Organic-silica hybrid triazine derivates for UV protection

Abstract

It relates to certain organic-silica hybrid triazine compounds, their pharmaceutically or cosmetically acceptable salts, stereoisomers of any of them or mixtures thereof, and to particulated compounds obtainable by hydrolysation-polycondensation of the previous compounds, as well as compositions comprising them. The particulate compounds are useful for the protection of a human, or animal living body, from ultraviolet radiation; and also, in a method for protecting a material from ultraviolet radiation which comprises treating the material with a composition comprising the particulated compounds.

Description

[0001] Organic-silica hybrid triazine derivates for UV protection

[0002] This application claims the benefit of European Patent Application EP24383115 filed 11 October 2024.

[0003] Technical Field

[0004] This invention relates to triazine derivates, a process for their preparation, their compositions comprising them, in particular sunscreen compositions, as well as their use for enhanced UV protection.

[0005] Background Art

[0006] The use of both organic and inorganic compounds in sunscreen compositions is well established in the field of UV protection. Inorganic filters, such as zinc oxide, titanium dioxide, and silica, are commonly used for their broad-spectrum UV-blocking properties and photostability.

[0007] These compounds are effective at scattering and reflecting harmful UV rays, offering a physical barrier that complements the UV absorption properties of organic filters. Together, these components create formulations that provide robust sun protection. However, despite their widespread use, the combination of organic and inorganic filters presents certain challenges, particularly in terms of solubility, formulation capabilities, and safety, which must be addressed to optimize sunscreen performance.

[0008] On the other hand, triazines are well-known for their UV protection capabilities. EP0933376A2 relates to a group of s-triazines, a process for their manufacture and the use thereof as UV-B filters in light screening compositions, especially for the preparation of a cosmetic composition useful for protecting human skin from sunlight radiation. Likewise, W02009053149A1 discloses s-triazine derivatives containing at least two particular silane aminobenzoate or silane aminobenzamide groups and to their cosmetic uses. The document also relates to photoprotective compositions comprising s-triazine derivatives containing at least two particular grafted silane aminobenzoate or silane aminobenzamide groups as sunscreens that are active in the UV-B radiation range.

[0009] Since triazine derivatives are generally insoluble, compounds such as branched saturated C15-19 alkanes are added to improve solubility. However, some safety concerns are still present, as this may lead to skin penetration and other adverse effects when used in sunscreen products. Thus, WO2022122838A1 discloses cosmetic composition comprising an ester of a fatty acid and dextrin, a mixture of branched and linear saturated C15-19 alkanes, wherein the mixture comprises primarily branched saturated C15-19 alkanes, and a UV-filter, ethylhexyl triazone. This cosmetic composition allows the solubilization of a higher amount of the ethylhexyl triazone. However, solubilizing high concentrations of UV filters like triazines can pose potential safety concerns such as skin penetration and irritation. Particulating them in this manner avoids these issues since these are not meant to be solubilized.

[0010] It is therefore desirable to provide compounds that can offer excellent formulability and enhanced safety, and with high SPF values to be able to provide the benefits of both organic and inorganic UV filters.

[0011] Summary of Invention

[0012] Inventors have found a way to address these issues by offering compounds that improves the formulation capabilities of triazines without compromising on safety. Inventor’s compounds avoid the common risks associated with solubilization while maintaining effective UV protection. This not only enhances their practical application in sunscreens but also ensures a safer product while also providing the benefits of the organic and inorganic compounds in one.

[0013] Unlike the s-triazine derivatives disclosed in EP0933376A2 or W02009053149A1 , the compounds of formula (I) according to the invention, thanks to their trisubstitution with specific inorganic functional groups (trialkoxysilyl group), have the capability to particulate to form organic-inorganic hybrid particles when submitted to a Stober condensation, and consequently, achieve better formulation capabilities and safety improvements.

[0014] Advantageously, the particulated compounds according to the invention begin to perform their filtering function immediately upon application or exposure. This distinct approach provides a safer and more effective solution compared to known compounds.

[0015] An aspect of the present invention relates to a compound of formula (I), a pharmaceutically or a cosmetically acceptable salt thereof, or a stereoisomer of any of them or mixtures thereof, wherein: R1 is independently selected from the group consisting of H and (Ci-Ce)alkoxy; p is equal to 3; and Z is a radical of formula (I’), wherein: X is selected from the group consisting of NH and O; Y is selected from the group consisting of NH and O; n is an integer from 0 to 1 ; o is an integer from 0 to 1 ; m is an integer from 1 to 5; and R2, R3, and R4 are selected from the group consisting of linear or branched (Ci-Ce)-alkyl, linear or branched (C2-Ce)-alkenyl, (C3-C6)-cycloalkyl, and phenyl; with the proviso that compound of formula (I) is other than compound of formula (I) where R1 is H, X is O, Y is NH, n is 1 , o is 1 , m is 3, R2, R3, R4 are OEt, and Z is in para position, having the formula below (h),

[0016] Compound (h) has the CAS RN 1380911-06-7. It has been disclosed in KR2012058345A and KR2015124828A. KR2012058345A discloses an organic / inorganic hybrid coating composition that includes a triazine sol-gel compound. The composition is designed for thermohardening coatings and is modified by trialkoxysilal kyl groups, intended for use in coatings for automobile manufacturing, shipbuilding, and other industrial applications. KR2015124828A discloses a thermosetting coating composition specifically designed for plastic substrates. It contains (a) an organic sol containing triazine compounds capable of sol-gel reactions, (b) an inorganic sol containing precursors of three or four atoms, and (c) mineral components.

[0017] Another aspect of present invention is a participated compound, obtainable by hydrolisation-polycondensation of compound of formula (I) as defined above, including compound (h) (i.e. compound of formula (I) where Ri is H, X is O, Y is NH, n is 1, o is 1, m is 3, R2, R3, R4are OEt, and Z is in para position, having the formula (h).

[0018] Another aspect of the present invention, the use of a particulated compound as defined above, for the protection of a human, or animal living body, from ultraviolet radiation.

[0019] Another aspect of the present invention is a method for protecting a material from ultraviolet radiation which comprises treating the material with a composition comprising a particulated compound as defined above. Another aspect of the present invention a composition selected from the group consisting of a cosmetic composition, a pharmaceutical composition, and a personal care composition, comprising at least an effective amount for the protection of either a human or animal living body, from ultraviolet radiation, of a compound as defined above, together with one or more pharmaceutically or cosmetically acceptable excipients or carriers, or alternatively, a composition comprising at least an effective amount for the protection of a material from ultraviolet radiation, of a particulated compound as defined above, together with appropriate components selected from at least a polymer, a solvent an additive, and a mixture thereof.

