HUE034912T2 - Benzoesav-észter vegyületek, készítmények, felhasználások és ezekhez kapcsolódó módszerek - Google Patents

Description

(12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C07C 219134 <20m 01> C07C 309142 <2006 01> 19.07.2017 Bulletin 2017/29 C07C 63I64<200601> A61K 31I216(200601> (21) Application number: 06725177.7 (86) International application number: PCT/EP2006/060886 (22) Date of filing: 20.03.2006 (87) International publication number: WO 2006/100225 (28.09.2006 Gazette 2006/39)

(54) BENZOIC ACID ESTER COMPOUNDS, COMPOSITIONS, USES AND METHODS RELATED THERETO

BENZOSAUREESTER, DIESBEZIJGLICHE ZUSAMMENSETZUNGEN, VERWENDUNGEN und METHODEN

ESTERS DE L’ACIDE BENZOIQUE, COMPOSITIONS, UTILISATIONS ET PROCEDES ASSOCIES (84) Designated Contracting States: (56) References cited: AT BE BG CH CY CZ DE DK EE ES FI FR GB GR WO-A2-02/095393 GB-A- 860 939 HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI US-A- 3 033 814 US-A- 3 751 563 SK TR US-A- 4 036 951 (30) Priority: 21.03.2005 EP 05102228 · YANAGISAWAM. ETAL: "Aldol Reaction of Enol

Esters Catalyzed by Cationic Species Paired with (43) Date of publication of application: Tetrakis(pentafluorophenyl)borate" CHEM. 26.12.2007 Bulletin 2007/52 PHARM BULL, vol. 48, no. 11,2000, pages 1838-1840, XP001208246

(73) Proprietor: Ferrer Internacional, S.A. · DATABASEC A [Online] CHEMICAL ABSTRACTS 08028 Barcelona (ES) SERVICE, COLUMBUS, OHIO, US; HUH, TAE-SONG ET AL: "Kinetics and mechanism of (72) Inventors: the hydrolysis of enol ester in strong acid

• MIRALLES, Ricardo solution" XP002363980 retrieved from STN E-08190 Sant Cugat Del Valles (barcelona (ES) Database accession no. 1994:680074 &amp;

• NONELL, Santiago JOURNAL OF THE KOREAN CHEMICAL E-08190 Sant Cugat Del Valles (barcelona (ES) SOCIETY , 38(5), 391-6 CODEN: JKCSEZ; ISSN: • RAGA, Manuel M. 1017-2548,1994, E-08024 Barcelona (ES) · RUPPIN C. ET AL: "Synthesis of Enol Esters from • GIUGLIETTA, Antonio Terminal Alkynes Catalyzed By Ruthenium E-08750 Molins De Rei (barcelona) (ES) Complexes" TETRAHEDRON LETTERS, vol. 27, • TEIXID0, Jordi no. 52,1986, pages 6323-6324, XP002363968

08302 Mataro (ES) · DATABASEC A [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; INOUE, (74) Representative: ZBM Patents - Zea, Barlocci &amp; YASUHIKO ET AL: "Hydroxybenzoate

Markvardsen derivatives" XP002363981 retrieved from STN

Plaza Catalunya, 1 Database accession no. 1987:439424 &amp; JP 61 08002 Barcelona (ES) 293952 A2 (SUMITOMO CHEMICAL CO., LTD., JAPAN) 24 December 1986 (1986-12-24)

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).

Description Technical field [0001] This invention is directed to photochemical precursors of ultraviolet absorbers, especially to benzoic acid ester compounds.

Background of the invention [0002] Overexposure to the sun’s invisible rays, ultraviolet A (UVA, 320-400 nm) and ultraviolet B (UVB, 290-320 nm) can cause skin damage. The damage can be immediate and long-term, with effects ranging from sunburn, rashes, and cell and tissue damage to premature wrinkling and skin cancer. One particularly deadly form of skin cancer, malignant melanoma, has been on the rise in recent decades, as tanning has become more popular. Over the same period, scientists have warned that the thin layer of ozone that protects life on Earth from the sun’s ultraviolet (UV) radiation is being depleted. This allows more UV radiation to get through, adding to the risk of overexposure. Indeed, many skin changes that often are identified with aging actually result from damage by too much sun.

[0003] Sunscreen is any substance or material that protects the skin from UV radiation. Sunscreens are available in the forms of topical lotion, cream, ointment, gel, or spray that can be applied to the skin; a salve or stick that can be applied to the lips, nose, and eyelids; a moistener in towelettes that can be rubbed against the skin; sunglasses that protect the eyes; and film screen that can be affixed to the windows of a car, room, or office.

[0004] Sunscreens help to prevent sunburn and reduce the harmful effects of the sun such as premature skin aging and skin cancer. But just how much protection they provide is a matter of debate. For many years, experts thought that only UVB was harmful. However, recent research suggests that UVA may be just as dangerous as UVB, although its effects may take longer to show up. In particular, UVA may play a role in causing melanoma. Most sunscreen products contain ingredients that provide adequate protection only against UVB rays. Even those labeled as "broad spectrum" sunscreens may offer only partial protection against UVA radiation. Those containing the ingredient avobenzone (4-ferf-butyl-4’-methoxydibenzoylmethane) give the most protection against UVA rays.

[0005] Sunscreens should be applied between 30 minutes and 2 hours before sun exposure. In general, they should be reapplied after every 80 minutes spent in the water or when perspiring heavily or every 2 hours spent out of the water.

[0006] UVB (290-320 nm) is the most erythemogenic solar radiation reaching the surface of the earth. It is also a potent skin carcinogen in animal studies. Sun Protection Factor (SPF) indicates the degree of protection against UVB induced erythema. The US Food and Drug Administration (FDA) regulates sunscreen products as over-the-counter drugs. The Final Over-the-Counter Drug Products Monograph on Sunscreens (Federal Register 1999: 64:27666-27963) established the conditions for safety, efficacy, and labeling of these products. The SPF is defined as the dose of ultraviolet radiation (UVR) required to produce 1 minimal erythema dose (MED) on protected skin after the application of 2 mg/cm2 of product divided by the UVR required to produce 1 MED on unprotected skin.

[0007] All sunscreens have a SPF on their labels. The SPF represents the length of time that sunscreen-protected skin can be exposed to UV rays before a minimal redness (erythema) appears, compared to the length of time it takes on unprotected skin. In other words, it indicates how much longer the skin can be exposed to the sun before getting a sunburn. For example, without a sunscreen, an individual might get a sunburn after 20 minutes or less in the sun. By applying a sunscreen of SPF 15, the individual might spend up to 300 minutes under the sun before sunburning, that is 15 times longer than if no protection is used.

[0008] Sunscreens with SPF numbers higher than 15 may work better for people who are fair-skinned, live at high altitudes, work or play outdoors much of the day, or perspire heavily. Swimming and perspiration reduce the actual SPF value of many sunscreens, even those that are water-resistant, so it is convenient to reapply the product often.

[0009] Table 1 shows some relevant broadly used sunscreen compounds.

Table 1

[0010] Avobenzone (4-ferf-butyl-4’-methoxydibenzoylmethane, Parsol 1789, US4387089) provides superior protection through a large portion of the UVA range, including UVA I. Potentially a significant addition to sunscreen products for true broad-spectrum UV protection, concerns have been raised regarding its photostability and its potential to degrade other sunscreen ingredients in products in which it is used.

[0011] Dioxybenzone (2,2’-dihydroxy-4-methoxybenzophenone, US2853521) is mainly used as an UV-absorber for polymers and coatings. It is used as a stabilizer for polyester film. It is effective against UVB and some UVA light.

[0012] Oxybenzone (2-hydroxy-4-methoxybenzophenone, US2773903, US2861104, US2861105 and US3073866) absorbs well through UVA II and can be considered a broad-spectrum absorber. It significantly enhances UVB protection when used in a given formula.

[0013] Sulisobenzone (5-benzoyl-4-hydroxy-2-methoxybenzenesulfonic acid, GB1136525) extends the coverage beyond the UVB range and into the UVA range, helping to obtain broad-spectrum sunscreen preparations.

[0014] Amino-substituted hydroxybenzophenones have been disclosed as photostable UVfilters to be used in cosmetic and dermatological compositions (US6409995).

[0015] Chemical sunscreens "block" the penetration of UV radiation through the epidermis by acting as filters and absorbing and reflecting high energy UV. The sunscreen molecules absorb the high energy UV photons causing the electronic structure to move to a higher energy state. This electronic energy is dissipated by conversion to vibrational and rotational energy within the molecule, ultimately being transferred to the molecule’s environment as heat.

[0016] The FDA has taken a position against the continued labeling of high SPF formulations, and has stated that the maximum SPF should not exceed 30 due to the additional costs and risks from increased concentrations of active ingredients. This is in spite of the fact that other than the expected occurrence of occasional allergic, phototoxic, and photoallergic cutaneous reactions, there is virtually no published evidence of harm from using high SPF sunscreen formulations.

[0017] There are, in fact, a number of reasons why high SPF formulations (> 30 SPF) may be the best choice for high risk individuals, especially when sun exposure is expected to be extensive. Rubbing, sweating, and water immersion diminish the effectiveness of all sunscreens, requiring frequent re-application of the product even with supposedly waterproof or sweat proof formulations. Another factor that enhances the damaging effects of lengthy exposures is a time-dependent diminution of SPF effect not related to removal of the product from rubbing or washing. Experiments in the hairless mouse model found a significant decrease in measured SPF occurring within the first few hours following sunscreen application. Studies in humans confirm that single applications of an SPF 25 sunscreen are frequently inadequate to prevent erythema, and that multiple applications are required to completely suppress erythema, even from a single day’s sun exposure.

[0018] A final factor that may not be fully compensated for, even with repeated application, is the effect of multi-day UV exposures. A significant multi-day exposure to sunlight (e.g., all day Saturday and Sunday) increases the sensitivity of the skin to UV damage on the second day of exposure. This means that even if the sunscreen functions as predicted by the rated SPF to prevent erythema on thefirstday of exposure, the heightened sensitivity on the second and subsequent days of exposure may lead to erythema development which would not have been predicted based solely on extrapolations of the SPF. In such instances, a sunscreen with an SPF >30 may provide significantly better protection from UVdamage, particularly in susceptible individuals.

[0019] Higher SPF sunscreen products have led to the use of multiple individual sunscreen agents used in combinations at maximum concentrations that may interact.

[0020] The current focus on erythema as the standard against which sunscreen potency is measured may have led to the assumption that erythema prevention is also the only important goal of sun protection, and ultimately to the FDA’s position against sunscreens more potent than 30 SPF. This assumption ignores experimental evidence that significant UV-induced damage occurs prior to the development of perceptible UV-induced redness. Human research using sunburn cells as the measure of UV damage supports the existence of significant sub-erythemal DNA damage in the skin, and the value of high SPF sunscreens in preventing it.

[0021] SPF testing is designed to evaluate protection against erythema produced by natural sunlight and, therefore, denotes principally the degree of protection against UVB, since the amount of UVA received from sunlight does not produce significant erythema. The only ingredient approved by the FDA for protection against UVA radiation is avoben-zone. However, if a product contains ingredients that absorb UV between 290-320 nm it can be labeled as a broad-spectrum sunscreen, meaning it will provide protection against both UVB and shortwave UVA radiation.

[0022] Adverse reactions to sunscreen comprise cutaneous problems, such as allergic contact reactions, photocontact reactions, and drying or tightening of the skin. Other side effects are rare, but possible, namely acne, burning, itching, or stinging of the skin, redness or swelling of the skin, rash, with or without blisters that ooze and become crusted, pain in hairy parts of body and pus in hair follicles.

[0023] Photostability refers to the ability of a molecule to remain intact with irradiation. Poor photostability is potentially a problem with all UV filters because they are deliberately selected as UVR-absorbing molecules. This issue has been raised specifically with avobenzone, with photolysis demonstrated, especially in vitro systems, that simultaneously irradiate and measure transmittance in situ. The photostability of the molecules also depends on the solvent or the vehicle used.

[0024] Subjective irritation associated with burning or stinging without objective erythema is the most common sensitivity com plaint from sunscreens. This irritation is most frequently observed in the eye area. However, persistent objective irritant contact dermatitis is a more common side effect. Virtually all sunscreen ingredients reported to cause contact allergy might be photoallergens. Sunscreen actives seem to have become the leading cause of photocontact allergic reactions. Individuals with preexisting eczematous conditions have a significant predisposition to sensitization associated with their impaired cutaneous barrier. In addition, certain antibiotics, birth control pills, diuretics, antihistamines, and antidepressants are among the commonly used drugs that can increase sensitivity to the sun’s rays.

[0025] A water resistance claim of two hours means the sunscreen should retain its full SPF protection even after two hours in the water. Even water resistant, sunscreen should be reapplied after any water sports.

[0026] It is therefore desirable to discover new sunscreen compounds with a lower risk of side effects, increased photostability, and increased persistence on the skin.

[0027] Yanagisawa M. et al ("Aldol Reaction of Enol Esters Catalyzed by Cationic Species Paired with Tetrakis(pen-tafluorophenyl) borate", Chem. Pharm. Bull. 2000, vol. 48, no. 11, pages 1838-1840) discloses crossed aldol reaction of enol esters with aldehydes. Among the enol esters, the following are cited:

wherein X is methoxy, H or trifluoromethyl, and Y is methoxy.

[0028] Huh, Tae-Song et al ("Kinetics and mechanism of the hydrolysis of enol ester in strong acid solution", Journal of the Korean Chemical Society 1994, 38(5), 391-6) investigates the kinetics of the hydrolysis in strong acidic solution of alpha-benzoyloxystyrenes of formula (I) :

wherein X is methyl, H, Cl or N02.

[0029] Ruppin C. et al ("Synthesis of Enol Esters from Terminal Alkynes Catalyzed By Ruthenium Complexes" Tetrahedron Letters 1986, vol. 27, no. 52, pages 6323-6324) discloses the regioselective enol ester formation that results from the addition of saturate and unsaturated carboxylic acids to phenylacetylene. As an example the following compound is prepared:

[0030] JP4065065(B2) discloses compounds of formula (I)

wherein R is alkyl, alkoxy or halogen; m and p are integers 1-5; n and q are 0 or integers 1-4; m+n is <5 and p+q is <5, including 3-hydroxyphenyl-2,4-dihydroxybenzoate useful as intermediates for UV absorber hydroxybenzophenones.

[0031] US4036951, US3751563 and WO02/095393 disclose sunscreen preparations containing phenyl esters of amino salicylic acid, salicylic acid and 4-amino benzoic acid. GB860939 discloses resorcinol monobenzoate as stabilizer for inhibiting degradation of unsaturated polyesters by ultraviolet light, and US3033814 discloses phenyl salicylates as stabilizers of poly-alpha olefin compositions against deterioration resulting from exposure to sunlight or ultraviolet light.

[0032] The present invention provides benzoic acid ester compounds for use in a method for protecting a human or animal living body from ultraviolet radiation comprising treating said human or animal living body with an effective amount of a composition comprising a benzoic acid ester compound with ultraviolet absorbing properties perse susceptible to be photochemically converted in situ to another sunscreen compound with a higher UV protection. Also the present invention provides a method for protecting a material from ultraviolet radiation comprising treating said material with an effective amount of a composition comprising a benzoic acid ester compound with ultraviolet absorbing properties per se susceptible to be photochemically converted in situ to another sunscreen compound with a higher UV protection.

Brief description of the drawings [0033]

Figure 1 shows the phototransposition kinetics of 1-phenylvinyl 4-methoxybenzoate;

Figure 2 shows the phototransposition kinetics of 1-(4-methoxyphenyl)-vinyl 4-tert-butylbenzoate;

Figure 3 shows the phototransposition kinetics of 1- (4-tert-butylphenyl)-vinyl 4-methoxybenzoate;

Figure 4 shows the phototransposition kinetics of 4-benzoyloxy-2-methoxybenzenesulfonic acid;

Figure 5 shows the phototransposition kinetics of 3-diethylaminophenyl benzoate; and Figure 6 shows the phototransposition kinetics of 3-methoxyphenyl benzoate.

