohexylcarbonyloxy) -1,8,9 anthracene.
Has a mixture of 3g of dihydroxy-1,8 phenyl-10 anthrone in 15 ~ m3 of cyclohexane carboxylic acid chloride, was slowly stirred 3.2 cm 3 of pyridine. The reaction medium is then brought to 100C for 3 hours.
is then diluted to normal temperature by adding 20Ucm9 of 1265 ~ 8 -methylene chloride, then washed with blcarbonated water and then with water. The organic phase is dried over sodium sulfate. After evaporation of the methylene chloride, 4.2 g of yellow soles are obtained which is recrystallized in a toluene / ethyl ether mixture. After filtration and drying we obtains 3.75 g of phenyl-10 tri- (cyclohexylcarbonyloxy) -1,8,9 anthracene under shape of color crystals ~ alder with melting point: 235C.
Elementary analysis: C41H44O6 Calculated: C: 77.82 H: 7.Q0 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 dihydroxy-1,8 phenyl-10 anthrone, of 3.16 cm3 pyridine, 4.8 cm3 of pivaloyl chloride in 100 cm3 of anhydrous toluene is stirred under an argon atmosphere for 10 hours at temperature solvent boiling. After cooling to the room temperature, the mllieu reaction is washed, plusliers fols with water. The organic phase is decanted, dried over magnesium sulfate and concentrated. The residue deposited on a column of slllce gel is then eluted using toluene. After concentrate on the elution phases, 2.38 g of a solid are obtained which is recrystallized from a toluene / hexane mixture.
1.4 g of dipivaloyloxy-1,8 phenyl-10 anthrone are thus isolated under form of white crystals with melting point: 160C.
Elementary analysis: C30H30O5 Calculated: C: 76.57 H: 6.420: 16.99 25 Found: 76.40 6.40 16.92 EXE ~ LPLE VI

Preparation of phenyl-10 tribenzoyloxy-1,8,9 anthracene To a mixture stirred at room temperature and under atmosphere inert of lg of 1,8-dihydroxy-phenyl-10 anthrone-9 in 15cm3 of chloride 30 benzoyl we have ~ drop 1.2cm3 of pyridine drop by drop.
After one hour of agitation, the entire starting anthone is transformed Pn corresponding triester. The reaction medium is concentrated under reduced pressure, dissolved in 100cm3 of methylene chloride, washed several times with water and finally dried over sodium sulfate.
The organic phase is then deposited on a column of gel of silica and eluted with toluene / methylene chloride, gradually enriched in methylene chloride.
After concentrating the elution phases, 1.55 g of trlester expected that one recrlstalllse in toluene. The crlstaux are wrung and dried. Is thus isolated lg of phenyl-10 tribenzoyloxy-1,8,9 anthracene under for ~ e of crystals ~ aunes of melting point: 255C.
Elementary analysis: C41H2606 Calculated: C: 80.12 H: 4.26 0: 15.62 Found: 80.08 4.32 15.79 EXAMPLE VII
-Preparation of diisobutyrylo ~ y-1,8 phenyl-10 anthrone.
A mixture, stirred away from light and in an inert atmosphere, L8 g of 1,8-dihydroxy-phenyl-10 anthrone, 19 cm3 of pyridine and 25 cm3 of isobutyryl chloride in 500 cm3 of anhydrous toluene is brought to reflux solvent for five hours.
After cooling, the reaction mixture is washed three times with water and dried over magnesium sulfate.
The residue obtained after evaporation under reduced pressure is then deposited on a column of silica gel. The column is eluted with toluene then with the toluene - methylene chloride mixture, the latter being gradually enriched in methylene chloride.
At the top of the chromatography, after isolation of the solvent, the following is isolated:
5 g of phenyl-10 triisobutyryloxy-1,8,9 anthracene described in Example III.
The following fractions rich in diester are concentrated and the product obtained is recrystallized from a toluene - pentane mixture.
1.5 g of diisobutyryloxy-1,8 phenyl-10 anthrone are obtained under form of beige crystals with melting point 136 C.
Elementary analysis: C28H2605 Calculated: C: 76.00 H: 5.92 0: 18.08 ~ found: 75.75 5.99 18.36.
EXAMPLE VIII
Preparation of phenyl-10 tributyryloxy-1,8,9 anthracene.
Has a stirred suspension ~ protected from light and under atmosphere 18 g of 1,8-dihydroxy-10-phenyl anthrone in 500 cm of toluene anhydrous, 19 cm3 of pyridine and 24.5 cm3 of butyryl chloride are added.
The mixture is then brought to toluene reflux for three hours, time to finish.
from which the starting material is completely transformed.
After cooling, the melan ~ e is washed three times with water and the toluene phase is dried over sodium sulfate. After concentration, the residue is deposited on a column of silica gel. The expected product is eluted with hexane - toluene mixture.