[0020] Another aspect of the present invention a process for preparing a particulated compound as defined above, which comprises a) hydrolysing a compound of formula (I) as defined above, including the compound of formula (I) where Ri is H, X is O, Y is NH, n is 1 , o is 1 , m is 3, R2, R3, R4are OEt, and Z is in para position (compound (h)); and b) polycondensating the compound obtained in step a).

[0021] Brief Description of Drawings

[0022] Fig. 1 shows General UV-Vis spectra recording of compound 3, 5 wt% vs. particles of compound 3, 5 wt%.

[0023] Fig. 2 includes the TEM image of a skin section where a placebo was applied, a skin section where the particle preparation from Example 3 was applied, and a third section where a nanometric ZnO formulation was applied, in which the clusters embedded in the epidermis are clearly visible. It shows the absence of particles in both the stratum corneum and deeper skin layers.

[0024] Detailed description of the invention

[0025] For the purposes of the invention, any ranges given include both the lower and the upper endpoints of the range. Ranges given, such as temperatures, times, sizes, and the like, should be considered approximate, unless specifically stated.

[0026] The term “room temperature” as disclosed herein refers to a temperature of the environment, without heating or cooling, and is generally comprised of from 20 to 25 °C.

[0027] The term "scanning electron microscope" (SEM) refers to an analytical device that utilizes a focused beam of electrons to produce high-resolution images of a specimen's surface by detecting emitted signals resulting from electron interactions with the sample.

[0028] The terms “(Ci-C6)-alkyl”, “(Ci-Ce)-alkoxy”, “(Ci-C6)-alkylamino”, and “(Ci-C6)-dialkylamino” shall be construed as straight or branched chains with the number of carbon atoms indicated such as e.g. methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, 2-ethylhexyl, , (1 ,1 ,2- trimethylpropyl) and, respectively, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert.butoxy, 2-ethylhexoxy, methylamino, ethylamino, propylamino, isopropylamio, n- butylamino, tertbutylamino, 2-ethylhexylamino, (1 ,1 ,2- trimethylpropylamino, dimethylamino, diethylamino, dipropylamino, diisopropylamio, di n-butylamino, di tertbutylamino, di 2-ethylhexylamino, or di(1 , 1 ,2- trimethylpropylamino.

[0029] The term OEt refers to the ethoxy group, which is a chemical group with the formula -OCH2CH3.

[0030] The term “pharmaceutically or cosmetically acceptable salts” used herein encompasses any salt formed from pharmaceutically or cosmetically acceptable non-toxic acids including inorganic or organic acids. There is no limitation regarding the salts, except that if used for therapeutic purposes, they must be pharmaceutically or cosmetically acceptable.

[0031] As some of the compounds of formula (I) are basic compounds, salts may be prepared from pharmaceutically acceptable non-toxic acids, including inorganic and organic acids. Such acids include for instance acetic, benzenesulfonic, benzoic, camphorsulfonic, citric, ethansulfonic, fumaric, gluconic, glutamic, hydrobromic, hydrochloric, lactic, maleic, malic, malonic, mandelic, methanesulfonic, phosphoric, succinic, sulfuric, nitric, adipic, aspartic, 1 ,5-naphtalendisulfonic, oxalic, pivalic, propionic, tartaric, p-toluensulfonic acid, and the like.

[0032] The preparation of pharmaceutically acceptable salts of the compounds of formula (I), can be carried out by methods known in the art. For instance, they can be prepared from the parent compound, which contains a basic moiety, by conventional chemical methods. Generally, such salts are, for example, prepared by reacting the base form of these compounds with a stoichiometric amount of the appropriate pharmaceutically acceptable acid in water or in an organic solvent or in a mixture of them.

[0033] The compounds of the invention may be in crystalline form either as free solvation compounds or as solvates (e.g., hydrates) and it is intended that both forms are within the scope of the present invention. Methods of solvation are generally known within the art. The term “solvate” refers to a molecular complex comprising any of the compounds of formula (I), or any of their salts, and a stoichiometric or non-stoichiometric amount of one or more solvent molecules bound by non-covalent intermolecular forces. When the one or more solvent molecules forming part of the molecular complex is water, the solvate is a hydrate.

[0034] The expression "effective amount for the protection of a human or animal living body, or a material, from ultraviolet radiation" as used herein, refers to the amount of a compound that, when administered, is sufficient to protect from UV radiation. In the case of human or animal living body this means that prevent skin damage. Thus, the effective amount as used herein refers to a therapeutically effective amount.

[0035] The expression "pharmaceutically or cosmetically acceptable excipients or carriers" refers to pharmaceutically acceptable materials, compositions, or vehicles. Each component must be pharmaceutically or cosmetically acceptable in the sense of being compatible with the other ingredients of the pharmaceutical or cosmetical composition. It must also be suitable for use in contact with the skin of humans and animals without excessive toxicity, irritation, allergic response, immunogenicity or other problems or complications commensurate with a reasonable benefit / risk ratio.

[0036] The term “cosmetically acceptable” which is herein used interchangeably refers to that excipients or carriers suitable for use in contact with skin or human and animals without undue toxicity, incompatibility, instability, allergic response, among others.

[0037] As mentioned above, one aspect of the present invention relates to a compound of formula (I), a pharmaceutically or a cosmetically acceptable salt thereof, or a stereoisomer of any of them or mixtures thereof, where: Ri is independently selected from the group consisting of H and (Ci-Ce)alkoxy; p is equal to 3; and Z is a radical of formula (I’) wherein: X is selected from the group consisting of NH and O; Y is selected from the group consisting of NH and O; n is an integer from 0 to 1 ; o is an integer from 0 to 1 ; m is an integer from 1 to 5; and R2, R3, and R4 are selected from the group consisting of linear or branched (Ci-Ce)-alkyl, linear or branched (C2-Ce)-alkenyl, (C3-C6)-cycloalkyl, and phenyl with the proviso that compound of formula (I) is other than compound of formula (I) where R1 is H, X is O, Y is NH, n is 1 , o is 1 , m is 3, R2, R3, R4are OEt, and Z is in para position, having the formula (h), as defined above.