Detailed description of the invention [0034] The present invention relates to benzoic acid ester compounds of formula (I):

wherein R-|-R5 are selected independently from hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, C^Cg-alkoxy, C3-C6-cy-cloalkoxy, hydroxy, amino, C-j-Cg-alkylamino, C-i-Cg-dialkylamino, wherein said two alkyl portions of said dialkylamino can form, together with the nitrogen atom to which they are attached, a heterocycle selected from pyrrolidine, piperidine, morpholine and piperazine optionally N-substituted by C1-C6-alkyl or C3-C6-cycloalkyl, C3-C6-cycloalkylamino, C-pCg-alkyl-C^-Cg-cycloalkylamino and C3-C6-dicycloalkylamino, or two groups on adjacent ring carbons form a fused 0-(CH2)m-0 group wherein m is 1 or 2, or two groups on adjacent ring carbons form a fused CH=CH-CH=CH group; R is a group selected from (i), (ii) and (iii):

wherein R’ is selected from hydrogen, C^Cg-alkyl and C3-C6-cycloalkyl; R6-R10 are selected independently from hydrogen, C^Cg-alkyl, C3-C6-cycloalkyl, C^Cg-alkoxy, C3-C6-cycloalkoxy, hydroxy, amino, C^Cg-alkylamino, C^Cg-dialkylamino, wherein said two alkyl portions of said dialkylamino can form, togetherwith the nitrogen atom to which they are attached, a heterocycle selected from pyrrolidine, piperidine, morpholine and piperazine optionally N-substituted byC1-C6-alkylorC3-Cg-cycloalkyl, C3-C6-cycloalkylamino, CrC6-alkyl-C3-C6-cy-cloalkylamino and C3-C6-dicycloalkylamino, or two groups on adjacent ring carbons form a fused 0-(CH2)n-0 group wherein n is 1 or 2, or two groups on adjacent ring carbons form a fused CH=CH-CH=CH group; R-i-i is selected from hydrogen, C^Cg-alkyl and C3-C6-cycloalkyl; R12 is selected from hydrogen, C^Cg-alkyl and C3-C6-cycloalkyl; R13 and R14 are selected independently from hydrogen, C^Cg-alkyl, C3-C6-cycloalkyl, C^Cg-alkoxy, C3-C6-cycloalkoxy, hydroxy, amino, C1-C6-alkylamino, C1-C6-dialkylamino, wherein said two alkyl portions of said dialkylamino can form, togetherwith the nitrogen atom to which they are attached, a heterocycle selected from pyrrolidine, piperidine, morpholine and piperazine optionally N-substituted by C1-C6-alkylorC3-C6-cycloalkyl, C3-C6-cycloalkylamino, C.|-C6-alkyl-C3-C6-cy-cloalkylamino and C3-C6-dicycloalkylamino; or the group OR12 and R14 form a fused 0-(CH2)p-0 group wherein p is 1 or 2; and R15 is selected from 1 -pyrrolidinyl, 1 -piperidinyl, 4-morpholinyl and 1 (4)-piperazinyl optionally N-substituted by C^Cg-alkyl or C3-Cg-cycloalkyl, C3-C6-cycloalkylamino, C1-C6-alkyl-C3-C6-cycloalkylamino and C3-C6-dicycloalkylamino; and R16-R18 are selected independently from hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C3-C6-cycloalkoxy, hydroxy, amino, C^Cg-alkylamino, C-j-Cg-dialkylamino, wherein said two alkyl portions of said dialkylamino can form, togetherwith the nitrogen atom to which they are attached, a heterocycle selected from pyrrolidine, piperidine, morpholine and piperazine optionally N-substituted by C^Cg-alkyl or C3-C6-cycloalkyl, C3-C6-cycloalkylamino, C1-C6-alkyl-C3-C6-cy-cloalkylamino and C3-C6-dicycloalkylamino, or two groups on adjacent ring carbons form a fused 0-(CH2)q-0 group wherein q is 1 or 2, or two groups on adjacent ring carbons form a fused CH=CH-CH=CH group; or a pharmaceutically acceptable salt thereof, for use in the protection of a human or animal living body from ultraviolet radiation.

[0035] Some compounds included in formula (I) have not been described previously in the literature. Accordingly, the present invention relates to the new benzoic acid ester compounds of formula (la):

wherein R is a group selected from (i), (ii) and (iii):

wherein R-1-R5 are selected independently from hydrogen, C-pCg-alkyl, C3-C6-cycloalkyl, Ci-C6-alkoxy, C3-C6-cy-cloalkoxy, hydroxy, amino, Ci-C6-alkylamino, C1-C6-dialkylamino, wherein said two alkyl portions of said dialkylamino can form, together with the nitrogen atom to which they are attached, a heterocycle selected from pyrrolidine, piperidine, morpholine and piperazine optionally N-substituted by C^Cg-alkyl or C3-C6-cycloalkyl, C3-C6-cycloalkylamino, C1-C6-alkyl-C3-Cg-cycloalkylamino and C3-C6-dicycloalkylamino, or two groups on adjacent ring carbons form a fused 0-(CH2)m-0 group wherein m is 1 or 2, or two groups on adjacent ring carbons form a fused CH=CH-CH=CH group; R’ is hydrogen;

Rg-Rio are selected independently from hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, C.|-Cg-alkoxy, C3-C6-cycloalkoxy, hydroxy, amino, C^Cg-alkylamino, C^Cg-dialkylamino, wherein said two alkyl portions of said dialkylamino can form, togetherwith the nitrogen atom to which they are attached, a heterocycle selected from pyrrolidine, piperidine, morpholine and piperazine optionally N-substituted byCi-C6-alkylorC3-C6-cycloalkyl, C3-C6-cycloalkylamino, C1-C6-alkyl-C3-C6-cy-cloalkylamino and C3-C6-dicycloalkylamino, or two groups on adjacent ring carbons form a fused 0-(CH2)n-0 group wherein n is 1 or 2, or two groups on adjacent ring carbons form a fused CH=CH-CH=CH group; R^ is selected from hydrogen, C^Cg-alkyl and C3-C6-cycloalkyl; R12 is selected from hydrogen, C^Cg-alkyl and C3-C6-cycloalkyl; R13 and R14 are selected independently from hydrogen, C^Cg-alkyl, C3-C6-cycloalkyl, C^Cg-alkoxy, C3-C6-cycloalkoxy, hydroxy, amino, C1-C6-alkylamino, C^Cg-dialkylamino, wherein said two alkyl portions of said dialkylamino can form, togetherwith the nitrogen atom to which they are attached, a heterocycle selected from pyrrolidine, piperidine, morpholine and piperazine optionally N-substituted byCi-C6-alkylorC3-C6-cycloalkyl,C3-C6-cycloalkylamino,C1-C6-alkyl-C3-C6-cy-cloalkylamino and C3-C6-dicycloalkylamino; or the group OR12 and R14 form a fused 0-(CH2)p-0 group wherein p is 1 or 2; R15 is selected from 1-pyrrolidinyl, 1-piperidinyl, 4-morpholinyl and 1(4)-piperazinyl optionally 4(1)-substituted by C^Cg-alkyl or C3-C6-cycloalkyl; and R16-R18 are selected independently from hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, C-pCg-alkoxy, C3-C6-cycloalkoxy, hydroxy, amino, C1-C6-alkylamino, C^Cg-dialkylamino, wherein said two alkyl portions of said dialkylamino can form, togetherwith the nitrogen atom to which they are attached, a heterocycle selected from pyrrolidine, piperidine, morpholine and piperazine optionally N-substituted by C.|-C6-alkylorC3-C6-cycloalkyl, C3-C6-cycloalkylamino, C.|-C6-alkyl-C3-C6-cy-cloalkylamino and C3-C6-dicycloalkylamino, or two groups on adjacent ring carbons form a fused 0-(CH2)q-0 group wherein q is 1 or 2, or two groups on adjacent ring carbons form a fused CH=CH-CH=CH group; with the proviso that when R^ R2, and R4-R10 are each hydrogen, R3 cannot be hydrogen or methoxy; and with the proviso that when R-|-R7, Rg and R10 are each hydrogen, R8 cannot be methyl; or a pharmaceutically acceptable salt thereof.

[0036] More preferably the present invention relates to new benzoic acid ester compounds of formula (la) wherein in said compounds, when R is (i), R3 is selected independently from C^Cg-alkyl, C3-C6-cycloalkyl, C^Cg-alkoxy and C3-C6-cycloalkoxy, R8 is selected independently from hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, C^Cg-alkoxy and C3-C6-cycloalkoxy, and R^ R2, R4-R7, Rg and R10 are each hydrogen; when R is (ii), R-|-R5, R^, R13 and R14 are each hydrogen and R12isC.|-C6-alkyland C3-C6-cycloalkyl; and when R is (iii), R15 is selected from 1-pyrrolidinyl, 1-piperidinyl, 4-morpholinyl and 1(4)-piperazinyl optionally 4(1)-substituted by C^Cg-alkyl or C3-C6-cycloalkyl and R-ig-R-is are each hydrogen; with the proviso that when R-p R2, and R4-R10 are each hydrogen, R3 cannot be hydrogen or methoxy; and with the proviso that when R-|-R7, Rg and R10 are each hydrogen, R8 cannot be methyl; or a pharmaceutically acceptable salt thereof.

[0037] The term "pharmaceutically acceptable salt" used herein encompasses any salt formed from organic and inorganic acids, such as hydrobromic, hydrochloric, phosphoric, nitric, sulfuric, acetic, adipic, aspartic, benzenesulfonic, benzoic, citric, ethanesulfonic, formic, fumaric, glutamic, lactic, maleic, malic, malonic, mandelic, methanesulfonic, 1,5-naphthalendisulfonic, oxalic, pivalic, propionic, p-toluenesulfonic, succinic, tartaric acids and the like, or any metal salt wherein the metal is selected from sodium, potassium, lithium, calcium, magnesium, zinc, aluminum and the like, or ammonium salts, or any salt formed from organic bases, such as 2-amino-1 -butanol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, benzathine, benzyldimethylamine, chloroprocaine, choline, dibenzylmethylamine, diethanolamine, diisopropanolamine, ethylenediamine, dimethyl stearamine, meglumine, 2-methyl-2-amino-1-propanol, monoamine glycols, monoethanolamine, monoisopropanolamine, morpholine, Ν,Ν-dibenzylethylenediamine, N,N-dime-thyl-2-amino-2-methyl-1-propanol, Ν,Ν-dimethylaniline, procaine, pyridine, quinoline, t-butyl-dimethylamine, triethanolamine, triethylamine, trihydroxymethylaminomethane, triisopropanolamine, trimethylamine and the like, and salts with amino acids such as glycine, lysine, arginine, taurine, histidine, alanine, valine, cysteine and the like.

[0038] The preferred compounds to be used in the uses of the present invention are shown below: 1-phenylvinyl 4-methoxybenzoate; 1-(4-methoxyphenyl)-vinyl 4-tert-butylbenzoate; 1-(4-tert-butylphenyl)-vinyl 4-methoxybenzoate; 1-phenylvinyl 4-tert-butylbenzoate; 4-benzoyloxy-2-methoxybenzenesulfonic acid; and 3- (1-pyrrolidinyl)phenyl benzoate; [0039] The preferred new compounds of the present invention are shown below: 1-(4-methoxyphenyl)-vinyl 4-tert-butylbenzoate; 1-(4-tert-butylphenyl)-vinyl 4-methoxybenzoate; 1-phenylvinyl 4-tert-butylbenzoate; 4- benzoyloxy-2-methoxybenzenesulfonic acid; and 3-(1-pyrrolidinyl)phenyl benzoate.

[0040] Compounds of formula (I) when R is (i) can be obtained by a great variety of methods disclosed in the literature.

[0041] Schemes 1a-1e illustrate some representative synthetic examples thereof.

Xiang, J et al., J.Amer.Chem.Soc., 119(18), <1997>, 4123- 4129

Scheme la

Edwards; Hodges, J.Chem.Soc., <19b4>, 761

Scheme lb

Opstal, T et al., Syn.Lett., <2003>, 314-320

Scheme lc

Nakagawa, H et al., Tetrahedron Lett., 44(1), <2003>, 103-106 Scheme Id

Claisen; Haase, Chem.Ber., 36, <1903>, 3679

Scheme le [0042] Compounds of formula (I) when R is (ii) have not been described yet in the literature, and consequently the present invention relates to said group of compounds perse.

[0043] Compounds of formula (I) when R is (iii) are commercially available or can be obtained alternatively by known methods of organic chemistry.

[0044] The present invention also relates to a process to prepare the compounds of formula (la). When R is (i), the process comprises reacting an acyl halide of formula (II), wherein R1-R5 are as defined above, X is an halogen atom selected from the group consisting of fluorine, chlorine or bromine, preferably chlorine, with a silylenol of formula (III), wherein R’ and R6-R10 are as defined above and R19-R21 are selected independently from C-pCg-alkyl, C3-C6-cycloalkyl and C6H5-(CH2)r-, wherein r is 1-4, or two groups can form, together with thesilicium atom a ring selected from silolane, sililane and silepane (Scheme 2a)

Rl O „ H_,R' D Λ H_R'

Rig C Rg Rl o C Rg

Ro A, C 1la 11 10 I 11 11 I x r20-sl_c./L.R7 r2^J^c c^k.r7

rAA, + *2? YT -- YI YY 3 T 5 R10" Rs Rs^Y R5 R10 | Rs 4 Rg R4 Rg (II) (III) (la, R = (i))

Scheme 2a [0045] Said reaction occurs conveniently in the presence of a catalyst selected from the group consisting of mercuric chloride, cuprous chloride and mixtures thereof. Optional solvents can be selected from Ν,Ν-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-piperidone, 1,3-dimethyl-2-imidazolidinone, and the like, and mixtures thereof. Preferably the solvent is 1,3-dimethyl-2-imidazolidinone.

[0046] Intermediate silylenols of formula (III) can be prepared by standard chemical methods. However, some intermediate silylenols of formula (III) have not been described previously in the literature and are included in the present invention. A representative of the new intermediate silylenols is 4-tert-butylacetophenone trimethylsilylenol.

[0047] When R is (ii), the process comprises reacting a benzoic acid ester of formula (IV), wherein R1-R5 and R12-R-14 are as defined above, with chlorosulfonic acid followed by an optional esterification reaction with C-i-Cg-alkyl-OH or Cg-Cg-cycloalkyl-OH to afford the corresponding C1-C6-alkyl or C3-C6-cycloalkyl sulfonic ester final compounds. Alternatively the process comprises firstly sulfonating a phenol of formula (V) with chlorosulfonic acid followed by esterification with an acid intermediate (VII) wherein R1-R5 are as defined above. Likewise, esterifying the sulfonic acid intermediates (VI) with C^Cg-alkyl-OH or C3-C6-cycloalkyl-OH provides the corresponding C^Cg-alkyl or C3-C3-cycloalkyl sulfonic acid esters thereof, which can be esterified with (VII) to afford the corresponding C^Cg-alkyl orC3-C3-cycloalkyl sulfonic acid ester final compounds (Scheme 2b).

Scheme 2b [0048] When R is (iii), the process comprises reacting an acyl halide of formula (II), wherein R1-R5 are as defined above, X is an halogen atom selected from the group consisting of fluorine, chlorine or bromine, preferably chlorine, with a phenol of formula (VIII):

(VIII) wherein R15-R18 are as defined above (Scheme 2c)

[0049] It is also d isclosed herein the use of benzoic acid ester com pounds of form ula (I) or salts thereof as photochemical precursors of ultraviolet absorbers.

[0050] The present invention also relates to compositions containing at least a benzoic acid ester compound of formula (la) or salts thereof.

[0051] Cosmetic or pharmaceutical compositions comprising an effective amount of at least a benzoic acid ester compound of formula (I) or an acceptable salt thereof susceptible to be photochemically converted in situ to a sunscreen compound with enhanced UV protection ability are also disclosed herein.

[0052] It is also disclosed herein a method for protecting a human or animal living body from ultraviolet radiation with a cosmetic or pharmaceutical composition comprising an effective amount of at least a benzoic acid ester compound of formula (I) or an acceptable salt thereof susceptible to be photochemically converted in situ to a sunscreen compound with enhanced UV protection ability.

[0053] It is also disclosed herein a method for protecting a human or animal living body from ultraviolet radiation with a cosmetic or pharmaceutical composition comprising an effective amount of at least a benzoic acid ester compound of formula (I) or an acceptable salt thereof susceptible to be photochemically converted in situ to a sunscreen compound with enhanced UV protection ability, wherein the human or animal living body is a human being.

[0054] Such compositions typically range from 0.01 to 40 wt % based on the total weight of the sunscreen. More typically, the amount falls within the range of 0.05 wt % to 25 wt %. The amount of organic sunscreen compound of formula (I) preferably ranges from about 0.1 wt % to about 15 wt % of the sunscreen formulation.

[0055] These sunscreen formulations can contain one or more additional organic sunscreen agents for filtering UVB or UVA rays or they may additionally contain one or more metal oxide sunscreen agents such as titanium dioxide or zinc oxide.

[0056] These sunscreen formulations may additionally contain a carrier and at least one component selected from the group consisting of dispersing agents, preservatives, anti-foams, perfumes, fragrances, oils, waxes, propellants, dyes, pigments, emulsifiers, surfactants, thickeners, humectants, exfoliants and emollients. These sunscreen formulations may be in the form of a cosmetic composition with a cosmetically acceptable carrier and one or more cosmetic adjuvants. The sunscreen formulation can optionally have conventional antioxidants or other stabilizers without UV absorbing characteristics.

[0057] Other ingredients referred to above and discussed more particularly below are generally used in an amount from about 0.1 wt % to about 10 wt % of the sunscreen formulation. The balance comprises a cosmetically or pharmaceutically acceptable carrier.

[0058] Suitable dispersing agents for the sunscreen formulations include those useful for dispersing organicor inorganic sunscreen agents in either a water phase, oil phase, or part of an emulsion, including, for example, chitosan.

[0059] Emulsifiers may be used in the sunscreen formulations to disperse one or more of the compounds of formula (I) or other components of the sunscreen formulation. Suitable emulsifiers include conventional agents such as, for example, glycerol stearate, stearyl alcohol, cetyl alcohol, dimethicone copolyol phosphate, hexadecyl-D-glucoside, oc-tadecyl-D-glucoside, etc.

[0060] Thickening agents may be used to increase the viscosity of the sunscreen formulations. Suitable thickening agents include carbomers, acrylate/acrylonitrile copolymers, xanthan gum and combinations of these. The carbomer thickeners include the crosslinked acrylic polymers. The amount of thickener within the sunscreen formulation, on a solids basis without water, may range from about 0.001 to about 5%, preferably from 0.01 to about 1% and optimally from about 0.1 to about 0.5% by weight.

[0061] Minor optional adjunct ingredients for the sunscreen formulations to be applied to skin or hair may include preservatives, waterproofing agents, fragrances, antifoam agents, plant extracts (aloe vera, witch hazel, cucumber, etc) opacifiers, skin conditioning agents and colorants, each in amounts effective to accomplish their respective functions.

[0062] The sunscreen formulations may optionally contain an ingredient which enhances the waterproof properties such as, compounds that form a polymeric film, such as dimethicone copolyol phosphate, diisostearoyl trimethylolpropane siloxysilicate and dilauroyl trimethylolpropane siloxysilicate, chitosan, dimethicone, polyethylene, polyvinylpyrrolidone (PVP), PVP/vinylacetate, PVP/eiconsene copolymer, adipic acids/diethylene glycol/glycerine crosspolymer and the like. Waterproofing agents may be present at levels of from about 0.01 to about 10% by weight.