After ~ concentration of the elution solvent, 23 g of product which is recrystallized from a toluene - pentane melsnge, which leads to 16 g of phenyl-10 tri6utyryloxy-1,8,9 anthracene in the form of light yellow fu ~ ion crystals: 150 C ~
Elementary analysis: C32H3206.
Calculated: C: 74.98 H: 6.29 0: 18.72 Found: 75.00 6.47 18.57.

EXAMPLES OF COSMETIC COMPOSITIONS

EXAMPLE 1 Hydrophobic Ointment - Diplvaloyloxy-1,8 phenyl-10 anthrone .., ... ,,, 1,00g - Vaseline. ,,, .. ...... ,,,, ......, ..... .., ......., 49.00g - Céréslne., ....,. ,,. ,,,,,,, ........... ,,,,,,, ..,. 15.00g - Aclde salicyllque ... ,,,,. ,, ...........................,. ,, ...... .. 0.30g - Vasellne oil .., ... ,, ... ,,,,,, .., ..,. ,,,, 34,70g Example 2 Non-ionic emulsion for a topical application - Phenyl-10 trlacetoxy-1,8,9 anthracene ,, ........................... 0.70g - Anhydrous Eucérlne .... ,,,, .. ,,,,,,,,,,, 70.00g - Hulle de vasellne ,,. ,,,,,,,,,,,,,, .. ,,,,,, ............... 10.00g - QS servicer - Butylhydroxytoluene QS
- Sterile demineral water ~ QSP ............................ 100.00g For good conservation, this emulslon should be stored at away from heat and light, Example 3 - Anhydrous gel Dlplvaloyloxy-1,8 phenyl-10 anthrone,. ,,,, ... 1,50g - "Aerosll 200" (silica) from the company DEGUSSA. 7.00g - Isopropyl myrlstate QSP ..........,. ,,,,, .............. 100.00g Example 4 - Lalt in two parts to be emulsified extemporaneously First part_e - Phenyl-10 triproplonyloxy-1,8 anthracene ... ,, 2,00g - "MIGLYOL 812" (trlglycérldes des acldes caprique / capryllque) from Soclété DYNAMIT
NOBEL * QSP ....., ............ ,, ..., .............,., ....... .......... ,, 20.00g * ~ trademark) Part Two - "Tween 80" (sorbltan mono-oleate polyoxyethylenated to 20 moles of ethylene oxide) from ATLAS ............................. 10.00g - QS preservatives - Sterile demineralised water QSP ................... 80.00g The first part is agitated in order to bring the active compound into suspension pUi9 the two parts are mixed before applying the milk Example 5 - Stick - Phenyl-10 trilsobutyryloxy-1,8,9 anthracene ..... 5.00g - Cocoa butter ................................. 12.50g - Ozokerite wax ................................ 18.50g - Refined white parafflne ...................... 6.25 g - Vaseline oil ............................... 12.75g - Isopropyl myristate QSP ...................... 100.00g Example 6 - Ointment - Diisobutyryloxy-1,8 phenyl-lO anthrone ......... l, OOg - "! IIGLYOL 812" (acid triglycerides caprylic / caprylic) of the Company DYNAMIT NOBEL .................................. 49.25g - White petrolatum, .............................. 49.25g - Salicylic acid .............................. 0.50g ~ (trademark)