[0038] In a particular embodiment, in combination with any of the embodiments above or below, the compounds of formula (I) are those were R2, R3, R4 are linear or branched (Ci-Ce)- alkyl. In a particular embodiment, in combination with any of the embodiments above or below, the compounds of formula (I) are those where R2, R3, R4 are ethyl.

[0039] In another particular embodiment, in combination with any of the embodiments above or below, the compounds of formula (I) are those where R1 is H or OCH3. In another particular embodiment, the compounds of formula (I) are those where two R1 are H and one R1 is OCH3.

[0040] In another particular embodiment, in combination with any of the embodiments above or below, the compounds of formula (I) are those where m is 3.

[0041] In another particular embodiment, in combination with any of the embodiments above or below, the compounds of formula (I) are selected from : a) X is NH, Y is NH, n is 1, and o is 1 ; b) X is O, Y is NH, n is 1 , and o is 1 ; c) Y is NH, and n is 0; and o is 1 ; and d) Y is O, n is 0, and o is 1 ,; and e) X is O, n is 1 , and o is 0.

[0042] In another particular embodiment, the compound of formula (I) is that where R1 is H, X is NH, Y is NH, n is 1, o is 1, m is 3, and R2, R3, R4 are ethyl.

[0043] In another particular embodiment, the compound of formula (I) is that, where R1 is H, X is O, Y is NH, n is 1, o is 1, m is 3, and R2, R3, R4 are ethyl.

[0044] In another particular embodiment, the compound of formula (I) is that where R1 is H, Y is NH, n is 0, o is 1, m is 3, and R2, R3, R4 are ethyl.

[0045] In another particular embodiment, the compound of formula (I) is that, where R1 is H, Y is O, n is 0, o is 1, m is 3, and R2, R3, R4 are ethyl.

[0046] In another particular embodiment, the compound of formula (I) is that, where R1 is H, X is O, n is 1, o is 0, m is 3, and R2, R3, R4 are ethyl.

[0047] In another particular embodiment, in combination with any of the embodiments above or below, in compounds of formula (I) Z is in position orto or meta with respect to the amino groups of the aminotriazines.

[0048] Particularly preferred compounds are those illustrated in the examples.

[0049] A participated compound, obtainable by hydrolyisation-polycondensation of compound of formula (I) as defined above and including compound (h), is also part of the invention. Thus, these particulated compounds are obtainable by a process known as Stober process. The product obtained is an organic-silica hybrid particulated compound.

[0050] The term Stober process refers to a chemical process in which a silica precursor compounds, in the present case compounds of formula (l)are hydrolysed in a solvent such an alcohol (methanol or ethanol) in the presence of ammonia as a catalyst. The reaction produces silanol groups. The silanol groups formed during hydrolysis then undergo condensation to create Si-O-Si bonds, forming a silica network.

[0051] The term hydrolysation refers to a chemical reaction in which a water molecule (H2O) is used to break chemical bonds, typically in the presence of a catalyst or specific conditions. In the context of the Stober process, hydrolysis involves the breakdown of silica precursors, such as a triethoxy silane derivative by water to form silanol (Si-OH) groups.

[0052] The term polycondensation refers to a type of chemical reaction in which multiple small molecules, such as silanol groups, combine through condensation reactions, resulting in the release of small by-products, often water or alcohol. In the Stober process, this polycondensation leads to the formation of Si-O-Si bonds, building a three-dimensional silica network or particle.

[0053] In a particular embodiment, in combination with any of the embodiments above or below, the particulated compounds as defined above are those which has formula (I), i.e. without including compound (h).

[0054] In a particular embodiment, in combination with any of the embodiments above or below, the particulated compounds as defined above, are those which has a mean particle size from 20 to 2000 nm measured by SEM imaging and imaging process, conducted at room temperature. In another particular embodiment, in combination with any of the embodiments above or below, the particulated compounds as defined above, are those which has a mean particle size from 50 to 1500 nm. In another particular embodiment, in combination with any of the embodiments above or below, the particulated compounds as defined above, are those which has a mean particle size from 100 to 1300 nm. In another particular embodiment, in combination with any of the embodiments above or below, the particulated compounds as defined above, are those which has a mean particle size from 150 to 1300 nm. In a particular embodiment, in combination with any of the embodiments above or below, the particulated compounds as defined above, are those which has a mean particle size from 220 to 2000 nm measured by SEM imaging and imaging process, conducted at room temperature. In another particular embodiment, in combination with any of the embodiments above or below, the particulated compounds as defined above, are those which has a mean particle size from 500 to 1500 nm. In another particular embodiment, in combination with any of the embodiments above or below, the particulated compounds as defined above, are those which has a mean particle size from 800 to 1300 nm. In another particular embodiment, in combination with any of the embodiments above or below, the particulated compounds as defined above, are those which has a mean particle size from 1000 to 1200 nm. In all embodiment, the mean particle size es measured by SEM imaging and imaging process conducted at room temperature.

[0055] In another particular embodiment, in combination with any of the embodiments above or below, the particulated compounds as defined above are those which have a spherical morphology.

[0056] As illustrated in the examples, the particulated compounds of the present invention exhibit ultraviolet sunscreen properties, in particular, they show an absorbance profile from 290 to 400 nm at least comparable to that form the non-particulated compounds including spectra profile, range of absorbance and molar absorption coefficient. Thus, the use of a particulated compound as defined above, for the protection of a human, or animal living body, from ultraviolet radiation is also part of the present invention. This aspect of the present invention may be formulated as a particulated compound as defined above, for use in the protection of a human, or animal living body, from ultraviolet radiation. It may also be formulated as the use of a particulated compound as defined above for the manufacture of a cosmetic composition, pharmaceutical composition, or a personal care composition for the protection of a human, or animal living body, from ultraviolet radiation.

[0057] A method for protecting a material from ultraviolet radiation which comprises treating the material with a composition comprising a particulated compound as defined above is also part of the invention.

[0058] Particulated compounds as defined above with small particle size (under 220 nm) may be particularly effective for protecting a material from ultraviolet radiation. In a particular embodiment, the method for protecting a material from ultraviolet radiation which comprises treating the material with a composition comprising a particulated compound as defined above, is that where the particulated compounds are those which has a mean particle size from 20 to 2000 nm measured by SEM imaging and imaging process, conducted at room temperature. It is also part of the present invention a composition selected from the group consisting of a cosmetic composition, a pharmaceutical composition, and a personal care composition, comprising at least an effective amount for the protection of either a human or animal living body, from ultraviolet radiation, of a particulated compound as defined above, together with one or more pharmaceutically or cosmetically acceptable excipients or carriers. The compositions of the present invention are topical compositions.