[0063] The sunscreen formulations may also optionally contain one or more skin conditioning agents. These include humectants, exfoliants and emollients.

[0064] Humectants are polyhydric alcohols intended for moisturizing, reducing scaling and stimulating the removal of built scale from the skin. Typically polyhydric alcohols include polyalkylene glycols and more preferably alkylene polyols and their derivatives. Illustrative are propylene glycol, dipropylene glycol, polypropylene glycol, polyethylene glycol, sorbitol, 2-pyrrolidone-5-carboxylate, hydroxypropyl sorbitol, hexylene glycol, ethoxydiglycol 1,3-butylene glycol, 1,2,6-hexanetriol, glycerin, ethoxylated glycerin, propoxylated glycerin and mixtures thereof. Most preferably the humectant is glycerin. Amounts of humectant can range anywhere from 1 to 30%, preferably from 2 to 20% and optimally from about 5 to 10% by weight of the sunscreen composition.

[0065] The exfoliants suitable for use in the present invention may be selected from alpha-hydroxy carboxylic acids, beta hydroxycarboxylic acids and salts of these acids. Most preferred are glycolic, lactic and salicylic acids and their alkali, metal or ammonium salts.

[0066] Suitable emollients include those agents known for softening the skin or hair which may be selected from hydrocarbons, fatty acids, fatty alcohols and esters. Petrolatum is a common hydrocarbon type of emollient conditioning agent. Other hydrocarbons that may be employed include alkyl benzoates, mineral oils, polyolefins such as polydecene, and paraffins, such as isohexadecane. Fatty acids and alcohols typically have from about 10 to 30 carbon atoms. Illustrative are myristic, isostearic, hydroxystearic, oleic, linoleic, ricinoleic, behenic and eruicic acids and alcohols. Oily ester emollients may be those selected from one or more of the following triglyceride esters, acetoglyceride esters, ethoxylated glycerides, alkyl esters of fatty acids, ether esters, polyhydric alcohol esters and wax esters. Additional emollients or hydrophobic agents include C12 to C15 alkyl benzoates, dioctyladipate, octyl stearate, octyldodecanol, hexyl laurate, octyldodecyl neopentanoate, cyclomethicone, dicapryl ether, dimethicone, phenyl trimethicone, isopropyl myristate, caprylic/capric glycerides, propylene glycol dicaprylate/dicaprate and decyl oleate.

[0067] The sunscreen formulations may optionally contain one or more inorganic sunscreen agents as discussed above including micro fine surface treated titanium dioxide and micro fine untreated and surface treated zinc oxide. Titanium dioxide in the sunscreen compositions preferably has a mean primary particle size of between 5 and 150 nm and preferably from 10 to 100 nm. The zinc oxide in the sunscreen compositions preferably has a mean primary particle size of between 5 nm and 150 nm, preferably between 10 nm and 100 nm.

[0068] The sunscreen compositions may also contain one or more additional monomeric organic chromophoric compounds. These can either be UVA, UVB or broad band filters. Examples of suitable UVA sunscreens include benzophe-none derivatives, menthyl anthranilate, butyl methoxydibenzoyl methane and benzylidene-dioxoimidazoline derivatives. Examples of suitable UVB sunscreens include cinnamate derivatives, salicylate derivatives, p-aminobenzoic acid derivatives, camphor derivatives, phenylbenzimidazole derivatives and diphenylacrylate derivatives. Examples of suitable broad-band sunscreen include benzotriazole derivatives and triazine derivatives such as anisotriazone. Others include ethylhexyltriazoneanddiethylhexylbutamidotriazone. Particularly useful organic sunscreen agents that can be introduced are avobenzone, 2-ethylhexyl p-methoxycinnamate, oxybenzone, octyldimethyl p-aminobenzoic acid, dioxybenzone, ethyl-4-[bis(hydroxypropyl)]aminobenzoate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, 2-ethylhexylsalicylate, glycerol p-aminobenzoate, 3,3,5-trimethylcyclohexylsalicylate, methylanthranilate, p-dimethylaminobenzoicacid, 2-ethylhexyl p-dimethylaminobenzoate, 2-phenyl benzimidazole-5-sulfonic acid, 2-p-dimethylaminophenyl-5-sulfoniobenzoxazoic acid, sulisobenzone, and mixtures thereof. Examples of useful commercially available organic sunscreen agents that can be introduced include 2-phenylbenzimidazole-5-sulphonic acid, 2-(4-methylbenzylidene)-camphor and 4-isopropyldiben-zoylmethane. Although not preferred, the sunscreen formulation may contain an additional antioxidant. Examples of suitable antioxidants which provide stability include p-hydroxybenzoicacid and its esters, salicylates, cumarin derivatives, flavones, hydroxy or methoxy substituted benzophenones, uric or tannic acid and its derivatives, hydroquinone, and benzophenones.

[0069] In addition to providing sunscreen activity at levels which provide UV absorption, the compounds of formula (I) can be introduced into a skin care formulation, a hair care formulation or other personal care formulations such as cosmetic or pharmaceutical compositions at levels which provide antioxidant activity. These compounds can be used with or without conventional antioxidants in personal care formulations such as hair care, skin care and cosmetic and pharmaceutical compositions.

[0070] In the cosmetics field, and in particular for make-up compositions such as foundation compositions, tinted creams, mascaras, blushers and eye shadows, lipsticks and nail varnishes, pigments are being sought which are capable of imparting to these various types of products a varied palette of colorations which are reproducible over time and are insoluble in most of the cosmetic media used such as water and cosmetically acceptable solvents. These pigments should, moreover, be stable at the pHs usually used or encountered in the cosmetics field.

[0071] Cosmetic or pharmaceutical products, such as skin lotions, collagen creams, sunscreen, facial make-up, etc., comprise synthetic materials such as antifoams, antioxidants, antiperspirants, colorants, dyes, emollients, emulsifiers, exfoliants, humectants, lipids, moisturizers, perfumes, fragrances, pigments, preservatives, propellants, skin conditioners, solvents, surfactants, thickeners, water proofing agents, etc.; as well as natural products such as collagen, proteins, mink oil, olive oil, coconut oil, carnauba wax, beeswax, lanolin, cocoa butter, xanthan gum, aloe, etc.

[0072] It is also disclosed herein a method to improve the photostability of a sunscreen formulation that comprises adding at least a benzoic acid ester compound of formula (I) or an acceptable salt thereof to said sunscreen composition in an amount sufficient to improve the photostability of said sunscreen agent.

[0073] The present invention also relates to a personal care composition which comprises at least a benzoic acid ester compound of formula (la) or an acceptable salt thereof in an amount effective to photostabilize composition ingredients from sun radiation.

[0074] The cosmetic, pharmaceutical and personal care compositions can be in the form of creams, ointments, milks, suspensions, powders, oils, lotions, gels, sticks, foams, emulsions, dispersions, sprays and aerosols, and the like. More specific forms include lipsticks, foundations, makeup, loose or press powders, eye blushes, eye shadows, mascaras, nail varnishes, nail lacquers and non permanent dyeing compositions for the hair, and the like.

[0075] It is also disclosed herein the use of compounds of formula (I) to prepare cosmetic or pharmaceutical compositions and, personal care compositions that, upon phototransformation, indicate the amount of UVB radiation received.

[0076] The compounds of the present invention are typically employed in amounts from about 0.01 to about 30% by weight, preferably from about 0.05 to about 20% by weight, and most preferably from about 0.1 to about 10% by weight, based on the weight of the material to be stabilized.

The compounds of the present invention can be incorporated into such materials in any one of a variety of conventional procedures, including for example, physical mixing or blending, optionally, with chemical bonding to the material (typically to a polymer), as a component in a light stabilizing or oxidation composition such as a coating or solution, or as a component in a UV screening composition such as a sunscreen composition. Natural or synthetic rubbers such as natural latex or lattices of carboxylated styrene/butadiene copolymers may be formulated as aqueous emulsions.

[0077] Organic dyes encompass azo dyes (diazo, triazo and polyazo), anthraquinones, benzodifuranones, polycyclic aromatic carbonyl dyes, indigoid dyes, polymethines, styryl dyes, di- and triaryl carbonium dyes, phthalocyanines, qui-nophthalones, sulfurdyes, nitro and nitroso dyes, stilbene dyes, formazan dyes, quinacridones, carbazoles and perylene tetracarboxylic diimides.

[0078] When compositions are used in the form of emulsions, they may additionally contain surface-active agents which are well known in the state of the art, such as anionic, nonionic, cationic or amphoteric surface-active agents or mixtures thereof.

[0079] These compositions may also contain fatty substances, organic solvents, silicones, thickening agents, softening agents, surfactants, sunscreen agents, anti-free-radical agents, anti-foaming agents, moisturizing agents, fragrances, preserving agents, antioxidants, fillers, sequestering agents, treatment agents such as nonionic, cationic, anionic or amphoteric polymers or mixtures thereof, propellants, and basifying or acidifying agents, or other pigments.

[0080] The fatty substances may consist of an oil or a wax or mixtures thereof, fatty acids, fatty alcohols, fatty acid esters, vaseline, paraffin, lanolin, hydrogenated lanolin or acetylated lanolin.

[0081] The oils are chosen from animal oils, vegetable oils, mineral oils or synthetic oils and especially hydrogenated palm oil, hydrogenated castor oil, liquid paraffin, paraffin oil, purcellin oil and silicone oils.

[0082] The waxes are chosen from animal waxes, fossil waxes, vegetable waxes, mineral waxes or synthetic waxes. Beeswaxes, carnauba wax, candelilla wax, sugar cane wax, Japan wax, ozokerites, montan wax, microcrystalline waxes and paraffin waxes may more particularly be mentioned.

[0083] The sunscreen activity of the benzoic acid ester compounds of the present invention is based on efficient phototransposition reactions showing a high chemical yield.

[0084] The phototransposition of compounds of formula (I) when R is (i) provides dibenzoylmethane compounds of formula (IX), according to Scheme 3.

Scheme 3 [0085] Such dibenzoylmethane compounds constitute a recognized chemical sunscreen series, being avobenzone the most representative. Thus, phototransposition of both 1-(4-methoxyphenyl)-vinyl 4-tert-butylbenzoate and 1-(4-tert-butylphenyl)-vinyl 4-methoxybenzoate yields the authorized and widely used avobenzone sunscreen compound.

[0086] The photo-Fries transposition of compounds of formula (I) wherein R is (ii) or (iii) provides benzophenone compounds of formula (X), according to Scheme 4:

Scheme 4 [0087] Such benzophenone compounds constitute a recognized and widely used chemical sunscreen series. Dioxy-benzone, oxybenzone and sulisobenzone are the most representative compounds in said series. Phototransposition of both 3-methoxyphenylsalicylate and phenyl 4-methoxysalicylate provides dioxybenzone. Phototransposition of 3-meth-oxyphenyl benzoate leads tooxybenzone. And phototransposition of 4-benzoyloxy-2-methoxybenzenesulfonic acid leads to sulisobenzone.

[0088] The photo-Fries transposition of compounds of formula (I) wherein R15 is a dialkylamino group provides a recent sunscreen benzophenone series, being 4-diethylamino-2-hydroxybenzophenone and 2-hydroxy-4-(1-pyrrolidinyl)benz-ophenone the most representative compounds in said series. Phototransposition of 3-diethylaminophenyl benzoate and 3-(1-pyrrolidinyl)phenyl benzoate provides 4-diethylamino-2-hydroxybenzophenone and 2-hydroxy-4-(1-pyrrolidi-nyl)benzophenone respectively.

[0089] The compounds of formula (I) show a progressive UV protection depending on the time to sun exposition and the degree of sun radiation. This progressive UV protection property is evidenced in their UVB and particularly UVA screening ability. Consequently, the compositions containing compounds of formula (I) constitute a safer method to take sunbaths and produce a more uniform and glamorous tanning than conventional sunscreens. Moreover the compounds resulting from the phototranspositions belong to recognized chemical sunscreen series which ensure the convenience of the method.

[0090] Accordingly, it is also disclosed herein the use of compounds of formula (I) to prepare cosmeticor pharmaceutical compositions, personal care compositions and industrial compositions characterized by a progressive UV protection depending on the time to sun exposition and the degree of sun radiation.

[0091] The following non-limiting examples illustrate the scope of the present invention.

Preparation example 1: 4-Methoxyacetophenone trimethylsilylenol [0092] A solution of 0.82 g (5.5 mmol) of 4-methoxyacetophenone in 3.4 mL of tetrahydrofuran was added to 7 mmol of lithium diisopropylamine (LDA) generated In situ. After stirring the solution for 30 minutes, 4.5 mL of trimethylsilyl chloride were added and the mixture was stirred for 17 h at room temperature under nitrogen atmosphere. Then pentane was added, the mixture was filtered to remove the lithium salts and the solvent was evaporated to dryness under reduced pressure. The obtained crude contained 78% (1H-NMR) of 4-methoxyacetophenone trimethylsilylenol. 1H-NMR: 3.78 (s, 3H), 4.32 (d, 1H, J = 2 Hz), 4.79 (d, 1H, J = 2 Hz), 6.85 (d, 2H, J = 9 Hz), 7.52 (d, 2H, J = 9 Hz) Preparation of LDA: Linder nitrogen atmosphere, 0.97 mL of distilled diisopropylamine were dissolved in 7 mL of anhydrous tetrahydrofuran at 0°C. Then 4.4 mL of butyl lithium 1,6M in hexane were added and the mixture was stirred for 20 minutes.

Preparation example 2: 4-Tert-butylacetophenone trimethylsilylenol [0093] A solution of 1.25 mL (6.7 mmol) of 4-ferf-butylacetophenone in 4 mL of tetrahydrofuran was added to LDA (7 mmol) generated in situ. After stirring the solution for 30 minutes, 4.5 mL of trimethylsilyl chloride were added and the mixture was stirred for 16 h at room temperature under nitrogen atmosphere. Then pentane was added, the mixture was filtered to remove the lithium salts and the solvent was evaporated to dryness under reduced pressure. The obtained crude contained 100% (1H-NMR) of 4-tert-butylacetophenone trimethylsilylenol. 1H-NMR: 1.32 (s, 9H), 4.38 (d, 1H, J = 2 Hz), 4.87 (d, 1H, J = 2 Hz), 7.34 (d, 2H, J = 9 Hz), 7.52 (d, 2H, J = 9 Hz)

Preparation example 3: 1-Phenylvinyl 4-tert-butylbenzoate [0094] A mixture of 4.16 g (21.62 mmol) of acetophenone trimethylsilylenol, 4.33 g (22.01 mmol) of 4-tert-butylbenzoyl chloride and 136 mg of mercuric chloride was heated at 100°C for 2 h. The mixture was then left to cool, water was added over the reaction crude and extracted with dichloromethane. The organic phase was dried over magnesium sulfate and the solvent was removed under reduced pressure. A 2.12 g sample was purified by flash chromatography (hex-ane:dichloromethane 3:1) giving 1.17 g of 1-phenylvinyl 4-tert-butylbenzoate. Yield 57%. 1H-NMR: 1.36 (s,9H),5.14(d, 1H, J = 2Hz),5.58 (d, 1H, J =2 Hz), 7.32 (m, 3H), 7.53(m, 2H), 8.13 (dt, 2 H, J =9 Hz, 2 Hz). 13C-NMR: 164.63/s -CO-, 157.23/s -C=CH2, 153.03/s -C-C-(CH3)3, 134.28/s -C-C=CH2, 129.94/d 2 CH aromatic, 128.81/d 1 CH aromatic, 128.41/d 2 CH aromatic, 126.55/s -C-CO-, 125.50/d 2 CH aromatic, 124.81/d 2 CH aromatic, 102.14/t CH2, 35.26/s -C-(CH3)3, 31.18/q 3 CH3. IR: 1737, 1642, 1607, 1249 cm'1.

Preparation example 4: 1-Phenylvinyl 4-methoxybenzoate [0095] A mixture of 2.38 g (12.37 mmol) of acetophenone trimethylsilylenol, 2.15 g (12.60 mmol) of 4-methoxybenzoyl chloride and 93 mg of mercuric chloride was heated at 100°C for 2 h. The mixture was then left to cool to room temperature, and then water was added over the reaction crude, and extracted with dichloromethane. The organic phase was dried over magnesium sulfate and the solvent was removed under reduced pressure. The obtained crude contained 75-85% of 1-phenylvinyl 4-methoxybenzoate as determined by 1H-NMR.

Preparation example 5: 1-(4-Methoxyphenyl)-vinyl 4-tert-butylbenzoate [0096] 4-tert-butylbenzoyl chloride (1.78 g, 9 mmol), 0.47 g of cuprous chloride and 4 mL of 1,3-dimethyl-2-imidazo-lidinone were added to crude 4-methoxyacetophenone trimethylsilylenol (4.3 mmol). After stirring the solution for 21 hours at room temperature, 1 mL of triethylamine and 10 mL of chloroform were added. Then the solution was chroma-tographied through flash silica column (hexane/ethyl acetate 10:1). The first collected fraction was purified by flash chromatography (hexane/dichloromethane 3:2) giving 0.34 g of 1-(4-methoxyphenyl)-vinyl 4-tert-butylbenzoate. Yield 25%. 1H-NMR: 1.37 (s, 9H), 3.80 (s, 3H), 5.03 (d, 1H, J = 2 Hz), 5.46 (d, 1H, J = 2 Hz), 6.85 (dt, 2H, J = 2 Hz, 9 Hz), 7.46 (dt, 2H, J = 2 Hz, 9 Hz), 7.52 (dt, 2H, J = 2 Hz, 9 Hz), 8.12 (dt, 2H, J = 2 Hz, 9 Hz). 13C-NMR: 164.69/s -CO-, 159.99/s -C-OCH3,157.18/s -C=CH2,152.83/s -C-C-(CH3)3,129.93/d 2 CH aromatic, 126.94/s 1 CH aromatic, 126.63/s 1 CH aromatic, 126.25/d 2 CH aromatic, 125.50/d 2 CH aromatic, 113.84/d 2 CH aromatic, 100.27/t CH2, 55.33/q CH3-0, 35.26/s -C-(CH3)3, 31,18/q 3 CH3. IR: 1735, 1608, 1512, 1245, 1176, 1095 cm-1.