Claims (12)

The embodiments of the invention, concerning the-which an exclusive property right or privilege is claimed, are defined as follows: 1. Mono, di and tri-esters of dihydroxy-1,8 phe-nyl-10 anthrone-9 or anthranol-9, characterized by the fact that they correspond to the general formula (I):
(I) in which:
p is 0 or 1 (a) when p = 0, t = 1 and R2 represents a hydro-gene or -COR3, (b) when p = 1, t = 0 and R1 and R2 represent independent each other 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 which is unsubstituted or substituted by a lower alkyl radical, lower alkoxy radical, halogen atom, a nitro function, a -CF3 radical or a hydroxyl function, and mixtures of said esters. 2. Compounds according to claim 1, character-laughed at by the fact that the alkyl radical having from 1 to 17 atoms of carbon is a methyl, ethyl, propyl, isopro- radical pyle, butyl, isobutyle, tertiobutyle, pentyle, isopentyle, heptyle, nonyle, undécyle, pentadécyle ou heptadécyle. 3. Compounds according to claim 1, character-laughed at by the fact that the cycloalkyl radical is the radical cyclopentyle or cyclohexyle. 4. Compounds according to claim 1, character-sés by the fact that the phenyl radical is substituted by at minus one methyl, ethyl, tert-butyl, methoxy radical, ethoxy, a fluorine or chlorine atom, a nitro function, the radical -CF3 or a hydroxyl function. 5. Compounds according to claim 1, character-sed by the fact that they are di-esters of formula:

in which R3 has the same meanings as those given in claim 1. 6. Compounds according to claim 1, character-sed by the fact that they are tri-esters of formula:

in which R3 has the same meanings as those given in claim 1. 7. Compounds according to claim 1, character-because they are chosen from the group by:
- 10-phenyl-triacetoxy-1,8,9 anthracene, - 10-phenyl-tripropionyloxy-1,8,9 anthracene, - 10-phenyl-tributyryloxy-1,8,9 anthracene, - 10-phenyl triisobutyryloxy-1,8,9 anthracene, - 1,8-diisobutyryloxy phenyl-10 anthrone-9, - 10-phenyl tricyclohexylcarbonyloxy-1,8,9 anthracene, - 1,8-dipivaloyloxy-phenyl-10 anthrone-9 - phenyl-10 tribenzoyloxy-1,8,9 anthracene, - 10-phenyl tricyclopentylcarbonyloxy-1,8,9 anthracene, - 10-phenyl-trioctanoyloxy-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, - 10-phenyl tri (p-methoxybenzoyloxy) -1,8,9 anthracene, - 10-phenyl tri [m- (trifluoromethyl) benzoyloxy] -1,8,9 anthracene. 8. Process for the preparation of mono, di and 1,8-dihydroxy-phenyl-10 anthrone-9 or anthra- tri-esters nol-9, corresponding to formula (I):
(I) in which:
p is 0 or 1 (a) when p = 0, t = 1 and R2 represents a hydro-gene or -COR3, (b) when p = 1, t = 0 and R1 and R2 represent independent each other 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 which is unsubstituted or substituted by a lower alkyl radical, lower alkoxy radical, halogen atom, a nitro function, a -CF3 radical or a hydroxyl function, and mixtures of said esters, characterized by the fact that it consists in reacting, with or without solvent, on the dihydroxy-1,8 phenyl-10 anthrone-9 an acid anhydride of formula: (R3CO) 2O or an acid chloride of formula:
R3COCl, in which R3 has the previous meanings, in the presence of a base at a temperature between 20 and 130 ° C. 9. Method according to claim 8, characterized by the fact that the base is pyridine. 10. The method of claim 8 or 9, charac-terified by the fact that the solvent is toluene. 11. Cosmetic composition, characterized by the fact that it contains as an active ingredient in a cosmetically acceptable vehicle, at least one of the components ses defined in claim 1. 12. Composition according to claim 11, charac-terrified by the fact that it contains the active ingredient in a concentration between 0.01 and 5% compared to the total weight of the composition.