[0059] In a particular embodiment, in combination with any of the embodiments above or below, the cosmetic or pharmaceutical compositions, or personal care compositions as defined above are those where the effective amount of the particulated compound as defined above ranges from 0.5 to 20 wt. % based on the total weight of the composition. In another particular embodiment, the cosmetic or pharmaceutical compositions, or personal care compositions as defined above are those where the effective amount of the particulated compound as defined above ranges from 1 to 15 wt. % based on the total weight of the composition. In another particular embodiment, the cosmetic or pharmaceutical composition, or personal care compositions as defined above are those where the effective amount ranges from 5 to 13 wt. % based on the total weight of the composition. In another particular embodiment, the cosmetic or pharmaceutical composition, or personal care compositions as defined above are those where the effective amount ranges from 8 to 11 wt. % based on the total weight of the composition. In another particular embodiment, the cosmetic or pharmaceutical composition, or personal care compositions as defined above are those where the effective amount is 10 wt. % based on the total weight of the composition.

[0060] In a particular embodiment, in combination with any of the embodiments above or below, the cosmetic or pharmaceutical compositions, or personal care composition as defined above are those where the composition is selected from the group consisting of creams, ointments, oils, lotions, gels, sticks, foams, milks, suspensions, powders, emulsions, dispersions, sprays, aerosols, lipsticks, foundations, makeup, loose or press powders, eye blushes, eye shadows, mascaras, nail varnishes, nail lacquers and non-permanent dyeing composition for the hair.

[0061] In another particular embodiment, the compositions of the present invention can contain one or more additional organic sunscreen agents for filtering IIV-A or IIV-B.

[0062] Appropriate excipients or carriers for the composition of the present invention are for instance, dispersing agents, preservatives, anti-foams, perfumes, fragrances, oils, waxes, propellants, dyes, pigments, emulsifiers, surfactants, thickeners, humectants, exfoliants and emollients. The topical compositions of the present invention can be produced by conventional processes known in the art, such as for instance by mixing the different components of the composition, in any order. The appropriate excipients and / or carriers, and their amounts, can readily be determined by those skilled in the art according to the type of composition being prepared.

[0063] Likewise, a composition comprising at least an effective amount for the protection of a material from ultraviolet radiation, of a particulated compound as defined above, together with appropriate components selected from at least a polymer, a solvent, an additive, and a mixture thereof is also part of the invention. Examples of additives are antioxidants, preservatives, thickeners, coloring agents, or opacifying agents. The composition may be an industrial composition which comprises the compound as defined above.

[0064] The particulated compounds of the present invention can be prepared by a process which comprises: a) hydrolysing a compound of formula (I) as defined above, including compounds of formula (h); and b) polycondensating the compound obtained in step a). This process named Stober process may be conducted in one-pot. The reactions are conducted in an appropriate solvent such as a (Ci-C4)-alcohol. In a particular embodiment, the (Ci-C4)-alcohol is ethanol. The reactions may be conducted in the presence of a catalyst such as NH3. Generally, the process is conducted at a temperature from 0 to 50 °C. In a particular embodiment the process is conducted at room temperature.

[0065] The process for preparing the particulated compounds of the present invention may comprise also first preparing the compounds of formula (I):

[0066] The compounds of formula (I) can be prepared by a process which comprises: reacting a compound of formula (II) with a compound of formula (III), where in compound of formula (II) Ri is independently selected from the group consisting of H and (Ci-Ce)alkoxy; p is equal to 3; and A is selected from the group consisting of NH2, COCI, COOH, OH; in compound of formula (III), m is an integer from 1 to 5; R2, R3, and R4 are selected from the group consisting of linear or branched (Ci-Ce)-alkyl, linear or branched (C2-Ce)-alkenyl, (C3-C6)-cycloalkyl, and phenyl, and B is selected from the group consisting -NCO, NH2, COOH, COCI, and OH; wherein: a) when A is NH2, B is NCO; b) when A is either COCI or COOH, B is either OH or NH2; and c) when A is OH, B is selected from the group consisting of NCO, COOH, and COCI.

[0067] (II)

[0068] Thus, when A is NH2, and B is NCO a urea bond is formed. This reaction can be conducted in the presence of an appropriate solvent such as tetrahydrofuran, toluene or CH2CI2. The reaction can be conducted at a temperature in the range from 0 to 150°C. In a particular embodiment, the reaction is conducted at room temperature, using tetra hydrofuran and without catalyst.

[0069] When A is either COCI or COOH, and B is OH an ester bond is formed. This reaction can be conducted in the presence of an appropriate solvent such as tetrahydrofuran, toluene, CH2CI2 or 1 ,2-dicloroethane. The reaction can be conducted at a temperature in the range of 0 to 150°C. Some catalyst as 4-dimethylaminopyridine, dicyclohexylcarbodiimide or tetrabutylammonium tribromide can be used as coupling agents.

[0070] When A is OH and B is either COCI or COOH an ester bond is formed. This reaction can be conducted in the presence of an appropriate solvent such as tetrahydrofuran, toluene, CH2CI2 or 1 ,2-dicloroethane and non-nucleophilic base such as triethylamine. The reaction can be conducted at a temperature in the range of 0 to 150°C. Some catalyst as 4-dimethylaminopyridine, dicyclohexylcarbodiimide or tetrabutylammonium tribromide can be used as coupling agents.

[0071] When A is either COCI or COOH, and B is NH2 an amide bond is formed. This reaction can be conducted in the presence of an appropriate solvent such as tetra hydrofuran, toluene, CH2CI2 or 1 ,2-dicloroethane. The reaction can be conducted at a temperature in the range of 0 to 150°C. Some catalyst as 4-dimethylaminopyridine or dicyclohexylcarbodiimide can be used as coupling agents. In a particular embodiment, the reaction is conducted at room temperature, using tetrahydrofuran as solvent and without catalyst.

[0072] When A is OH, and B is NCO a carbamate bond is formed. This reaction can be conducted in the presence of an appropriate solvent such as tetra hydrofuran, toluene, CH2CI2 or 1 ,2-dicloroethane. The reaction can be conducted at a temperature in the range of O to 150°C.

[0073] Compound of formula (II) with A = COCI can be prepared from a compound of formula (II) with A=COOH by reaction for instance with thionyl chloride.