Mp: 87-89°C

Preparation example 6: 1-(4-Tert-butylphenyl)-vinyl 4-methoxybenzoate [0097] 4-methoxybenzoyl chloride (2.35 g, 13.8 mmol), 0.65 g of cuprous chloride and 5.6 mL of 1,3-dimethyl-2-imidazolidinone were added to crude 4-ferf-butylacetophenone trimethylsilylenol (6.7 mmol). After stirring the solution for 20 hours at room temperature, 1.4 mL of triethylamine and 10 mL of chloroform were added. Then the solution was chromatographied through flash silica column (hexane/ethyl acetate 10:1). The first collected fraction was purified twice by flash chromatography (hexane/dichloromethane 3:2 and next, hexane/dichloromethane 4:1) giving 0.14 g of an uncolored oil corresponding to 1-(4-ferf-butylphenyl)-vinyl 4-methoxybenzoate. Yield 7%. 1H-NMR: 1.29 (s, 9H), 3.86 (s, 3H), 5.09 (d, 1H, J = 2 Hz), 5.53 (d, 1H, J = 2 Hz), 6.97 (2H), 7.35 (dt, 2 H, J = 2 Hz, 9 Hz), 7.46 (dt, 2H, J = 2 Hz, 9 Hz), 8.15 (dt, 2H, J = 2 Hz, 9 Hz). 13C-NMR: 164.37/s -CO-, 163.63/s -C-OCH3,153.01/s -C=CH2,151,80/s -C-C-(CH3)3,132.06/d 2 CH aromatic, 131,42/s -C-C=CH2, 125.32/d2CH aromatic, 124.48/d 2 CH aromatic, 121.67/s C-CO, 113.72/d2CH aromatic, 101.29/tCH2, 55.44/q CH3-0, 34.62/s -C-(CH3)3, 31.21/q 3 CH3. IR: 1732, 1606, 1510, 1246, 1167, 1090 cm-1.

Preparation example 7: 4-Benzoyloxy-2-methoxybenzenesulfonic acid [0098] A solution of 0.47 mL (7.01 mmol) of chlorosulfonic acid in 7 mL of dichloromethane was added drop by drop to a solution of 1.6 g (7.01 mmol) of 3-methoxyphenyl benzoate in 12 mL of dichloromethane at 0°C. Once the addition was completed, the mixture was left to react for 18 h at room temperature. The formed precipitate was filtered, giving 300 mg of 4-benzoyloxy-2-methoxybenzenesulfonic acid. Yield 15%. 1H-NMR: 3.76 (s, 3H), 6.77 (dd, 1H, J = 2 Hz, 8 Hz), 6.94 (d, 1H, J = 2 Hz), 7.62 (m, 2H), 7.76 (m, 2H), 8.15 (m, 2H). 13C-NMR: 164.23/s CO, 156.84/s C-OCH3, 151,87/s C-OCOPh, 133.89/d 1 CH aromatic, 133.21/s C-COO, 129.64/d2 CH aromatic, 128.89/d 1 CH aromatic, 128.81 /d 2 CH aromatic, 128.73/s C-SOsH, 112.03/d 1 CH aromatic, 106.04/d 1 CH aromatic, 55.84/d CH3. IR: 3500, 1727, 1264, 1198 cm-1.

Reference Preparation example 8: 3-Diethylaminophenyl benzoate (not according to the invention) [0099] A mixture of 1.53 g (9.3 mmol) of 3-diethylaminophenol, 1.35 mL (11.8 mmol) of benzoyl chloride and 1 mL of pyridine in 50 mL of toluene was refluxed for 3 hours. The mixture was then left to cool and the solvent was removed by distillation under reduced pressure. The obtained crude was purified by flash chromatography (hexane/ethyl acetate 7:1) providing a red oil fraction (235 mg) containing mainly 3-diethylaminophenyl benzoate.

Reference Preparation example 9: 3-Methoxyphenyl benzoate [0100] Phosphorus oxychloride (3.16 mL) was added over a mixture of 2.95 g (24.16 mmol) of benzoic acid and 3 g (24.16 mmol) of 3-methoxyphenol, and the resulting mixture was heated at 125°Cfor45 minutes under argon atmosphere. The mixture was cooled to room temperature, water was added over the reaction crude and extracted with diethyl ether. The organic phase was dried over magnesium sulfate and the solvent was removed under reduced pressure yielding 5.0 g of a dark red oil. The obtained crude was purified by flash chromatography (hexane/ethyl acetate 10:1) to afford 2.10 g of 3-methoxyphenyl benzoate. Yield 38%.

Reference Preparation example 10: Phenyl 4-methoxysalicylate [0101] Phosphorus oxychloride (2 mL) was added over a mixture of 2.00 g (11.89 mmol) of 4-methoxysalicylic acid and 2.13 g (22.65 mmol) of phenol, and the resulting mixture was heated at 115°C for 15 minutes under argon atmosphere. The mixture was cooled to room temperature, water was added over the reaction crude and extracted with dichloromethane. The organic phase was dried over magnesium sulfate and the solvent was removed under reduced pressure yielding 4.5 g of a dark red oil. The obtained crude was purified by flash chromatography (hexane/ethyl acetate 8.5:1) to afford 1.97 g of phenyl 4-methoxysalicylate. Yield 65%.

Reference Preparation example 11: 3-Methoxyphenyl salicylate [0102] Phosphorus oxychloride (2 mL) was added over a mixture of 2.00 g (14.48 mmol) of salicylic acid and 3.3 mL (28.96 mmol)of3-methoxyphenol, and the resulting mixture was heated at 115°C for 15 minutes under argon atmosphere. The mixture was cooled to room temperature, water was added over the reaction crude and extracted with dichlorometh-ane. The organic phase was dried over magnesium sulfate and the solvent was removed under reduced pressure yielding 4.0 g of a black oil. The obtained crude was purified by flash chromatography (hexane/ethyl acetate 9:1) to afford 2.36 g of 3-methoxyphenyl salicylate. Yield 85%.

Preparation example 12: 3-(1-pyrrolidinyl)phenyl benzoate [0103] A mixture of 1.52 g (9.3 mmol) of 3-(1-pyrrolidinyl)phenol, 1.35 mL (11.8 mmol) of benzoyl chloride and 1 mL of pyridine in 50 mL of toluene was refluxed for 3 hours. The mixture was then left to cool and the solvent was removed by distillation under reduced pressure. The obtained crude was purified by flash chromatography (hexane/ethyl acetate 7:1) providing a red oil fraction (233 mg) containing mainly 3-(1-pyrrolidinyl)phenyl benzoate.

Phototransposition example 1: Phototransposition of 1-phenylvinyl 4-methoxybenzoate [0104] A solution of 5 mg of 1-phenylvinyl 4-methoxybenzoate in 10 mL of methanol was irradiated with UVB lamps (60 W-nr2) for 20 minutes at 35°C. The crude reaction spectrum showed a new absorption band in UVA zone due to dibenzoylmethane fragment. The conversion to benzoyl-4-methoxybenzoyl-methane was observed from the beginning, being the complete conversion in 5 minutes. The phototransposition kinetics is shown in Figure 1.

Phototransposition example 2: Phototransposition of 1-(4-methoxyphenyl)-vinyl 4-tert-butylbenzoate [0105] A sample of 4 mL of a solution containing 0.231 mg of 1-(4-methoxyphenyl)-vinyl 4-tert-butylbenzoate in 50 mL of methanol was irradiated with UVB lamps (60 W-nr2) for 10 minutes at 35°C. The conversion to avobenzone was completed in 5 minutes. The phototransposition kinetics is shown in Figure 2.

Phototransposition example 3: Phototransposition of 1-(4-tert-butylphenyl)-vinyl 4-methoxybenzoate [0106] A sample of 4 mL of a solution containing 0.400 mg of 1-(4-tert-butylphenyl)-vinyl 4-methoxybenzoate in 50 mL of methanol was irradiated with UVB lamps (60 W-rrr2) for 10 minutes at 35°C. The conversion to avobenzone was completed in 5 minutes. The phototransposition kinetics is shown in Figure 3.

Phototransposition example 4: Phototransposition of 4-benzoyloxy-2-methoxybenzenesulfonic acid [0107] Asolution containing 5 mgof4-benzoyloxy-2-methoxybenzenesulfonicacid in 10 mL of methanol was irradiated with UVB lamps (60 W-nr2) for 20 minutes at 35°C. The absorption spectrum was then recorded minute by minute. The conversion to sulisobenzone was complete in 10 minutes. The phototransposition kinetics is shown in Figure 4.

Phototransposition example 5: Phototransposition of 3-diethylaminophenyl benzoate [0108] A sample of 4 mL of a solution containing 0.395 mg of 3-diethylaminophenyl benzoate in 50 mL of methanol was irradiated with UVB lamps (60 W-nr2) for 20 minutes at 35°C. The phototransformation to 4-diethylamino-2-hy-droxybenzophenone was completed in 10 minutes. The phototransposition kinetics is shown in Figure 5.

Phototransposition example 6: Phototransposition of 3-methoxyphenyl benzoate [0109] A sample of 5 mg of 3-methoxyphenyl benzoate in 10 mL of polydimethylsiloxane (viscosity 10000 cSt) was irradiated with UVB lamps (60 W-m"2) for 15 hours and 20 minutes at 35°C. The phototransformation to oxybenzone was completed in 40 minutes. The phototransposition kinetics is shown in Figure 6.

Phototransposition example 7: Phototransposition of 1-phenylvinyl 4-tert-butylbenzoate [0110] Asolution of 5 mg of 1-phenylvinyl 4-tert-butylbenzoate in 10 mL of tert-butanol was irradiated with UVB lamps (60 W-rrr2) for 5 hours at 35°C. Some different compounds were detected by thin layer chromatography (hexane/ethyl acetate 2:1), one of said compounds being benzoyl-4-tert-butylbenzoylmethane, desmethoxyavobenzone, identified by 1H-NMR.

Composition example 1: Sunscreen Composition 1

Procedure [0111] Phase B ingredients were combined. The mixture was stirred and heated to 70-75°C. Phase A ingredients were combined. The mixture was heated to 70-75°C while stirring. Phase B was added to phase A while stirring. Preservative was added. The mixture was stirred, allowing to cool to room temperature.

Composition example 2: Sunscreen Oil/Water Spray Lotion

Procedure [0112] The A-1 ingredients were combined; the mixture was stirred and heated to 60°C until all solids were dissolved. A-2 was dispersed in A-1 with agitation. The B-1 ingredients were combined; the mixture was stirred and heated to 60°C. B-2 was dispersed in B-1 with agitation. A was added to B while stirring vigorously. The mixture was gently homogenized allowing to cool to40°C. C was added to A/B; the mixture was gently homogenized until mixture was uniform. The mixture was stirred with another mixer allowing mixture to reach 25°C prior to packaging. Dispensing is made conveniently by a high shear pump spray device.

Composition example 3: Sunscreen Cream

Procedure [0113] Phase A ingredients were added to a main vessel under impeller agitation. The mixture was heated to 75-80°C. Phase B ingredients were combined; the suspension was heated and mixed to 85°C. Phase B was added slowly to batch and mixed for 15 minutes at 85°C. After removing the mixture from heat, it was switched to paddle mixing and cooled to room temperature.

Composition example 4: Water/Oil

Broad Spectrum Sunscreen Lotion (continued)

Composition example 5: UVA/UVB Sun Protection Cream with Avobenzone

Procedure [0114] Phase A-1 ingredients were combined; the mixture was heated to 50°C while stirring until methylparaben was dissolved. A-2 was dispensed in A-1 with a sifter. The resulting mixture A was heated to 65°C. Phase B ingredients were combined; the mixture was heated to 65-70°C while stirring until solids were dissolved. B was added to A. The mixture was homogenized and C was added at 55-60°C. Homogenizing was continued allowing mixture to cool to 40-45°C. Phase D was added; the mixture was stirred with propeller mixer until uniform. pH was adjusted to 6.5-7.0 with triethanolamine.

Composition example 6: Oil/water Sunscreen Lotion

(continued)

Procedure [0115] Phase B was prepared by dispersing Carbopol in water. The dispersion was heated to 70-75°C. Phase A ingredients were combined. The mixture was stirred and heated to 70-75°C. Phase B was added to phase A while stirring. Phase C was added. The mixture was homogenized until it cooled to45-40°C. Phase D was added. The mixture was stirred allowing to cool to room temperature.

Composition example 7: Oil/water Sunscreen Lotion with Avobenzone

Procedure [0116] Phase B was prepared by dispersing Carbopol in water. The dispersion was heated to 70-75°C. Phase A ingredients were combined. The mixture was stirred and heated to 70-75°C. Phase B was added to phase A while stirring. Phase C was added. The mixture was homogenized until it cooled to 45-40°C. Phase D was added. The mixture was stirred allowing to cool to room temperature.

Composition example 8: Sun Care Lipstick

Composition example 9: Sunscreen Gel

Composition example 10: Sunscreen Cream

(continued)

Composition example 11: Water-resistant Sunscreen Cream

Composition example 12: Sunscreen Milk

(continued)

Composition example 13: Sunscreen Makeup Powder

Composition example 14: Sunscreen Nail Varnish

Claims 1. Benzoic acid ester compounds of formula (I):

wherein R1-R5 are selected independently from hydrogen, C^Cg-alkyl, C3-Cg-cycloalkyl, C^Cg-alkoxy, C3-C6-cy-cloalkoxy, hydroxy, amino, C1-C6-alkylamino, CrC6-dialkylamino, wherein said two alkyl portions of said dialkylami-no can form, together with the nitrogen atom to which they are attached, a heterocycle selected from pyrrolidine, piperidine, morpholine and piperazine optionally N-substituted by C-j-Cg-alkyl or C3-C6-cycloalkyl, C3-C6-cy-cloalkylamino, C.|-C6-alkyl-C3-C6-cycloalkylamino and C3-C6-dicycloalkylamino, or two groups on adjacent ring carbons form a fused 0-(CH2)m-0 group wherein m is 1 or 2, or two groups on adjacent ring carbons form a fused CH=CH-CH=CH group; R is a group selected from (i), (ii) and (iii):

wherein R’ is selected from hydrogen, C1-C6-alkyl and C3-C6-cycloalkyl;

Rg-Rio are selected independently from hydrogen, C-j-Cg-alkyl, C3-C6-cycloalkyl, C-j-Cg-alkoxy, C3-C6-cycloalkoxy, hydroxy, amino, C1-C6-alkylamino, C-j-Cg-dialkylamino, wherein said two alkyl portions of said dialkylamino can form, together with the nitrogen atom to which they are attached, a heterocycle selected from pyrrolidine, piperidine, morpholine and piperazine optionally N-substituted by C.|-Cg-alkyl or C3-C6-cycloalkyl, C3-C6-cycloalkylamino, C^Cg-alkyl-Cj-Cg-CyCloalkylamino and C3-C6-dicycloalkylamino, or two groups on adjacent ring carbons form a fused 0-(CH2)n-0 group wherein n is 1 or 2, or two groups on adjacent ring carbons form a fused CH=CH-CH=CH group; R^ is selected from hydrogen, C1-C6-alkyl and C3-C6-cycloalkyl; R12 is selected from hydrogen, C1-C6-alkyl and C3-C6-cycloalkyl; R13 and R14 are selected independently from hydrogen, C.|-Cg-alkyl, C3-C6-cycloalkyl, C.|-Cg-alkoxy, C3-C6-cy-cloalkoxy, hydroxy, amino, C-pCg-alkylamino, C^Cg-dialkylamino, wherein said two alkyl portions of said dialkylamino can form, together with the nitrogen atom to which they are attached, a heterocycle selected from pyrrolidine, piperidine, morpholine and piperazine optionally N-substituted by C-j-Cg-alkyl or C3-C6-cycloalkyl, C3-C6-cy-cloalkylamino, C1-C6-alkyl-C3-Cg-cycloalkylamino and C3-C6-dicycloalkylamino; or the group OR12 and R14 form a fused 0-(CH2)p-0 group wherein p is 1 or 2; R15 is selected from 1-pyrrolidinyl, 1-piperidinyl, 4-morpholinyl and 1(4)-piperazinyl optionally N-substituted by C1-C6-alkyl or C3-C6-cycloalkyl, C3-C6-cycloalkylamino, C1-C6-alkyl-C3-Cg-cycloalkylamino and C3-C6-dicy-cloalkylamino; and