[0074] Compounds of formula (II) with A=COOH can be prepared by reaction of compound (IV) where Q is selected from Cl and Br, with a compound (V) where R1 and p have the same meaning as in compound (II),

[0075] In a particular embodiment, the compound of formula (IV) is the compound (IVa) below:

[0076] (IVa). In another particular embodiment, compound of formula (V) is that where Ri is H and p is

[0077] 3, having the formula (Va) below:

[0078] (Va).

[0079] Compounds of formula (II) with A=NH2 can be obtained by submitting the corresponding nitro compounds of formula (VI) to a reduction reaction, where in compound (VI) Ri and p have the same meaning as in compound (II),

[0080] (VI). This reaction may be conducted for instance in the presence of SnCh. 2H2O and an acid such as acetic acid: The reaction is conducted at an appropriate temperature. In a particular embodiment, the reaction is conducted at a temperature in the range from 60 to 80 °C. Compound of formula (VI) can be prepared analogously to compound (II) with A = COOH but using an amino-nitrobenzene instead of compound (V). Compounds of formula (II) with A=OH can be prepared by reaction of compound (IV) where Q is selected from Cl and Br, with a compound (VII) where Ri and p have the same meaning as in compound (II),

[0081] (VII).

[0082] In a particular embodiment, the compound of formula (IV) is the compound (IVa) below:

[0083] In another particular embodiment, the compound of formula (VII) is that where Ri is H and p is 3, having the formula (Vila) below:

[0084] (Vila).

[0085] Compounds of formula (III) are commercially available and can be obtained by known methods in the art.

[0086] Throughout the description and claims the word comprise and variations of the word, are not intended to exclude other technical features, additives, components, or steps. Furthermore, the word “comprise” encompasses the case of “consisting of”. Additional objects, advantages and features of the invention will become apparent to those skilled in the art upon examination of the description or may be learned by practice of the invention. The following examples and drawings are provided by way of illustration, and they are not intended to be limiting of the present invention. Reference signs related to drawings and placed in parentheses in a claim, are solely for attempting to increase the intelligibility of the claim and shall not be construed as limiting the scope of the claim. Furthermore, the present invention covers all possible combinations of particular and preferred embodiments described herein.

[0087] Examples

[0088] Example 1. Preparation of nitro product 1 (i.e., a compound of formula (VI) with Ri= H)

[0089] A 500 mL round-bottom flask was charged with 5.0 g of cyanuric chloride and 18.7 g of 4- nitroaniline. To this mixture, 300 mL of solvent (acetic acid) was added, and the suspension was stirred at room temperature. After 10-15 minutes, temperature was raised to 120°C, and the reaction was left to evolve overnight. Once reaction was completed, solid product is filtered, washed with ethanol and dried affording 12.1 g (91% yield) of green solid (1).1H-NMR (DMSO-d6, 300 MHz) 5 (ppm): 10.32 (s, 3 H), 8.22 (d, J = 9.36 Hz, 6 H), 8.11 (d, J = 9.36 Hz, 6 H.).13C-NMR (DMSO-d6, 75 MHz) 5 (ppm): 163.9, 146.3, 141.3, 124.7, 119.5. Example 2. Preparation of amino product 2 (i.e., compound of formula (II) with Ri= H and

[0090] A= NH2)

[0091] A 250 mL round-bottom flask was charged with 5.0 g of product 1 and 23.1 g of SnCI22H2O. To this mixture, 60 mL of solvent (acetic acid) was added. After 5-10 minutes, temperature was raised to 70°C, and the reaction was left to evolve overnight. Once reaction was completed, solid product was filtered and dissolved in 50 mL of water. pH is set to 10-12 and product’s precipitation occurs, then solid is filtered and dried affording 3.2 g (78% yield) of brownish solid (2).1H-NMR (DMSO-d6, 300 MHz) 5 (ppm): 8.47 (s, 3 H), 7.34 (d, J = 8.37 Hz, 6 H), 6.49 (d, J = 8.37 Hz, 6 H), 4.75 (br. s, 6 H).13C- NMR (DMSO-d6, 75 MHz) 5 (ppm): 164.5, 144.2, 129.8, 122.7, 114.2.

[0092] Example 3. Preparation of urea product 3 (i.e., a compound of formula (I) with Ri= H, A 250 mL round-bottom flask was charged with 1.0 g of product 2 and 100 mL of solvent (dry THF) was added. Then, 2.04 mL of triethoxy(3-isocyanatopropyl)silane was added and the reaction was left to evolve overnight. Once reaction was completed, solvent was removed using rotary evaporator affording 2.6 g (91% yield) of brownish solid (3).1H-NMR (DMSO-d6, 300 MHz) 5 (ppm): 8.94 (s, 3 H), 8.25 (s, 3 H), 7.62 (m, 6 H), 7.27 (d, J = 8.76 Hz, 6 H), 6.07 (br. s, 3 H), 3.75 (q, J = 7.06 Hz, 18 H), 3.04 (m, 6 H), 1.48 (m, 6 H), 1.15 (t, J = 7.06 Hz, 27 H), 0.56 (m, 6 H).13C-NMR (DMSO-d6, 75 MHz) 5 (ppm): 163.9, 155.3, 135.1 , 133.7, 120.9, 117.9, 57.7, 41.8, 23.4, 18.2, 7.3.

[0093] Example 4. Preparation of nitro product 4 (i.e., a compound of formula (VI) with Ri= H)

[0094] A 250 mL round-bottom flask was charged with 4.2 g of cyanuric chloride and 15.7 g of 3- nitroaniline. To this mixture, 120 mL of solvent (acetic acid) was added, and the suspension was stirred at room temperature. After 10-15 minutes, temperature was raised to 120°C, and the reaction was left to evolve 1 hour. Once reaction was completed, solid product is filtered, washed with water and dried affording 11.0 g (99% yield) of yellowish solid (4).1H-NMR (DMSO-d6, 300 MHz) 5 (ppm): 9.96 (s, 3 H), 8.62 (s, 3 H), 8.22 (br. s, 3H), 7.86 (ddd, J = 8.24, 2.28, 1.04 Hz, 3 H), 7.95 (t, J = 8.24 Hz, 3 H).13C-NMR (DMSO- d6, 75 MHz) 5 (ppm): 163.9, 148.0, 140.8, 129.8, 126.5, 116.8, 114.6.