Rig-Rig are selected independently from hydrogen, C1-C6-alkyl, C3-Cg-cycloalkyl, C1-C6-alkoxy, C3-Cg-cycloalkoxy, hydroxy, amino, C1-C6-alkylamino, C^Cg-dialkylamino, wherein said two alkyl portions of said dialkylamino can form, together with the nitrogen atom to which they are attached, a heterocycle selected from pyrrolidine, piperidine, morpholine and piperazine optionally N-substituted by C-pCg-alkyl or C3-C6-cycloalkyl, C3-C6-cycloalkylamino, C1 -Cg-aIkyl-C3-C6-cycloaIkylamino and C3-C6-dicycloalkylamino, or two groups on adjacent ring carbons form a fused 0-(CH2)q-0 group wherein q is 1 or 2, or two groups on adjacent ring carbons form a fused CH=CH-CH=CH group; or a pharmaceutically acceptable salt thereof, for use in the protection of a human or animal living body from ultraviolet radiation. 2. The benzoic acid ester compounds of claim 1 wherein, in the benzoic acid ester compound, when R is (i), R3 is selected independently from methoxy and tert-butyl, R8 is selected independently from hydrogen, methoxy and tert-butyl, and R’, Ri, R2, R4, R5, Rg, R7, Rg and R10 are each hydrogen; when Ris(ii), R^ R2, R3, R4, R5, R-(-(, R13and R14 are each hydrogen and R12 is methyl; and when R is (iii), R1 is selected independently from hydrogen and hydroxy, R3 is selected independently from hydrogen and methoxy, R15 is 1-pyrrolidinyl, and R2, r4, r5, r16, r17 and R18 are each hydrogen. 3. The benzoic acid ester compounds of claim 2, wherein the benzoic acid ester compound is selected from the group consisting of: 1-phenylvinyl 4-methoxybenzoate; 1-(4-methoxyphenyl)-vinyl 4-ferf-butylbenzoate; 1-(4-ferf-butylphenyl)-vinyl 4-methoxybenzoate; 1-phenylvinyl 4-ferf-butylbenzoate; 4-benzoyloxy-2-methoxybenzenesulfonic acid; and 3-(1 -pyrrolidinyl)phenyl benzoate. 4. The benzoic acid ester compounds for use according to claim 1, wherein the human or animal living body is a human being. 5. The benzoic acid ester compounds for use according to claim 1, wherein the benzoic acid ester compound is contained in a cosmetic or pharmaceutical composition, or a personal care composition. 6. The benzoic acid ester compounds for use according to claim 5, wherein the cosmetic or pharmaceutical composition com prises an effective amount of at least a benzoic acid ester com pound susceptible to be photochemically converted in situ to a sunscreen compound with enhanced UV protection ability. 7. The benzoic acid ester compounds for use according to claim 5, wherein said cosmetic or pharmaceutical or personal care composition is selected from creams, ointments, milks, suspensions, powders, oils, lotions, gels, sticks, foams, emulsions, dispersions, sprays, aerosols, lipsticks, foundations, makeup, loose or press powders, eye blushes, eye shadows, mascaras, nail varnishes, nail lacquers, and non permanent dyeing compositions for the hair. 8. The benzoic acid ester compounds for use according to claim 5, wherein the cosmetic or pharmaceutical or personal care composition comprises an effective amount of the benzoic acid ester compound that ranges from 0.01 to 40 wt % based on the total weight of the composition. 9. The benzoic acid ester compounds for use according to claim 8, wherein the effective amount of the benzoic acid ester compound ranges from 0.05 to 25 wt % based on the total weight of the composition. 10. The benzoic acid ester compounds for use according to claim 9, wherein the effective amount of the benzoic acid ester compound ranges from 0.1 wt % to about 15 wt % of the composition. 11. The benzoic acid ester compounds for use according to claim 5, wherein the benzoic acid ester compound in the personal care composition photostabilizes composition ingredients from sun radiation. 12. A benzoic acid ester compound of formula (la):

wherein R is a group selected from (i), (ii) and (iii):

wherein R-|-R5 are selected independently from hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, CrC6-alkoxy, C3-C6-cy-cloalkoxy, hydroxy, amino, C1-C6-alkylamino, C1-C6-dialkylamino, wherein said two alkyl portions of said dialkylami-no can form, together with the nitrogen atom to which they are attached, a heterocycle selected from pyrrolidine, piperidine, morpholine and piperazine optionally N-substituted by C1-C6-alkyl or C3-C6-cycloalkyl, C3-C6-cy-cloalkylamino, C1-C6-alkyl-C3-C6-cycloalkylamino and C3-C6-dicycloalkylamino, or two groups on adjacent ring carbons form a fused 0-(CH2)m-0 group wherein m is 1 or 2, or two groups on adjacent ring carbons form a fused CH=CH-CH=CH group; R’ is hydrogen; R6-R10are selected independently from hydrogen, C^Cg-alkyl, C3-C6-cycloalkyl, C^Cg-alkoxy, C3-C6-cycloalkoxy, hydroxy, amino, C^Cg-alkylamino, C^Cg-dialkylamino, wherein said two alkyl portions of said dialkylamino can form, together with the nitrogen atom to which they are attached, a heterocycle selected from pyrrolidine, piperidine, morpholine and piperazine optionally N-substituted by C1-C6-alkyl or C3-C6-cycloalkyl, C3-C6-cycloalkylamino, C1-C6-alkyl-C3-C6-cycloalkylamino and C3-C6-dicycloalkylamino, or two groups on adjacent ring carbons form a fused 0-(CH2)n-0 group wherein n is 1 or 2, or two groups on adjacent ring carbons form a fused CH=CH-CH=CH group; R^ is selected from hydrogen, C^Cg-alkyl and C3-C6-cycloalkyl; R12 is selected from hydrogen, C^Cg-alkyl and C3-C6-cycloalkyl; R13 and R14 are selected independently from hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, CrCg-alkoxy, C3-C6-cy-cloalkoxy, hydroxy, amino, C^Cg-alkylamino, C^Cg-dialkylamino, wherein said two alkyl portions of said dialkylamino can form, together with the nitrogen atom to which they are attached, a heterocycle selected from pyrrolidine, piperidine, morpholine and piperazine optionally N-substituted by C^Cg-alkyl or C3-C6-cycloalkyl, C3-C6-cy-cloalkylamino, C^Cg-alkyl-Cg-Cg-cycloalkylamino and C3-C6-dicycloalkylamino; or the group OR12 and R14 form a fused 0-(CH2)p-0 group wherein p is 1 or 2; R15 is selected from 1-pyrrolidinyl, 1-piperidinyl, 4-morpholinyl and 1(4)-piperazinyl optionally 4(1)-substituted by C^Cg-alkyl or C3-C6-cycloalkyl; and

Rie-Rie are selected independently from hydrogen, C-pCg-alkyl, C3-C6-cycloalkyl, C-j-Cg-alkoxy, C3-C6-cycloalkoxy, hydroxy, amino, C^Cg-alkylamino, Cj-C6-dialkylamino, wherein said two alkyl portions of said dialkylamino can form, together with the nitrogen atom to which they are attached, a heterocycle selected from pyrrolidine, piperidine, morpholine and piperazine optionally N-substituted by C.|-Cg-alkyl or C3-C6-cycloalkyl, C3-C6-cycloalkylamino, C1-Cg-alkyl-C3-C6-cycloalkylamino and C3-C6-dicycloalkylamino, or two groups on adjacent ring carbons form a fused 0-(CH2)q-0 group wherein q is 1 or 2, or two groups on adjacent ring carbons form a fused CH=CH-CH=CH group; with the proviso that when R^ R2, and R4-Ri0 are each hydrogen, R3 cannot be hydrogen or methoxy; and with the proviso that when RrR7, Rg and R10 are each hydrogen, R8 cannot be methyl; or a pharmaceutically acceptable salt thereof. 13. The benzoic acid ester compound according to claim 12, wherein in said compound, when R is (i), R3 is selected independently from C1-C6-alkyl, C3-C6-cycloalkyl, C^Cg-alkoxy, C3-C6-cycloalkoxy, R8 is selected independently from hydrogen, C^Cg-alkyl, C3-C6-cycloalkyl, C^Cg-alkoxy and C3-C6-cycloalkoxy, and R^ R2, R4-R7, Rg and R10 are each hydrogen; when R is (ii), R-|-R5, R^, R13 and R14 are each hydrogen and R12 is C^Cg-alkyl and C3-C6-cy-cloalkyl; and when R is (iii), R15 is selected from 1-pyrrolidinyl, 1-piperidinyl, 4-morpholinyl and 1(4)-piperazinyl optionally 4 (1) -substituted by C1-C6-alkyl or C3-C6-cycloalkyl and R16-R18 are each hydrogen; with the proviso that when R^ R2, and R4-R10 are each hydrogen, R3 cannot be hydrogen or methoxy; and with the proviso that when RrR7, Rg and R10 are each hydrogen, R8 cannot be methyl; or a pharmaceutically acceptable salt thereof. 14. The benzoic acid ester compound according to claim 13, wherein said compound is selected from the group consisting of: 1-(4-methoxyphenyl)-vinyl 4-ferf-butylbenzoate; 1-(4-ferf-butylphenyl)-vinyl 4-methoxybenzoate; 1-phenylvinyl 4-ferf-butylbenzoate; 4-benzoyloxy-2-methoxybenzenesulfonic acid; and 3-(1 -pyrrolidinyl)phenyl benzoate. 15. A cosmetic or pharmaceutical composition, or a personal care composition containing at least a benzoic acid ester compound as defined in any of claims 12-14, or a salt thereof. 16. A process to prepare a benzoic acid ester compound as defined in claim 12 wherein: if R is (i), the process is performed by reacting an acyl halide of formula (II):

wherein R-|-R5 are as defined in claim 12, and X is an halogen atom selected from the group consisting of fluorine, chlorine and bromine, with a silylenol of formula (III):

wherein R’ and R6-R10 are as defined in claim 12 and R-19-R21 are selected independently from C^-Cg-alkyl, C3-C6-cycloalkyl and C6H5-(CH2)r-, wherein r is 1-4, or two groups can form, together with the silicium atom a ring selected from silolane, sililane and silepane, in the presence of a catalyst selected from the group consisting of mercuric chloride, cuprous chloride and mixtures thereof; if R is (ii), the process if performed by reacting a benzoic acid ester of formula (IV): ^13

Rl 9 ill R2V^^C"o/y^OR12 R3^f Rs Rl4 r4 (IV) wherein R1-R5 and R12-Ri4 are as defined in claim 12, with chlorosulfonic acid followed by an optional esterification reaction with C1-C6-alkyl-OH or C3-C6-cycloalkyl-OH; or when R is (ii) and Rn is hydrogen, by esterifying an intermediate (VI):

wherein R^ is hydrogen and R^'^m are as defined in claim 12, with an acid intermediate (VII):

wherein R1-R5 are as defined in claim 12; or when R is (ii), by esterifying the intermediate (VI):

wherein R^ is C.|-C6-alkyl or C3-C6-cycloalkyl and R12-Ri4 are as defined in claim 12, with (VII); and if R is (iii), by reacting an acyl halide of formula (II) :

wherein R1-R5 are as defined in claim 12, and X is an halogen atom selected from the group consisting of fluorine, chlorine and bromine, with a phenol of formula (VIII):

wherein R-|5-R-|8 are as defined in claim 12. 17. The silylenol of formula (III) as defined in claim 16 which is 4-ferf-butylacetophenone trimethylsilylenol. Patentansprüche 1. Benzoesäureesterverbindungen der Formel (I):

wobei R-1-R5 unabhängig voneinander aus Wasserstoff, C^Cg-Alkyl, C3-C6-Cycloalkyl, C.|-Cg-Alkoxy, C3-C6-Cyc-loalkoxy, Hydroxy, Amino, C^Cg-Alkylamino, C^Cg-Dialkylamino ausgewählt sind, wobei die zwei Alkylanteile des Dialkylaminorests, zusammen mit dem Stickstoffatom mit dem sie verbunden sind, ein Heterocyclus ausgewählt aus Pyrrolidin, Piperidin, Morpholin und Piperazin wahlweise N-substituiert durch C1-C6-AlkyloderC3-Cg-Cycloalkyl, C3-Cg-Cycloalkylamino, C1-C6-Alkyl-C3-Cg-cycloalkylamino und C3-C6-Dicycloalkylamino bilden können, oder zwei Gruppen von angrenzenden Ringkohlenstoffatomen eine kondensierte 0-(CH2)m-0 Gruppe bilden, worin m = 1 oder 2, oder zwei Gruppen von angrenzenden Ringkohlenstoffatomen eine kondensierte CH=CH-CH=CH Gruppe bilden; R eine Gruppe ist, die aus (i), (ii) und (iii) ausgewählt ist:

wobei R’ aus Wasserstoff, C.|-Cg-Alkyl und C3-C6-Cycloalkyl ausgewählt ist; R6-R10 unabhängig voneinander aus Wasserstoff, C^Cg-Alkyl, C3-C6-Cycloalkyl, C-j-Cg-Alkoxy, C3-C6-Cycloalkoxy, Hydroxy, Amino, C1-C6-Alkylamino, C1-C6-Dialkylamino ausgewählt sind, wobei die zwei Alkylanteile des Dialkylaminorests, zusammen mit dem Stickstoffatom mit dem sie verbunden sind, ein Heterocyclus ausgewählt aus Pyrrolidin, Piperidin, Morpholin und Piperazin wahlweise N-substituiert durch C1-C6-Alkyl oder C3-C6-Cycloalkyl, C3-C6-Cycloalkylamino, C-pCg-Alkyl-C^-Cg-cycloalkylamino und C3-C6-Dicycloalkylamino bilden können, oder zwei Gruppen von angrenzenden Ringkohlenstoffatomen eine kondensierte 0-(CH2)n-0 Gruppe bilden, worin n = 1 oder 2, oder zwei Gruppen von angrenzenden Ringkohlenstoffatomen eine kondensierte CH=CH-CH=CH Gruppe bilden; R-i-i aus Wasserstoff, C1-C6-Alkyl und C3-C6-Cycloalkyl ausgewählt ist; R12 aus Wasserstoff, C1-C6-Alkyl und C3-C6-Cycloalkyl ausgewählt ist; R13 und R14 unabhängig voneinander aus Wasserstoff, C^Cg-Alkyl, C3-C6-Cycloalkyl, C^Cg-Alkoxy, C3-C6-Cyc-loalkoxy, Hydroxy, Amino, C1-C6-Alkylamino, C^Cg-Dialkylamino ausgewählt sind, wobei die zwei Alkylanteile des Dialkylaminorests, zusammen mit dem Stickstoffatom mit dem sie verbunden sind, ein Heterocyclus ausgewählt aus Pyrrolidin, Piperidin, Morpholin und Piperazin wahlweise N-substituiert durch Ci-C6-AlkyloderC3-C6-Cycloalkyl, C3-C6-Cycloalkylamino, C^Cg-Alkyl-C^Cg-cycloalkylamino und C3-C6-Dicycloalkylamino bilden können, oder die Gruppe OR12 und R14 eine kondensierte 0-(CH2)p-0 Gruppe bilden, worin p = 1 oder 2; R15 ausgewählt ist aus 1 -Pyrrolidinyl, 1 -Piperidinyl, 4-Morpholinyl und 1 (4) -Piperazinyl wahlweise N-substituiert durch C^Cg-Alkyl oder C3-C6-Cycloalkyl, C3-C6-Cycloalkylamino, Ci-C6-Alkyl-C3-C6-Cycloalkylamino und C3-Cg-Dicycloalkylamino; und R16-R18 unabhängig voneinander aus Wasserstoff, C-|-Cg-Alkyl, C3-C6-Cycloalkyl, C^Cg-Alkoxy, C3-C6-Cycloalk-oxy, Hydroxy, Amino, C^Cg-Alkylamino, C^Cg-Dialkylamino ausgewählt sind, wobei die zwei Alkylanteile des Dialkylaminorests, zusammen mit dem Stickstoffatom mit dem sie verbunden sind, ein Heterocyclus ausgewählt aus Pyrrolidin, Piperidin, Morpholin und Piperazin wahlweise N-substituiert durch C^Cg-Alkyl oder C3-C6-Cycloalkyl, C3-Cg-Cycloalkylamino, Ci-C6-Alkyl-C3-C6-cycloalkylamino und C3-C6-Dicycloalkylamino bilden können, oder zwei Gruppen von angrenzenden Ringkohlenstoffatomen eine kondensierte 0-(CH2)q-0 Gruppe bilden, worin q = 1 oder 2, oder zwei Gruppen von angrenzenden Ringkohlenstoffatomen eine kondensierte CH=CH-CH=CH Gruppe bilden; oder ein pharmazeutisch akzeptables Salz davon, zur Verwendung zum Schutz eines menschlichen oder tierischen lebenden Körpers vor UV-Strahlung. 2. Die Benzoesäureesterverbindungen des Anspruchs 1, wobei, in der Benzoesäureesterverbindung, wenn R = (i), R3 unabhängig aus Methoxy und tert-Butyl ausgewählt ist, R8 unabhängig aus Wasserstoff, Methoxy und tert-Butyl ausgewählt ist, und R’, R^ R2, R4, R5, R6, R7, Rg und R10 jeweils Wasserstoff sind; wenn R = (ii), R^ R2, R3, R4, R5, R^, R13 und R14 jeweils Wasserstoff sind und R12 Methyl ist; und wenn R = (iii), R1 unabhängig aus Wasserstoff und Hydroxy ausgewählt ist, R3 unabhängig aus Wasserstoff und Methoxy ausgewählt ist, R15 1-Pyrrolidinyl ist, und R2, R4, R5, R16, R17 und R18 jeweils Wasserstoff sind. 3. Die Benzoesäureesterverbindungen des Anspruchs 2, wobei die Benzoesäureesterverbindung ausgewählt ist aus der Gruppe bestehend aus: 1-Phenylvinyl 4-methoxybenzoat; 1-(4-Methoxyphenyl)-vinyl 4-ferf-butylbenzoat; 1-(4-ferf-Butylphenyl)-vinyl 4-methoxybenzoat; 1-Phenylvinyl 4-ferf-butylbenzoat; 4-Benzoyloxy-2-methoxybenzolsulfonsäure; und 3-(1 -Pyrrolidinyljphenyl benzoat. 4. Die Benzoesäureesterverbindungen zur Verwendung nach Anspruch 1, wobei der menschliche oder tierische lebende Körper ein Mensch ist. 5. Die Benzoesäureesterverbindungen zur Verwendung nach Anspruch 1, wobei die Benzoesäureesterverbindung in einer kosmetischen oder pharmazeutischen Zusammensetzung, oder in einer Zusammensetzung zur Körperpflege enthalten ist. 6. Die Benzoesäureesterverbindungen zur Verwendung nach Anspruch 5, wobei die kosmetische oder pharmazeutische Zusammensetzung eine wirksame Menge von mindestens einer Benzoesäureesterverbindung umfasst, die photochemisch in situ in eine Sonnenschutzverbindung mit erhöhter UV-Schutzfähigkeit umgewandelt werden kann. 7. Die Benzoesäureesterverbindungen zur Verwendung nach Anspruch 5, wobei die kosmetische oder pharmazeutische Zusammensetzung bzw. Zusammensetzung zur Körperpflege ausgewählt ist aus Cremen, Salben, Körpermilch, Suspensionen, Pulvern, Ölen, Lotionen, Gelen, Sticks, Schäumen, Emulsionen, Dispersionen, Sprays, Aerosolen, Lippenstiften, Grundlagen, Make-up, losen oder pressfertigen Pulvern, Rouges, Lidschatten, Mascara, Nagellacken, Nagellackfarben, und nicht-permanenten Farbstoffzusammensetzungen für das Haar. 8. Die Benzoesäureesterverbindungen zur Verwendung nach Anspruch 5, wobei die kosmetische oder pharmazeutische Zusammensetzung bzw. Zusammensetzung zur Körperpflege eine wirksame Menge der Benzoesäureesterverbindung von 0,01 bis 40 Gew.-% bezogen auf das gesamte Gewicht der Zusammensetzung umfasst. 9. Die Benzoesäureesterverbindungen zur Verwendung nach Anspruch 8, wobei die wirksame Menge der Benzoe säureesterverbindung von 0,05 bis 25 Gew.-% bezogen auf das gesamte Gewicht der Zusammensetzung reicht. 10. Die Benzoesäureesterverbindungen zur Verwendung nach Anspruch 9, wobei die wirksame Menge der Benzoesäureesterverbindung von 0,1 bis ca. 15 Gew.-% der Zusammensetzung reicht. 11. Die Benzoesäureesterverbindungen zur Verwendung nach Anspruch 5, wobei die Benzoesäureesterverbindung in der Zusammensetzung zur Körperpflege Inhaltstoffe der Zusammensetzung gegenüber der Sonnenstrahlung photostabilisiert. 12. Eine Benzoesäureesterverbindung der Formel (la):

wobei R eine Gruppe ist, die aus (i), (ii) und (iii) ausgewählt ist:

wobei R.|-R5 unabhängig voneinander aus Wasserstoff, C-pCg-Alkyl, C3-C6-Cycloalkyl, C.|-Cg-Alkoxy, C3-C6-Cyc-loalkoxy, Hydroxy, Amino, C^Cg-Alkylamino, C^Cg-Dialkylamino ausgewählt sind, wobei die zwei Alkylanteile des Dialkylaminorests, zusammen mit dem Stickstoffatom mit dem sie verbunden sind, ein Heterocyclus ausgewählt aus Pyrrolidin, Piperidin, Morpholin und Piperazin wahlweise N-substituiert durch C^Cg-Alkyl oder C3-C6-Cycloalkyl, C3-Cg-Cycloalkylamino, C-pCg-Alkyl-C^Cg-cycloalkylamino und C3-C6-Dicycloalkylamino bilden können, oder zwei Gruppen von angrenzenden Ringkohlenstoffatomen eine kondensierte 0-(CH2)m-0 Gruppe bilden, worin m = 1 oder 2, oder zwei Gruppen von angrenzenden Ringkohlenstoffatomen eine kondensierte CH=CH-CH=CH Gruppe bilden; R’ Wasserstoff ist;

Rg-R10 unabhängig voneinander aus Wasserstoff, C1-C6-Alkyl, C3-C6-Cycloalkyl, C1-C6-Alkoxy, C3-C6-Cycloalkoxy, Hydroxy, Amino, C-j-Cg-Alkylamino, C-j-Cg-Dialkylamino ausgewählt sind, wobei die zwei Alkylanteile des Dialkylaminorests, zusammen mit dem Stickstoffatom mit dem sie verbunden sind, ein Heterocyclus ausgewählt aus Pyrrolidin, Piperidin, Morpholin und Piperazin wahlweise N-substituiert durch C^Cg-Alkyl oder C3-C6-Cycloalkyl, C3-Cg-Cycloalkylamino, C.|-Cg-Alkyl-C3-C6-cycloalkylamino und C3-C6-Dicycloalkylamino bilden können, oder zwei Gruppen von angrenzenden Ringkohlenstoffatomen eine kondensierte 0-(CH2)n-0 Gruppe bilden, worin n = 1 oder 2, oder zwei Gruppen von angrenzenden Ringkohlenstoffatomen eine kondensierte CH=CH-CH=CH Gruppe bilden; Rll aus Wasserstoff, C^Cg-Alkyl und C3-C6-Cycloalkyl ausgewählt ist; R12 aus Wasserstoff, C^Cg-Alkyl und C3-C6-Cycloalkyl ausgewählt ist; R13 und R14 unabhängig voneinander aus Wasserstoff, C^Cg-Alkyl, C3-C6-Cycloalkyl, C^Cg-Alkoxy, C3-C6-Cyc-loalkoxy, Hydroxy, Amino, C^Cg-Alkylamino, C^Cg-Dialkylamino ausgewählt sind, wobei die zwei Alkylanteile des Dialkylaminorests, zusammen mit dem Stickstoffatom mit dem sie verbunden sind, ein Heterocyclus ausgewählt aus Pyrrolidin, Piperidin, Morpholin und Piperazin wahlweise N-substituiert durch C^Cg-AlkyloderC^Cg-Cycloalkyl, C3-C6-Cycloalkylamino, C1-C6-Alkyl-C3-C6-cycloalkylamino und C3-C6-Dicycloalkylamino bilden können, oder die Gruppe OR12 und R14 eine kondensierte 0-(CH2)p-0 Gruppe bilden, worin p = 1 oder 2; R15 ausgewählt ist aus 1 -Pyrrolidinyl, 1-Piperidinyl, 4-Morpholinyl und 1(4)-Piperazinyl wahlweise 4(1)-substituiert durch C^Cg-Alkyl oder C3-C6-Cycloalkyl; und R16-R18 unabhängig voneinander aus Wasserstoff, C^Cg-Alkyl, C3-C6-Cycloalkyl, C1-C6-Alkoxy, C3-C6-Cycloalkoxy, Hydroxy, Amino, C1-C6-Alkylamino, C1-C6-Dialkylamino ausgewählt sind, wobei die zwei Alkylanteile des Dialkylaminorests, zusammen mit dem Stickstoffatom mit dem sie verbunden sind, ein Heterocyclus ausgewählt aus Pyrrolidin, Piperidin, Morpholin und Piperazin wahlweise N-sub-stituiert durch C1-C6-Alkyl oder C3-C6-Cycloalkyl, C3-C6-Cycloalkylamino, C1-C6-Alkyl-C3-C6-cycloalkylamino und C3-C6-Dicycloalkylamino bilden können, oder zwei Gruppen von angrenzenden Ringkohlenstoffatomen eine kondensierte 0-(CH2)q-0 Gruppe bilden, worin q = 1 oder 2, oder zwei Gruppen von angrenzenden Ringkohlenstoffatomen eine kondensierte CH=CH-CH=CH Gruppe bilden; mit der Maßgabe, dass, wenn R^ R2, und R4-R10jeweils Wasserstoff sind, R3 nicht Wasserstoff oder Methoxy sein kann; und mit der Maßgabe, dass, wenn R1-R7, Rg und R10 jeweils Wasserstoff sind, R8 nicht Methyl sein kann; oder ein pharmazeutisch akzeptables Salz davon. 13. Die Benzoesäureesterverbindung nach Anspruch 12, wobei in der Verbindung, wenn R = (i), R3 unabhängig aus C-|-C6-Alkyl, C3-C6-Cycloalkyl, C^Cg-Alkoxy, C3-C6-Cycloalkoxy ausgewählt ist, R8 unabhängig aus Wasserstoff, C1-C6-Alkyl, C3-Cg-Cycloalkyl, C^Cg-Alkoxy und C3-C6-Cycloalkoxy ausgewählt ist, und R^ R2, R4-R7, Rg und R10 jeweils Wasserstoff sind; wenn R _ (ii), R.|-R5, R^, R13 und R14jeweils Wasserstoff sind und R12 C^Cg-Alkyl und C3-Cg-Cycloalkyl ist; und wenn R = (iii), R15 ausgewählt aus 1 -Pyrrolidinyl, 1 -Piperidinyl, 4-Morpholinyl und 1(4)-Pi-perazinyl wahlweise 4(1 )-substituiert durch C^Cg-Alkyl oder C3-C6-Cycloalkyl ist und R16-R18 jeweils Wasserstoff sind; mit der Maßgabe, dass, wenn R^ R2, und R4-R10jeweils Wasserstoff sind, R3 nicht Wasserstoff oder Methoxy sein kann; und mit der Maßgabe, dass, wenn R1-R7, Rg und R10 jeweils Wasserstoff sind, R8 nicht Methyl sein kann; oder ein pharmazeutisch akzeptables Salz davon. 14. Die Benzoesäureesterverbindung nach Anspruch 13, wobei die Verbindung ausgewählt ist aus der Gruppe bestehend aus: 1-(4-Methoxyphenyl)-vinyl 4-tert-butylbenzoat; 1-(4-tert-Butylphenyl)-vinyl 4-methoxybenzoat; 1-Phenylvinyl 4-tert-butylbenzoat; 4-Benzoyloxy-2-methoxybenzolsulfonsäure; und 3-(1-Pyrrolidinyl)phenyl benzoat. 15. Eine kosmetische oder pharmazeutische Zusammensetzung, oder eine Zusammensetzung zur Körperpflege enthaltend mindestens eine Benzoesäureesterverbindung wie in einem der Ansprüche 12-14 definiert, oder ein Salz davon. 16. Ein Verfahren zur Herstellung von einer Benzoesäureesterverbindung wie in Anspruch 12 definiert, wobei: falls R = (i), das Verfahren durch die Reaktion von einem Acylhalogenid der Formel (II) durchgeführt wird:

wobei R1-R5 wie in Anspruch 12 definiert sind, und X ein Halogenatom ausgewählt aus der Gruppe bestehend aus Fluor, Chlor und Brom ist, mit einem Silylenol der Formel (III) :

wobei R’ und R6-R10 wie in Anspruch 12 definiert sind und R-19-R21 unabhängig voneinander aus C^Cg-Alkyl, C3-C6-Cycloalkyl und 06Η5-(0Η2)Γ- ausgewählt sind, wobei r = 1-4, oder zwei Gruppen, zusammen mit dem Siliciumatom einen Ring ausgewählt aus Silolan, Sililan und Silepan bilden können, in Gegenwart eines Katalysators ausgewählt aus der Gruppe bestehend aus Quecksilber(ll)-chlorid, Kupfer(l)-chlorid und Mischungen davon; falls R = (ii), das Verfahren durch die Reaktion von einem Benzoesäureester der Formel (IV) durchgeführt wird:

wobei R-1-R5 und R^-R^wie in Anspruch 12 definiert sind, mit Chlorosulfonsäure gefolgt von einer fakultativen

Esterifizierungsreaktion mit C-pCg-Alkyl-OH oder C3-C6-Cycloalkyl-OH; oder wenn R = (ii) und R^ Wasserstoff ist, durch die Esterifizierung eines Zwischenprodukts (VI):

wobei R11 Wasserstoff ist und R^-R^wie in Anspruch 12 definiertsind, miteinem sauren Zwischenprodukt (VII):

wobei R1-R5 wie in Anspruch 12 definiert sind; oder wenn R = (ii), durch die Esterifizierung des Zwischenprodukts (VI):

(VI) wobei R11 crc6 -Alkyl oder C3-C6-Cycloalkyl ist und R-12-R14 wie in Anspruch 12 definiert sind, mit (VII); und falls R = (iii), durch die Reaktion von einem Acylhalogenid der Formel (II):

UV wobei R-1-R5 wie in Anspruch 12 definiert sind, und X ein Halogenatom ausgewählt aus der Gruppe bestehend aus Fluor, Chlor und Brom ist, mit einem Phenol der Formel (VIII) :

wobei R-15-R18 wie in Anspruch 12 definiert sind. 17. Das Silylenol der Formel (III) wie in Anspruch 16 definiert, welches 4-ferf-Butylacetophenon trimethylsilylenol ist. Revendications 1. Composés d’ester de l’acide benzoïque de formule (I) :

dans laquelle R-|-R5 sont indépendamment choisis parmi l’hydrogène, alkyle en (C^Cg), cycloalkyle en (C3-C6), alcoxy en (CrC6), cycloalkoxy en (C3-C6), hydroxy, amino, alkylamino en (C^Cg), dialkylamino en (C^Cg), où les deux parties alkyle dudit dialkylamino peuvent former, conjointement avec l’atome d’azote auquel elles sont reliées, un hétérocycle choisi parmi la pyrrolidine, la pipéridine, la morpholine et la pipérazine facultativement N-substituées par alkyle en (C^-Cg) ou cycloalkyle en (C3-C6), cycloalkylamino en (C3-C6), (alkyle en C1-C6)-(cycloalkylamino en C3-C6) et dicycloalkylamino en (C3-C6), ou deux groupes sur des atomes de carbone adjacents de l’anneau forment un groupe 0-(CH2)m-0 condensé, où m est 1 ou 2, ou deux groupes sur des atomes de carbone adjacents de l’anneau forment un groupe CH=CH-CH=CH condensé ; R est un groupe choisi parmi (i), (ii) et (iii) :

dans lequel R’ est choisi parmi l’hydrogène, alkyle en (CrC6) et cycloalkyle en (C3-C6) ; R6-R10 sont indépendamment choisis parmi l’hydrogène, alkyle en (CrC6), cycloalkyle en (C3-C6), alcoxy en (0Γ06), cycloalkoxy en (C3-C6), hydroxy, amino, alkylamino en (CrC6), dialkylamino en (CrC6), où les deux parties alkyle dudit dialkylamino peuvent former, conjointement avec l’atome d’azote auquel elles sont reliées, un hétérocycle choisi parmi la pyrrolidine, la pipéridine, la morpholine et la pipérazine facultativement N-substituées par alkyle en (CrC6) ou cycloalkyle en (C3-C6), cycloalkylamino en (C3-C6), (alkyle en CrC6) - (cycloalkylamino en C3-C6) et dicycloalkylamino en (C3-C6), ou deux groupes sur des atomes de carbone adjacents de l’anneau forment un groupe 0-(CH2)n-0 condensé, où n est 1 ou 2, ou deux groupes sur des atomes de carbone adjacents de l’anneau forment un groupe CH=CH-CH=CH condensé ;

Ru est choisi parmi l’hydrogène, alkyle en (C^Cg) et cycloalkyle en (C3-C6) ; R12 est choisi parmi l’hydrogène, alkyle en (C^Cg) et cycloalkyle en (C3-C6); R13 et R14 sont indépendamment choisis parmi l’hydrogène, alkyle en (C^Cg), cycloalkyle en (C3-C6), alcoxy en (CrC6), cycloalkoxy en (C3-C6), hydroxy, amino, alkylamino en (CrC6), dialkylamino en (CrC6), où les deux parties alkyle dudit dialkylamino peuventformer, conjointement avec l’atome d’azote auquel elles sontreliées, un hétérocycle choisi parmi la pyrrolidine, la pipéridine, la morpholine et la pipérazine facultativement N-substituées par alkyle en (C-pCg) ou cycloalkyle en (C3-C6), cycloalkylamino en (C3-C6), (alkyle en C1-C6)-(cycloalkylamino en C3-C6) et dicycloalkylamino en (C3-C6) ; ou le groupe OR12 et R14 forment un groupe 0-(CH2)p-0 condensé dans lequel p est 1 ou 2 ; R15 est choisi parmi le 1-pyrrolidinyle, le 1-pipéridinyle, le 4-morpholinyle et le 1 (4) -pipérazinyle facultativement N-substitués par alkyle en (C^-Cg) ou cycloalkyle en (C3-C6), cycloalkylamino en (C3-C6), (alkyle en C^-CgHcy-cloalkylamino en C3-C6) et dicycloalkylamino en (C3-C6) ; et R"i6"Rl8 sor|t indépendamment choisis parmi l’hydrogène, alkyle en (C^-Cg), cycloalkyle en (C3-C6), alcoxy en (CrC6), cycloalkoxy en (C3-C6), hydroxy, amino, alkylamino en (CrC6), dialkylamino en (CrC6), où les deux parties alkyle dudit dialkylamino peuventformer, conjointement avec l’atome d’azote auquel elles sont reliées, un hétérocycle choisi parmi la pyrrolidine, la pipéridine, la morpholine et la pipérazine facultativement N-substituées par alkyle en (CrC6) ou cycloalkyle en (C3-C6), cycloalkylamino en (C3-C6), (alkyle en CrC6)-(cycloalkylamino en C3-C6) et dicycloalkylamino en (C3-C6), ou deux groupes sur des atomes de carbone adjacents de l’anneau forment un groupe 0-(CH2)q-0 condensé, où q est 1 ou 2, ou deux groupes sur des atomes de carbone adjacents de l’anneau forment un groupe CH=CH-CH=CH condensé ; ou un sel pharmaceutiquement acceptable de celui-ci, pour l’utilisation dans la protection d’un corps vivant humain ou animal contre le rayonnement ultraviolet. 2. Les composés d’ester de l’acide benzoïque de la revendication 1 où, dans le composé d’ester de l’acide benzoïque, lorsque R est (i), R3 est indépendamment choisi parmi le méthoxy et le tert-butyle, R8 est indépendamment choisi parmi l’hydrogène, le méthoxy et le tert-butyle, et R’, Ri, R2, R4, R5, Rß, R7, Rg et Ri0sonttous hydrogène ; lorsque R est (ii), R^ R2, R3, R4, R5, Ru, R13 et R14 sont tous hydrogène et R12 est méthyle ; et lorsque R est (iii), Ri est indépendamment choisi parmi l’hydrogène et l’hydroxy, R3 est indépendamment choisi parmi l’hydrogène et le méthoxy, R15 est le 1-pyrrolidinyle, et R2, R4, R5, Ri6, R17 et R18 sont tous hydrogène. 3. Les composés d’ester de l’acide benzoïque de la revendication 2, où le composé d’ester de l’acide benzoïque est choisi dans le groupe constitué de : 1-phénylvinyl 4-méthoxybenzoate ; 1-(4-méthoxyphényl)-vinyl 4-ferf-butylbenzoate ; 1-(4-ferf-butylphényl)-vinyl 4-méthoxybenzoate ; 1-phénylvinyl 4-ferf-butylbenzoate ; acide 4-benzoyloxy-2-méthoxybenzènesulfonique ; et 3-(1-pyrrolidinyl)phényl benzoate. 4. Les composés d’ester de l’acide benzoïque pour l’utilisation selon la revendication 1, où le corps vivant humain ou animal est un être humain. 5. Les composés d’ester de l’acide benzoïque pour l’utilisation selon la revendication 1, où le composé d’ester de l’acide benzoïque est contenu dans une composition cosmétique ou pharmaceutique, ou dans une composition de soins personnels. 6. Les composés d’ester de l’acide benzoïque pour l’utilisation selon la revendication 5, où la composition cosmétique ou pharmaceutique comprend une quantité efficace d’au moins un composé d’ester de l’acide benzoïque qui peut être transformé /ns/fu parvoie photochimique dans un composé écran solaire ayant une capacité accrue de protection contre le rayonnement UV. 7. Les composés d’ester de l’acide benzoïque pour l’utilisation selon la revendication 5, où ladite composition cosmétique ou pharmaceutique ou composition de soins personnels est choisie parmi des crèmes, des onguents, des laits, des suspensions, des poudres, des huiles, des lotions, des gels, des sticks, des mousses, des émulsions, des dispersions, des sprays, des aérosols, des rouges à lèvres, des fonds de teint, du maquillage, des poudres libres ou compactes, des fards à paupières, des ombres à paupières, des mascaras, des vernis à ongles, des laques à ongles, et des compositions pour la teinture non permanente des cheveux. 8. Les composés d’ester de l’acide benzoïque pour l’utilisation selon la revendication 5, où la composition cosmétique ou pharmaceutique ou la composition de soins personnels comprend une quantité efficace du composé d’ester de l’acide benzoïque qui va de 0,01 à 40% par rapport au poids total de la composition. 9. Les composés d’ester de l’acide benzoïque pour l’utilisation selon la revendication 8, où la quantité efficace du composé d’ester de l’acide benzoïque va de 0,05 à 25% par rapport au poids total de la composition. 10. Les composés d’ester de l’acide benzoïque pour l’utilisation selon la revendication 9, où la quantité efficace du composé d’ester de l’acide benzoïque va de 0,1% à environ 15% par rapport au poids de la composition. 11. Les composés d’ester de l’acide benzoïque pour l’utilisation selon la revendication 5, où le composé d’ester de l’acide benzoïque dans la composition de soins personnels photostabilise des ingrédients de la composition face au rayonnement solaire. 12. Un composé d’ester de l’acide benzoïque de formule (la) :