[0095] Example 5. Preparation of amino product 5 (i.e., a compound of formula (II) with Ri= H and A =NH2) A 500 mL round-bottom flask was charged with 2.2 g of product 4 and 13.8 g of SnCl2'2H2O. To this mixture, 250 mL of solvent (ethanol) was added. After 5-10 minutes, temperature was raised to 50°C, and the reaction was left to evolve overnight. Once reaction was completed, solvent was removed using a rotary evaporator. The remaining solid was dispersed in 250 mL of saturated NaHCO3aqueous solution, then, product was extracted using ethyl acetate. Solvent vas removed using rotary evaporator affording 1.4 g of white solid (5).1H-NMR (DMSO-d6, 300 MHz) 5 (ppm): 8.76 (s, 3 H), 7.09 (s, 3 H), 6.90 (m, 6 H), 6.26-6.24 (m, 3 H), 4.91 (br. s, 6 H).13C-NMR (DMSO-d6, 75 MHz) 5 (ppm): 164.1 , 148.6, 140.5, 128.6, 108.9, 108.5, 106.7.

[0096] Example 6. Preparation of urea product 6 (i.e., a compound of formula (I) with Ri= H,

[0097] A 25 mL round-bottom flask was charged with 0.1 g of product 5 and 4 mL of anhydrous dichloromethane was added. Then, 0.28 mL of triethoxy(3-isocyanatopropyl)silane was added and the reaction was left to evolve overnight. Once reaction was completed, solvent was removed using rotary evaporator affording 0.26 g (93% yield) of white solid (6).1H-NMR (DMSO-d6, 300 MHz) 5 (ppm): 9.09 (s, 3 H), 8.24 (s, 3 H), 7.55 (m, 3 H), 7.47 (s, 3 H), 7.12-7.10 (m, 6 H), 6.19 (m, 3 H), 3.74 (q, J = 6.95 Hz, 18 H), 3.07 (m, 6 H), 1.49 (m, 6 H), 1.16 (t, J = 6.95 Hz, 27 H), 0.57 (m, 6 H).13C-NMR (DMSO-d6, 75 MHz) 5 (ppm): 164.2, 155.2, 140.5, 140.1, 128.4, 114.0, 112.1 , 110.2, 57.7, 41.8, 23.4, 18.2, 7.3. Example 7. Preparation of nitro product 7 (i.e., a compound of formula (VI) with two Ri= H

[0098] A 500 mL round-bottom flask was charged with 5.0 g of cyanuric chloride and 22.8 g of 2- methoxy-4-nitroaniline. To this mixture, 100 mL of solvent (acetic acid) was added, and the suspension was stirred at room temperature. After 10-15 minutes, temperature was raised to 120°C, and the reaction was left to evolve overnight. Once reaction was completed, solid product is filtered, washed with water and dried affording 12.8 g (83% yield) of yellowish solid (7).1H-NMR (DMSO-d6, 300 MHz) 5 (ppm): 8.36 (m, 3 H), 7.92- 7.85 (m, 9 H), 4.01 (s, 9 H).

[0099] Example 8. Preparation of amino product 8 (i.e., a compound of formula (II) with two Ri=

[0100] A 250 mL round-bottom flask was charged with 5.0 g of product 7 and 19.5 g of SnCl2'2H2O. To this mixture, 60 mL of solvent (acetic acid) was added. After 5-10 minutes, temperature was raised to 70°C, and the reaction was left to evolve overnight. Once reaction was completed, solid product was filtered and dissolved in 50 mL of water. pH is set to 10-12 and product’s precipitation occurs, then solid is filtered and dried affording 2.1 g (50% yield) of brownish solid (8).1H-NMR (DMSO-d6, 300 MHz) 5 (ppm): 7.43z (d, J = 8.18 Hz, 3 H), 7.34 (s, 3 H), 6.27 (d, J = 2.08 Hz, 3 H), 6.08 (d, J = 8.19 Hz, 3 H), 4.84 (br. s, 6 H), 3.71 (s, 9 H).13C-NMR (DMSO-d6, 75 MHz) 5 (ppm): 165.1 , 152.1 , 146.3, 117.4, 105.7, 98.2, 55.6.

[0101] Example 9. Preparation of urea product 9 (i.e., a compound of formula (I) with two Ri= H

[0102] A 250 mL round-bottom flask was charged with 1.5 g of product 8 and 60 mL of solvent (dry THF) was added. Then, 2.5 mL of triethoxy(3-isocyanatopropyl)silane was added and the reaction was left to evolve overnight. Once reaction was completed, solvent was removed using rotary evaporator affording 3.2 g (86% yield) of brownish solid (9).1H-NMR (DMSO-d6, 300 MHz) 5 (ppm): 8.39 (br. s, 3 H), 7.70 (m, 6H), 7.29 (s, 3 H), 6.76 (m, 3 H), 6.13 (br. s, 3 H), 3.80-3.70 (m, 27 H), 3.06 (m, 6 H), 1.57-1.42 (m, 6 H), 1.18-1.12 (m, 27 H), 0.60-0.52 (m, 6 H)13C-NMR (DMSO-d6, 75 MHz) 5 (ppm): 164.3, 152.2, 147.1 , 137.0, 123.3, 121.3, 109.0, 101.4, 57.7, 55.4, 41.8. 23.4, 18.2, 7.3.

[0103] Example 10. Preparation acid product 10 (i.e., a compound of formula (II) with Ri= H and A =COOH)

[0104] A 250 mL round-bottom flask was charged with 5.0 g of cyanuric chloride and 18.6 g of 4- aminobenzoic acid. To this mixture, 260 mL of solvent (acetic acid) was added, and the suspension was stirred at room temperature. After 10-15 minutes, temperature was raised to 120°C, and the reaction was left to evolve overnight. Once reaction was completed, solid product is filtered, washed with water and dried affording 12.0 g (91% yield) of white solid (10).1H-NMR (DMSO-d6, 300 MHz) 5 (ppm): 10.64 (brd.s, 3 H),9.84 (brd.s, 3 H), 8.00-7.74(m,12H).13C-NMR (DMSO-d6, 90 MHz) 5 (ppm): 167.0, 163.8, 144.0, 130.3, 124.0, 119.4. Example 11. Preparation of amide product 11 (i.e., a compound of formula (I) with Ri= H A 25 mL round-bottom flask was charged with 1.0 g of product 10 and was dissolved with 8 mL of tionyl chloride. After 5-10 minutes, the temperature was raised to 80°C, and the reaction was left to evolve 8 hours. Then, tionyl chloride was removed and 50 mL of THF and 1.45 mL of APTES were added, and the reaction was left to react overnight. Once the reaction was finished solvent was removed using a rotary evaporator affording 2.02 g (89% yield) of white solid.1H-NMR (DMSO-d6, 300 MHz) 5 (ppm): 9.55 (br. s, 3 H), 8.32 (m, 12 H), 8.05 (m, 3 H), 3.78 (q, J = 7.53 Hz, 18 H), 3.25 (m, 6 H), 1.63 (m, 6 H), 1.21 (t, J = 7.53 Hz, 27 H), 0.69 (m, 6 H).13C-NMR (DMSO-d6, 90 MHz) 5 (ppm): 169.0, 140.5, 127.5, 125.9, 117.8, 57.4, 41.0, 22.3, 18.2, 9.3.