dans laquelle R est un groupe choisi parmi (i), (ii) et (ici) :

dans laquelle R-|-R5 sont indépendamment choisis parmi l’hydrogène, alkyle en (CrC6), cycloalkyle en (C3-C6), alcoxy en (CrC6), cycloalkoxy en (C3-C6), hydroxy, amino, alkylamino en (CrC6), dialkylamino en (CrC6), où les deux parties alkyle dudit dialkylamino peuvent former, conjointement avec l’atome d’azote auquel elles sont reliées, un hétérocycle choisi parmi la pyrrolidine, la pipéridine, la morpholine et la pipérazine facultativement N-substituées par alkyle en (C-|-C6) ou cycloalkyle en (C3-C6), cycloalkylamino en (C3-C6), (alkyle en C1-C6)-(cycloalkylamino en C3-C6) et dicycloalkylamino en (C3-C6), ou deux groupes sur des atomes de carbone adjacents de l’anneau forment un groupe 0-(CH2)m-0 condensé, où m est 1 ou 2, ou deux groupes sur des atomes de carbone adjacents de l’anneau forment un groupe CH=CH-CH=CH condensé ; R’ est l’hydrogène ; R6-Rio sont indépendamment choisis parmi l’hydrogène, alkyle en (C^Cg), cycloalkyle en (C3-C6), alcoxy en (C^Cg), cycloalkoxy en (C3-C6), hydroxy, amino, alkylamino en (C1-C6), dialkylamino en (C1-C6), où les deux parties alkyle dudit dialkylamino peuvent former, conjointement avec l’atome d’azote auquel elles sont reliées, un hétérocycle choisi parmi la pyrrolidine, la pipéridine, la morpholine et la pipérazine facultativement N-substituées par alkyle en (CrC6) ou cycloalkyle en (C3-C6), cycloalkylamino en (C3-C6), (alkyle en C1-C6)-(cycloalkylamino en C3-C6) et dicycloalkylamino en (C3-C6), ou deux groupes sur des atomes de carbone adjacents de l’anneau forment un groupe 0-(CH2)n-0 condensé, où n est 1 ou 2, ou deux groupes sur des atomes de carbone adjacents de l’anneau forment un groupe CH=CH-CH=CH condensé; R-i-i est choisi parmi l’hydrogène, alkyle en (C^Cg) et cycloalkyle en (C3-C6) ; R12 est choisi parmi l’hydrogène, alkyle en (C^Cg) et cycloalkyle en (C3-C6) ; R13 et R-I4 sont indépendamment choisis parmi l’hydrogène, alkyle en (C^Cg), cycloalkyle en (C3-C6), alcoxy en (C^Cg), cycloalkoxy en (C3-C6), hydroxy, amino, alkylamino en (C^Cg), dialkylamino en (0Γ06),ού les deux parties alkyle dudit dialkylamino peuventform er, conjointement avec l’atome d’azote auquel elles sontreliées, un hétérocycle choisi parmi la pyrrolidine, la pipéridine, la morpholine et la pipérazine facultativement N-substituées par alkyle en (CrC6) ou cycloalkyle en (C3-C6), cycloalkylamino en (C3-C6), (alkyle en C1-C6)-(cycloalkylamino en C3-C6) et dicycloalkylamino en (C3-C6) ; ou le groupe OR12 et R14 forment un groupe 0-(CH2)p-0 condensé dans lequel p est 1 ou 2 ; R15 est choisi parmi le 1-pyrrolidinyle, le 1-pipéridinyle, le 4-morpholinyle et le 1(4)-pipérazinyle facultativement 4(1)-substitués par alkyle en (C^Cg) ou cycloalkyle en (C3-C6) ; et

Ri6-Rl8 sont indépendamment choisis parmi l’hydrogène, alkyle en (C^Cg), cycloalkyle en (C3-C6), alcoxy en (C-|-Cg), cycloalkoxy en (C3-C6), hydroxy, amino, alkylamino en (C1-C6), dialkylamino en (CrC6), où les deux parties alkyle dudit dialkylamino peuventform er, conjointement avec l’atome d’azote auquel elles sont reliées, un hétérocycle choisi parmi la pyrrolidine, la pipéridine, la morpholine et la pipérazine facultativement N-substituées par alkyle en (C^Cg) ou cycloalkyle en (C3-C6), cycloalkylamino en (C3-C6), (alkyle en C-i-CgHcycloalkylamino en C3-C6) et dicycloalkylamino en (C3-C6), ou deux groupes sur des atomes de carbone adjacents de l’anneau forment un groupe 0-(CH2)q-0 condensé, où q est 1 ou 2, ou deux groupes sur des atomes de carbone adjacents de l’anneau forment un groupe CH=CH-CH=CH condensé; à condition que lorsque R.,, R2, et R4-Ri0 sont tous hydrogène, R3 ne peut pas être hydrogène ou méthoxy ; et à condition que lorsque RrR7, R9 et R10 sont tous hydrogène, R8 ne peut pas être méthyle ; ou un sel pharmaceutiquement acceptable de celui-ci. 13. Le composé d’ester de l’acide benzoïque selon la revendication 12, où dans ledit composé, lorsque R est (i), R3 est indépendamment choisi parmi alkyle en (C-|-C6), cycloalkyle en (C3-C6), alkoxy en (C^Cg), cycloalkoxy en (C3-C6), R8 est indépendamment choisi parmi l’hydrogène, alkyle en (CrC6), cycloalkyle en (C3-C6), alkoxy en (Cf-Cß) et cycloalkoxy en (C3-C6), et R·,, R2, R4-R7, Rg et R10 sont tous hydrogène ; lorsque R est (ii), R1-R5, Ru, R13 et R14 sont tous hydrogène et R12 est alkyle en (C^Cg) et cycloalkyle en (C3-C6) ; et lorsque R est (iii), R15 est choisi parmi le 1-pyrrolidinyle, le 1-pipéridinyle, le 4-morpholinyle et le 1(4)-pipérazinyle facultativement 4(1 )-subs-titués par alkyle en (0Γ06) ou cycloalkyle en (C3-C6) et R16-R.|8 sont tous hydrogène ; à condition que lorsque R.,, R2, et R4-R10 sont tous hydrogène, R3 ne peut pas être hydrogène ou méthoxy ; et à condition que lorsque R.|-R7, Rg et R10 sont tous hydrogène, R8 ne peut pas être méthyle ; ou un sel pharmaceutiquement acceptable de celui-ci. 14. Le composé d’ester de l’acide benzoïque selon la revendication 13, où ledit composé est choisi dans le groupe constitué de : 1-(4-méthoxyphényl)-vinyl 4-ferf-butylbenzoate ; 1-(4-ferf-butylphényl)-vinyl 4-méthoxybenzoate ; 1-phénylvinyl 4-ferf-butylbenzoate ; acide 4-benzoyloxy-2-méthoxybenzènesulfonique ; et 3-(1-pyrrolidinyl)phényl benzoate. 15. Une composition cosmétique ou pharmaceutique, ou une composition de soins personnels contenant au moins un composé d’ester de l’acide benzoïque tel que défini dans l’une quelconque des revendications 12-14, ou un sel de celui-ci. 16. Un procédé de préparation d’un composé d’ester de l’acide benzoïque tel que défini dans la revendication 12 dans lequel : si R est (i), alors le procédé est mis à exécution moyennant la réaction d’un halogénure d’acyle de formule (II) :

dans laquelle Ri-R5 sont tels que définis dans la revendication 12, et X est un atome d’halogène choisi dans le groupe constitué du fluor, du chlore et du brome, avec un silylénol de formule (III) :

dans laquelle R’ et R6-R.|0 sont tels que définis dans la revendication 12 et R19-R21 sont indépendamment choisis parmi alkyle en (C^Cg), cycloalkyle en (C3-C6) et C6H5-(CH2)r-, où r est 1-4, ou deux groupes peuvent former, conjointement avec l’atome de silicium un anneau choisi parmi le silolane, le sililane et le silépane, en présence d’un catalyseur choisi dans le groupe constitué du chlorure mercurique, du chlorure cuivreux et des mélanges de ceux-ci ; si R est (ii), alors le procédé est mis à exécution moyennant la réaction d’un ester de l’acide benzoïque de formule (IV) :

dans laquelle R-|-R5 et R-|2_R14 sont tels que définis dans la revendication 12, avec acide chlorosulfonique suivie d’une réaction d’estérification facultative avec alkyl-OH en (C^Cg) ou cycloalkyl-OH en (C3-C6) ; ou lorsque R est (ii) et Rn est hydrogène, moyennant l’estérification d’un produit intermédiaire (VI) : (VI)

où R^ est hydrogène et R12-Ri4 sont tels que définis dans la revendication 12, avec un acide intermédiaire (Vil) :

où R1-R5 sont tels que définis dans la revendication 12 ; ou lorsque R est (ii), moyennant l’estérification du produit intermédiaire (VI) :

(Vi) où R11 est alkyle en (C^Cg) ou cycloalkyle en (C3-C6) et R-|2_R14 sont tels que définis dans la revendication 12, avec (Vil) ; et si R est (iii), moyennant la réaction d’un halogénure d’acyle de formule (II) :

dans laquelle R-1-R5 sont tels que définis dans la revendication 12, et X est un atome d’halogène choisi dans le groupe constitué du fluor, du chlore et du brome, avec un phénol de formule (VIII) :

dans laquelle R-15-R-18 sont tels que définis dans la revendication 12. 17. Le silylénol de formule (III) tel que défini dans la revendication 16quiestle4-ferf-butylacétophenonetriméthylsilylénol.

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description • US 4387089 A [0010] · US 6409995 B [0014] • US 2853521 A [0011] · JP 4065065 B [0030] • US 2773903 A [0012] · US 4036951 A [0031] • US 2861104 A [0012] · US 3751563 A [0031] • US 2861105 A [0012] · WO 02095393 A [0031] • US 3073866 A [0012] · GB 860939 A [0031] • GB 1136525 A [0013] · US 3033814 A [0031]

Non-patent literature cited in the description • Federal Register, 1999, vol. 64, 27666-27963 [0006] · HUH, TAE-SONG et al. Kinetics and mechanism of • YANAGISAWA M. et al. Aldol Reaction of Enol Es- the hydrolysis of enol ester in strong acid solution, ters Catalyzed by Cationic Species Paired with Tet- Journal of the Korean Chemical Society, 1994, vol. rakis(pentafluorophenyl) borate. Chem. Pharm. Bull., 38 (5), 391-6 [0028] 2000, vol. 48 (11), 1838-1840 [0027] · RUPPIN C. et al. Synthesis of Enol Esters from Ter minal Alkynes Catalyzed By Ruthenium Complexes. Tetrahedron Letters, 1986, vol. 27 (52), 6323-6324 [0029]

Claims (8)

1. ΕΡ 1868 984 81 SENZGESAV-ÉSZTER VEGYQLETEK, KÉSZÍTMÉNYEK, FELHASZNÁLÁSOK ÉS EZEKHEZ KAPCSOLÓDÓ MÓDSZEREK Igénypontok •1* Senzoesev-észter vegyülitek az (!) képlettel jaiíemezve;

   ahol RvRs egymástól függetlenéi hidrogén, Gi»C$-alkü, C«-C<H5ikl0aikif. Gí-Ga-alkaxI, :Gs-C«-cikíoaikoxi, hidroxs. amino Cí~e«saiki!amino, Ci-Cr-o'taikilamino közűt választott, ahoí az említett diaikiiamirioosaport két említett aíkilesoportja azzal a niljfogénatommaí együtt. amelyhez kapcsolódnak, heteroclkíust alkomat psrroüdtn, pípeudin, morfolin és piperazm kézül választva, ami adott esetben Cs-Cs-alkii- vagy C?-ű?;· ctkioafkii··, (><-C&amp;-cikioalKii-amino- CvCe-aikil-Cí-Cn-cikioalkil-stbino-· és Cá'Cs-dtakfoalkiiamfno-csqsoraal N-szubsztituáit. vagy a gyűrű szomszédos szénatomjain lévő két csoport agy lűzienáll O-CCkfejteO csoportéi .alkot, ahol m jelentése .1 vagy 2. vagy a gyűrű szomszédos szénatomjain lévő két csoport egy fuzionált CH~CH-CH=CH csoportot alkot, R jelentése egy csoport az {ű, ni) és íiézűi yá'SSZtva:

   ahol R' hidrogén. Cr-Ckvaíkli ésiGs-Cc cskíoaíklt kezűi választott, Rí-RisiSgymástó! függetlenül hidrogén, Ci*Cs-a!kil: Cs-Cs-cikloaiklI, C^Cs-aike», Gs-Cs-eikioalköxi, tíldrox:· amine, Gi-Ce-alkitamirso. Ci-Cs-disiklIarnino közti! vrjtasztott, ahoi az említeti dialkilamíno^csoport kot említett alkitesoportia azzal a nitrogénetomma! együtt, amelyhez kapcsolódnak, heieroojkkisl alkomat plrfoltdin. flipedéin, morfolin és piperazln közti! választva, ami adott esetései Ci-Cs-aiklI-vagy C.vCr cikloalkli-, Cs'Cs-cíkiosikil-amlnc-. Gi-es-alkii-C?,'Ca-cikioa!kil-amirto·· ás Cs Ca-dicmloaiklfarntno esopoittal N-szubsztiíűáU, vagy ti gyűrű szomszédos szénatomjain lévő két csoport egy fuzionált O (CH?) -O csoportot alkot ahol n jelentése 1 vagy 2. vagy a gyűrű szomszédos szénatomjain tévő két csoport egy fuzlonéit CH::iGH-CH=GH c-soportot alkot, Rí, hidrogén, Cv-Ce-atkil ás G.vGeolktoaikil közül választolt; .. R;? hidrogén, Ci-Cr-alM! és C,-Cf.-okíoaikii közút választót·; 11 jjijj lj| jjijj jjijjj jj J|