[0105] Example 12. General synthetic procedure for preparing the particulated compounds from compounds of formula (I)

[0106] A 500 mL round-bottom flask was charged with 3.0 g of corresponding product (3, 6, 9 or 11) and was dissolved in appropriate solvent (ethanol). To this mixture, a catalytic amount of NH3 (32%) was added and the reaction was left to evolve overnight. Once reaction was completed, solid product is filtered, washed with water and ethanol, and dried, affording 2.25 g of white solid.

[0107] Example 13. General UV-Vis spectra recording procedure by transmittance

[0108] To measure the absorbance spectrum of a sylilated compounds 3, 6, 9 and 11 dissolved in methanol using a cuvette spectrophotometer, the following steps were followed. First, the sample was prepared by weighing an appropriate amount of the solid, in order to achieve a concentration around 2 10-5M, using an analytical balance. The solid was then transferred into a volumetric flask (10 or 25 mL), and a small amount of methanol was added. The mixture was stirred until the solid is completely dissolved. Once dissolved, a new solution could be necessary in order to avoid too high absorbance values. Measurements were performed using 1 cm quartz cuvette in a HP UVA / is 8453 spectrophotometer.

[0109] Example 14. General UV-Vis spectra recording procedure by diffuse transmittance

[0110] Compounds or particles were dissolved or dispersed in phenethyl benzoate at 5 wt%. Then, solution or dispersion was applied to a PMMA plate following ISO 24443:2021. Measurements were recorded using a LABSPHERE UV2000S equipment.

[0111] Comparison shows that particles have a very similar absorbance profile from 290 to 400 nm than non-particulated compound 3 (See Fig. 1). Similarities include spectra profile, range of absorbance and molar absorption coefficient.

[0112] Example 15. Percutaneous permeation test in reconstituted human epidermis (RHE) of the particulated product of Example 3 - urea product 3

[0113] Upon receipt of the RHE inserts, they were unpacked immediately and carefully inspected for any signs of damage. At the same time, the maintenance medium was pre-warmed to 37 °C. The tissues were then transferred into 12-well plates, each well containing 2 mL of maintenance medium. Finally, the inserts were incubated in proper medium at 37 °C in a 5% CO2atmosphere for at least 24 hours before treatment.

[0114] The test substance (particles from urea product 3) was prepared at a concentration of 2.5% w / w in 1,3-propanediol. Before performing the permeation experiments, the inserts were rinsed with sterile HBSS buffer (Hank’s Balanced Salt Solution) to remove any residual medium and then transferred to fresh 12-well plates containing 2 mL of sterile HBSS buffer, which serves as the acceptor phase. Subsequently, 100 pL of the prepared test solution was applied to the donor compartment. The RHE inserts were then incubated for 24 hours under standard culture conditions (37 °C, 5% CO2).

[0115] 24 hours after application of the test compound, the inserts were transferred to a new 12- well plate and gently washed 3 times with 250 pL of PBS (Phosphate Buffered Saline) per insert. Immediately after washing, the inserts were moved to a 24-well plate. For the permeability assay, 200 pL of a 1 mM Lucifer Yellow solution in HBSS were applied to the apical compartment, while 750 pL of enriched HBSS were added to the basal compartment. The inserts were then incubated for 2 hours under standard culture conditions. Following incubation, 100 pL from both the apical and basal compartments were collected and transferred to a 96-well plate for fluorescence measurement using a plate reader (excitation at 428 nm; emission at 540 nm).

[0116] The inserts exposed to the test item were subsequently transferred to a new 24-well plate, where 750 pL of fixation buffer was added to both the apical and basal compartments. The plate is sealed, protected from light, and stored at 4 °C until further analysis.

[0117] TEM samples were prepared by tissue fixation with 4% glutaraldehyde. After that, the tissue was transferred to phosphate-buffered saline (PBS). Post-fixation was performed in a 1% osmium tetroxide solution, followed by dehydration in a graded ethanol / water series. After dehydration, resin infiltration was performed. After that, thin slices of 80 nm size of the embedded tissue sample were prepared. Slices were deposited onto carbon-coated TEM grids and additional staining with UranyLess and lead citrate were performed. TEM measurements of the stained tissue samples were performed on a JEOL JEM-1400 transmission electron microscope.

[0118] The distribution of particles was then examined to determine whether they remained on the surface, became localized within the stratum corneum or penetrated deeper into the tissue, into the epidermis. This approach allowed a direct evaluation of particle retention and depth of permeation within the skin layers.

[0119] Fig. 2 demonstrates the absence of particles in both the stratum corneum and deeper skin layers.

[0120] For reasons of completeness, various aspects of the invention are set out in the following numbered clauses:

[0121] Clause 1 . A compound of formula (I), a pharmaceutically or a cosmetically acceptable salt thereof, or a stereoisomer of any of them or mixtures thereof, wherein: Ri is independently selected from the group consisting of H and (Ci-Ce)-alkoxy; p is equal to 3; and Z is a radical of formula (I’) wherein: X is selected from the group consisting of NH and O; Y is selected from the group consisting of NH and O; n is an integer from 0 to 1 ; o is an integer from 0 to 1 ; m is an integer from 1 to 5; and R2, R3, and R4 are selected from the group consisting of linear or branched (Ci-Ce)-alkyl, linear or branched (C2-Ce)-alkenyl, (C3-C6)-cycloalkyl, and phenyl; with the proviso that compound of formula (I) is other than compound of formula (I) where R1 is H, X is O, Y is NH, n is 1 , o is 1 , m is 3, R2, R3, R4 are OEt, and Z is in para position.

[0122] Clause 2. The compound according to clause 1 , wherein R2, R3, R4 are ethyl.

[0123] Clause 3. The compound according to any of the clauses 1-2, wherein R1 is H or OCH3.

[0124] Clause 4. The compound according to any of the clauses 1-3, wherein m is 3.