   j j f Ρ 1, 868 984 8.1 R>s éss Rí,·! egymástól: föggétlértöí bjdf ogér . Gr^e-s Ikii, Ós-Gsosiki öaiki i (1¾ bidroxí, arainoi ÍSíkessálkílaminö, Ct'Ge-dialkiia.'íimo közül váiasztött, ahol az említett dratkilamino-csöpötí két..említett aikiiosoportja azzal á.riifragáBatornmat együtt, amelyhez kapcsolódnak, heterocíklust alkothat pitroíidin. pípertdin, mörfoíin és piperazín közöl választva. ami adott esetben Ci-Ct^alkik vagy Cs>C«« cíkíoaRil-. Cs-C-'r-cikioalkii-amino·. ii· Ce-aikt!~C.yC«--cikSoaikihamino·· és O-s-Cs···;icikloaik: iámino· csapon!aí •észi.íbsziitoáít. vagy a:: OR;,:és Rí* csoport egy fuzionált 0*{CH?irO-csoportot alkot. ahol p jelentése t vagy 2. : R-;, az alábbiak közel.....választott: 1 -p:rroisdir«t. 1 -piperid;r!ií. adott esetben Ci-C«-aikli- vagy C.vCe-clkloalkil-, C;-C:vcik!oalkil--amlno·. {ii Gft-aikil-Cn-Gs cikioaikH-a'nino· és Cs-Cí-diciktoalkiiamino-csoporttal N-ezubsztitoáit; és Rsö-Rt? egymástól függetlenül hidrogén, Ci-Cs-atkii, CsrCs-cikloalkib Ci«C<s-alkoxt. Cs-Ca-oik.ioaikoxI, hidroki, amirtO: Cs-Cti-alkiíamino, Gr-Gfr-dfsikiiamino közűi választolt, .ahol az emStietidmikilamino csoport !fe&amp;í^i©rhíiieií -:^ítííí^!i3p|£3i^j3;:.^^^" :kálÖj^(?|^fán^!|í;y:;:h^t«rQ<S^;íU^t-^^OÍh:^it: gífroíidin, pipertcnn, morícím és piperszln közül választva. and adott esetben Ct-0*-aikii- vagy Ge-Csé cikloalkil·. C:-C:v-cikk>aikJ an'Íínű·. C--{Vsikif--Ci-Gs--rikloaikii--amino·· és G^-Cs-didkloalkiiamino-csopornal N-szubsztitoáit......vagy a gyűrű szomszédos sZéftatön^ain tévé két csoport egy fuzionált C-(CHs.krO csoportot alkot, ahol q jelentése 1 vagy 2. vagy a gyűrű szomszédos szénatomjai lévő két csoport egy fuzionál* CH»CII~CH«CH csoportot alant: vagy ezek gyégyászatiiag elfogadható sója, βίο próbát! vagy álla* szervezet UV-sugátxásíöi va-ő vád-ámében vak; felhasználásra '% Az. 1 igénypont szerinti benzcesav-észte: vegyüleíek. ahol amikor a benzcesavtösztér vögydetbén: R jelentése fi), akkor Rs függetlenül választolt metoxs és íerobutll közöl. R« függetlenül válaszlott hidrogén, m<-ío>! <, <ot <υ?ν valamim R\. Re R:o R* Rs, Re.. Rv. Rsés Rio jelentése-egyaránt hidrogén: amikor R jelentése {irt akkor r·,. R;:, Rs, r,. r<.. Ru. Rués R;/. jelentése egyaránt hidrogén é^izjéWé8e-:h#S|í és amikor R jelentése (iii}, akkor Rt függetlenül választott hidrogén és hídfője közöl Rs függetlenül ; választott hidrogén és meíox: közöl, Rw jelentése a-pirroiicilnif és R,:. R.y R$, R:§. Rí·? és R<« jelentése egyaránt mdrogőn. 3. A 2. igénypont szerinti benzoesav-észter vogyóíetek. ahol a benzoesav-észior vegyesei a következő CÖOpOltbÓI Vál.BSZiOlt i-(4-ir-otO!<iter:!Í}-vi!i!i-4-e;;/z:-bisÍ:ibenzoá;; |,f4,rBr^b!jfj|f8nil)-vífa!v.-i,fn®íozít5?5nzo3t: 1 -feniívlnii-4-fen?--butilbenzQát; 4-benzo8ow-2-metojd-benzoSszulfonssv; és 3··(ΡρΐΓίοΐΐίΙίη!ΐ}··ίβηί)>θ6πζοθί,
2. 4. A henzoesáv-észte' vesydeiek az 1 igénypont szerinti felhasználásra. ahol az élő emberi vagy általi szervézíít ember,
3. 5. A berszoesav-ószíer vegyületek az 1. Igénypont szennti felhasználásra, ahol a benzoesav-észter vegyuletekét kozmetikai vagy gyógyászati készítmény vagy testápolási készítmény tartalmazza. FF 1 868 984 B.t
4. 6. A benzoesav-észter vagyúletek ág 5. igénypont szerinti felhasználásra, ahol a kozmetikai vagy gyógyászat: készítmény itatásos mennyiségbe·-! tarfaímaz legalább egy olyan beíszoesáv-észtöt vegyüietet. ami alkalmas arra. hogy >n -sitii- fctokémiatlag átalakítható legyen erős UV-sztirő képességű: napvédő vegyüietté.
5. 7- A benzoesav-észter vegyültök az 5. igénypont szenntl felhasználásra. ahol az említett ikozi^élikailvagylf gyógyászati vagy les-ápolási készítmény az alábbiak közöl választól:::; kiéinek, kenőcsök teiékll szuszpanziók. hintőporok. ók'iii:iii;:^i^|ífek; stiftek, habok, emulziók, diszperziók, apráy~||| aeroszolok, rúzsok. alapozók, sminkek, por· vagy kompaktpúOerek. szemhéjpúderek, szemhéjfestékek szempillafestékek. korom fen yesitök. körömlakkok és nőm tartós najfessó készítmények.
6. 8.. A benzOésSy-éSztár vegyáiéfek:: az 6 igénypont :szenníi fel Használásra, ahol M közmatikair -vágy gyógyászati vagy tastápojáé; íkáSzíímény hatásos: : mennyiségű, 0,01 és: fDsújyszázalék Ikóáötti benzoesav-észter vegyoistet tartalmaz a készítmény teljes súlyára vonatkoztatva.

   8. A DénZoésávsésfféf vegyiilefek a 8 Igénypont szerinti felhasználásra, ahol a benzoesav észter vegyülő; hatásos rnéb:Óyiáé|é 6,05 iffeÉSíSŰlyszazaiék vohaikozlátva.
7. 10. A berizpesaSkésztef végyöléfeík a S igénypont szenntlíJelbaszóÉásfa: ahöi a benzoesav-észter vágyóiét hatásos mennyisége 0,1 sűiyszázalék és körUlfcefúkífSsöíyszázaíék között van.
8. 11. A benzoesav-észter vegyietek az 5. igénypont szerinti felhasználásra, ahol a testápolási készítményben található benzoesav-észier vegyüíet fotostafciíizálja a készítmény összetevőit a nap sugárzásával szemben. m Benzoesav-észter vegyulet az {fa) képiedéi jellemezve

   ahol R jelentésű égy csapon az (i). (::} és (P- kozúi választva:

   állói ;Rí-'Rs egymástól függeílenúl áidíbSéh· Ci-:§e-:Ékíl:, Cskis^iiöaikíi, Oi-Co-atköki, (Is-Qs-eíkiöaiközi, hidfpki: amino, C^Cfzaiiulamino, Éö2i1'-VálaSsított, áléi az említett dialkíiaminö-csopört kéi ernííietl aikiíesosx;r|(a azzal a öl^ígliiiilöyhsitií -W$%> ameiyhfez kápssplödnak, heíetöcikíbsi alkothat kP .1 868 984 Β1 pírrsiidírt, piperiöir;, mörföiirf és pspefaztn kőiül választva, ami adott esetben C^Oe-alkik· vagy Gs-C<n cikiosikíí-, Cs-CfegíkÍDalkil-aniiRD', Ci -Ceaikjl-Gs-Cedkioatkll- ara;no- ös Ca“Ce<<titt{tte5ik«amÍRO-»C$ő^rttal R-szubsztituáit, vagy a gyűrű: $zoms2édo$ szénatomjain lévő két csoport egy fuzionált ORCH2),trO csoportot alkot, ehöl m jelentése 1 vagy vagy a §yörö· szomszédos szénatomjain lével két csoport egy teionált CH«CB*CM=CM csoportot alkot: R'jeierűése hidrogén: Re~R egymástól-függetlenii! hidrogén, C^Ce-alkil, Gs-Cri-cikloalkii. Ci-Cs-aikoxi, Gs-Ge-cikioalkoxi. hsaroxi. árnino, G: -Gealkilamlno. GvGfc-dtalkiiamino közöl választott, ahol az említett dlsikiiemino-osypyrt két említett aikilcsoportja azzal a oitrögénaíornntai együtt, amelyhez kapcsolódnak, heteröcrklusi alkothat ptrroiidm. pipettám. marfűim és piperazis közül választva. ami adott esetben CsGé-aiki!-· vsgy C:<--Oe, .ctidoaiki!-, CsnCíHákioatkihaminO'.; C.tkGévaJki.kGákC8^Woalkil·amino^ és Cs<Oardic(k!os!kilanána,«söporttai Nkpubsztituáít, vagy a gyűrű szomszédos szénatomja®» lévő két csoport egy fuzionált O-íCHzVO csoportot alkot, ahol: n jelentése 1 vágy 2. Vágy a gyűrű szomszédos, szénaíömiain lévő két csoport egy fűziooslt CH«CH-.GH-C.H csoportot alkot: Ri> hidrogén. Gí-Ce-alkil és C^C-s-ciklóalkil közül választott; Riz hidrogén, Gi-Cs-alkií és Gs-Gsoikloalkii közét választott; Rí λ és :R« egymástól függétiénül hidrogén, G-i-Ce-alki!, Cs-Ceclkloalkil. Ct-Cs-alkoxi, Cs-CsOlkloalkoki, hidfoxt, amino; OiGoalkiiamino, Ci Ce dialkilafníno közűi választott, ahol az emlitett diaikiiamino-csoport kel említett aikliosopor^a azzal a niírogénstommal együtt, amelyhez kaposeíódnak. hateroctklnsí alkothat pííröiiciin.. pipettáin. morfin· és píperazin közűi választva, ami adott esetben CG-Cs-alkH- vagy Ca-Cs-. síkloalkíl-. Ca-Ce-fákioaiRikarwno-. Cí Cf:-alkll-Ga'Cs clkloaikii-amino· és GHiedidklöaikiiamlno-csöpDtltai N-szubsztituálí. vagy az OR:; és Rv, csoport -reejy fazronált O^CHíV-O-csopodot alkot, ahol p jelentése 1 vagy 2; R’i. a következők közül választott' 1-pifroltdlfMl. í>piperidinii. 4-morfölinii és 1 (dÍTptporszinil-adott esetben ti 1 s-pöziolóban C-:-C">aikil- vagy C.:.-C;eci!<!oa!kii-csüporttal szubsztttuálva; és R:s-R(o egymástól lutjgallenűl hidrogén. Gi-Cealkíl. Os-Gv-CiKloalkíi, Ci-C&amp;-ai*axi, Cí-Ce-cikioaikoxí, hídféxi, amíno, CnCv-alkilsmlno. 0s~|Í3!^:íyi^Íiliöm>nö::liNiö iáis?£teitt, ahol az említett dialkiiaminc-csoport :kát:ámIítélt álkiiesöpefljá; ázzál a nmogénatonimal együtt, ame|héz kS^K3sóÍósf.riáKi: pirreiidm. pipendln, mottóim: ás piperazm közül választva, ami; ttdötl: esetben ch-Ge-aikiI· vagy C>-C«·· öikjbpikih Ι|^-οΙΗ1©8

   Ι||ΡϊΙ”ιΟγ, Giiki:-Gs-©6-GitiioaIkil--arr-rffrö- és Gó-G;vdielklplalkilamlnö-csepöÉá| -vagy- szeátszádss széldtomiain lévő két csoport egy fuzionált ö-CÉtj^Ö· Gáéportot ájkőt, ahol: g jpiéntésé 1 vágy:2, vágy ;S;:gyű!'ö szomsáádps &amp;zénátep|áih lévé kát csoport egy fuzionált CH=CH-CH::CH csoportot alkot: azzá! a felíéiellei. hogy ámlkor R. Rí és R;-Rv jelentése egyaránt hidrogén. akkor az R>. nem tehet serit méregén. sem msicx· ás: azzal a feltétellé!, hogy amikor R*-R·.. R» és F.::·: jelentőse egyaránt hidrogén. , akkor az Fű nem lehet metil, vagy ezek gyógyászntüag elfogadható sója. •!3. A l|. Igénypont szenoh benzoosav-észter vegyüiet ahol amikor az említett vecyüieitsen R jelentése {i}, ,....... Ókkor R:t föggátlenül Választott G:r::Gs-alkiÍ, GzRJáájiklorttkil,, Gc-Geralköki:,: .^éiGétriiftlS^lid^h :!^köl', R§: függétlehűl: ;ySlásztott hidlrégéh. GyCs-áikii; Ca-Ge-ölkídálkií. CiRSs-mlkoxf -M Ga-GmPíkiöalköki közöl, amikorRljélehSésé (ib, #kör Ri'RspRr-pRia és FA,·, jelentése egyaránt hizirop-irít és Re; jelentőse C; C>;-alkii és Cs-Cs-ciklöalkil; es amikor R jelentési? (ifi), akkor Rio a következők közűi váSeszraít: 1 •nirfoiidinii. l-pipendinű, 4·η?οΓ?ο!!ΐ··ΙΙ és 'lídi-piperazinii adok esetben 4 (ι )·ρο,?:ί·?.:όί;οη C > C<v.olkil- vagy C<'.-CR;-cikioalkil-csopertta! szubsztituálva es ijs-R:?» jelértiése ÍP 1 868 984 BJ egyaránt hidrogén. azzal a feltéteüel, hogy amikor R:. R; és R-rR··:.· jelentése egyaránt hidrogén. akkor az Rj nem lehet som hidrogén sem meloxi: ás azzal a feiiéleliol. hagy amikor Rt-R>. R<> és R<s jelentése egyaránt hídfogerv,, akkor az: R« herr! lehet metii; vagy ezek gyógyászafsiag elfogadható sója. 14. lr|:3. igénypont szenet: Penzoesav észter vegyület. .^é||^:éSÍÍÍ^: vegyüfei a: következe; csapodból :: válaszfolt: 1 •(4-mekíxlferiií)..v;n:Mfo:>m.t;utli;xmzo3t. 1 '(4-ó^m.45utiifenil)-vlnil-4..mat<z/ILieiUzoát l-fenliviníM-förc-butliCenzöét; 4.penzoiloxt-2.me!oxifoehxo!sziíiionsav. os I S. Kszmatíkai vagy gyógyászati: készítmény vagy testápolási készítmény;: á l|ki4; igénypoéidk básTneiyikésxoririti béh^öt sav-észior vagy 18,: Eljárás a 12. igénypont szerint: óenzoesav-öszter vegyüieí előállítására, ahol: ha R jelentése (i>. akkor az eljárást úgy hailiok végre, hogy égy. a (II; képlettel jellemzőt! acii-haiogenfoei

   ahol Ri-Rsjoleníésé megegyezik a 12. igénypont meghatározásával, és X jelentése egy haiogénatom az alábbi -csoportból választva: fluor, klór ás bróm, ráágáÍfeitohk ágy. a (Ül) képiettei jeiiwtóM sziiiieriOliai:

   ahol R és Re-Rio jelentése megegyezik a 12. igénypont meghatározásával és Ri&amp;-R^ egymástól föggátferióí píasziött G:M^aÍkiíí................... és CiHe-iCH:·!.- kézül, ahoi r jelentése 1b, vagy két I csoport azzal a sziiieiurnntommal együtt. amihez kapcsolódnak. egy gyűrű; alkothat, amely a következők közit yájásztott; özjlol 021111 és szi!ep^;^fe

   ií':|^f#ében..ameiy árkOvétkazö ssQpótihöllláiapztoft:: iiigány-ikiorio. iééíkfendíés ézek kéyerékéf: ha R jelentése rii). akkor az eljárást úgy hajtjuk végre, hogy egy. a (IV) kápfeíteí jsiigmzeí:| benzoesav-észtert: EP 1 ·%8 984 8i

   λ< y i anoí Rj-Rsés R-12-Rujeieméss» megegyezik· a 12. igénypont meghatározásává:. reagáítatunk klömzutfensavval.. amit egy opcionális áíatefezési reakció Követ Gt-C«-a!kií-OH-da; vagy (;.·> Oe-oikioatkii-OH>dai: vagy amikor R jeieniéso 00 és R:: jelentése h:d;ogén. skxor úgy hííjtsui-: végre, hogy a {Vi} képiéMi ietiemzeti ihíértnediail é?5,?bsfpsaük:

   ahol Ro jelentése hidrogén és R< · H-« Sertése megegyezik a 12 ^éovpont.Wégptajf^áss{f;»gJ «*** intenmediei rei amit a ·Vtí) képlet jellemez

   ahol R<-R;> jelentésé; megegyez;:*; a 12. igényfior't.meghatámzásava;; vagy amikor R jelentése {«). akkor úgy ha&amp;uk végre, hogy a {Vi^képiette!j6Jiep^©fe{n|é^^fep;é$2tt^?.8k.:

   (Vi; ahol Rí '! jí; C i Cft-aíkl! vagy G.vCr.vúiíIoaikiÍ és Ro-Rv: jelentése megegyezik a 12. igénypont .meghatározásával, a (Víi) képtetü vegyüiéttei: és n.a R jsföntéée {»p-( akkor úgy Hajtjuk végre, hogy a (11) képletet acii-nalogenidet reactáitatjuK. IP 1868 984 81

   69 shöi Rrfísjeienlésa msgagybzik a 12. i§^s.ypofi{' m#9haíát»2ásávai, és X jeieotésö égy haiögéaatöra az alábbi: ósoportbdf választva: fluor,, klór és broro, agy. a (VHi) képiatreí jaíiamzsá: fenoiiat:

   ahol Rís-RssiéleritéSé niégectyezlk a 12. igénypont biéghalarazásSvai. 1?. A 161 igénypont szenbts (lií} képlétte; jeiiBfnzött sinÍ.ienoi, árrá egy 4^ríNl3Plií--g{:>slofáéOMfiH^.i:'^?-lil.iaf'(OÍ.