[0125] Clause 5. The compound according to any of the clauses 1-4, wherein: a) X is NH, Y is NH, n is 1 , and o is 1 ; b) X is O, Y is NH, n is 1 and o is 1 ; c) Y is NH, n is 0, and o is 1 ; d) Y is O, n is 0, and o is 1 ; and e) X is O, n is 1 , and o is 0.

[0126] Clause 6. A particulated compound, obtainable by hydrolysation-polycondensation of compound of formula (I) as defined in any of the clauses 1-5 including the compound of formula (I) where Ri is H, X is O, Y is NH, n is 1, o is 1 , m is 3, R2, R3, R4 are OEt, and Z is in para position.

[0127] Clause 7. The particulated compound according to clause 6, which has a mean particle size from 220 to 2000nm measured by SEM imaging and imaging process.

[0128] Clause 8. The particulated compound according to any of the clauses 6-7, which have a spherical morphology.

[0129] Clause 9. Use of a compound as defined in any of the clauses 6-8, for the protection of a human, or animal living body, from ultraviolet radiation.

[0130] Clause 10. A method for protecting a material from ultraviolet radiation which comprises treating the material with a composition comprising a particulated compound as defined in any of the clauses 6-8.

[0131] Clause 11. A composition selected from the group consisting of a cosmetic composition, a pharmaceutical composition, and a personal care composition, comprising at least an effective amount for the protection of either a human or animal living body, from ultraviolet radiation, of a particulated compound as defined in any of the clauses 6-8, together with one or more pharmaceutically or cosmetically acceptable excipients or carriers, or alternatively, a composition comprising at least an effective amount for the protection of a material from ultraviolet radiation, of a particulated compound as defined in any of the clauses 6-8, together with appropriate components selected from at least a polymer, a solvent an additive, and a mixture thereof.

[0132] Clause 12. The cosmetic or pharmaceutical composition, or a personal care composition according to clause 11 , wherein the effective amount ranges from 0.5 to 20 wt.% based on the total weight of the composition.

[0133] Clause 13. The cosmetic or pharmaceutical composition, or a personal care composition according to any of the clause 11-12, wherein the composition is selected from the group consisting of creams, ointments, oils, lotions, gels, sticks, foams, milks, suspensions, powders, emulsions, dispersions, sprays, aerosols, lipsticks, foundations, makeup, loose or press powders, eye blushes, eye shadows, mascaras, nail varnishes, nail lacquers and non-permanent dyeing composition for the hair.

[0134] Clause 14. A process for preparing a compound as defined in any of the clauses 6-8, which comprises: a) hydrolysing a compound of formula (I) as defined in any of the clauses 1-5, including the compound of formula (I) where Ri is H, X is O, Y is NH, n is 1 , o is 1 , m is 3, R2, R3, R4 are OEt, and Z is in para position; and b) polycondensating the compound obtained in step a).

[0135] Clause 15. The process according to clause 14, further comprising a previous step which comprises: reacting a compound of formula (II),

[0136] Wherein R1 is independently selected from the group consisting of H and (Ci-Ce)-alkoxy; p is equal to 3; and A is selected from the group consisting of NH2, COCI, COOH, OH, with a compound of formula (III), wherein: m is an integer from 1 to 5; R2, R3, and R4 are selected from the group consisting of linear or branched (Ci-Ce)-alkyl, linear or branched (C2-Ce)-alkenyl, (Cs-Ce)- cycloalkyl, and phenyl; and B is selected from the group consisting -NCO, NH2, COOH, COCI, and OH; and wherein: a) when A is NH2, B is NCO; b) when A is either COCI or COOH, B is either OH or NH2; and c) when A is OH, B is selected from the group consisting of NCO, COOH, and COCI. Citation List

[0137] Patent Literature

[0138] -EP0933376A2 -W02009053149A1

[0139] -WO2022122838A1

Claims

1. Claims1. A compound of formula (I), a pharmaceutically or a cosmetically acceptable salt thereof, or a stereoisomer of any of them or mixtures thereof,wherein:Ri is independently selected from the group consisting of H and (Ci-Ce)-alkoxy; p is equal to 3; andZ is a radical of formula (I’)wherein:X is selected from the group consisting of NH and O;Y is selected from the group consisting of NH and O; n is an integer from 0 to 1 ;o is an integer from 0 to 1 ; m is an integer from 1 to 5; andR2, R3, and R4 are selected from the group consisting of linear or branched (Ci-Ce)-alkyl, linear or branched (C2-Ce)-alkenyl, (C3-C6)-cycloalkyl, and phenyl; with the proviso that compound of formula (I) is other than compound of formula (I) where R1 is H, X is O, Y is NH, n is 1 , o is 1 , m is 3, R2, R3, R4 are OEt, and Z is in para position.

2. The compound according to claim 1 , wherein R2, R3, R4 are ethyl.

3. The compound according to any of the claims 1-2, wherein R1 is H or OCH3.

4. The compound according to any of the claims 1-3, wherein m is 3.

5. The compound according to any of the claims 1-4, wherein: a) X is NH, Y is NH, n is 1 , and o is 1 ; b) X is O, Y is NH, n is 1 and o is 1 ; c) Y is NH, n is 0, and o is 1 ; d) Y is O, n is 0, and o is 1 ; and e) X is O, n is 1 , and o is 0.

6. A particulated compound, obtainable by hydrolysation-polycondensation of compound of formula (I) as defined in any of the claims 1-5.

7. The particulated compound according to claim 6, which has a mean particle size from 20 to 2000nm measured by SEM imaging and imaging process.

8. The particulated compound according to claim 7, which has a mean particle size from 220 to 2000nm measured by SEM imaging and imaging process.

9. The particulated compound according to any of the claims 6-8, which have a spherical morphology.

10. A compound as defined in any of the claims 6-9, for use in the protection of a human, or animal living body, from ultraviolet radiation.11 . A method for protecting a material from ultraviolet radiation which comprises treating the material with a composition comprising a particulated compound as defined in any of the claims 6-9.

12. A composition selected from the group consisting of a cosmetic composition, a pharmaceutical composition, and a personal care composition, comprising at least an effective amount for the protection of either a human or animal living body, from ultraviolet radiation, of a particulated compound as defined in any of the claims 6-9, together with one or more pharmaceutically or cosmetically acceptable excipients or carriers, or alternatively, a composition comprising at least an effective amount for the protection of a material from ultraviolet radiation, of a particulated compound as defined in any of the claims 6-9, together with appropriate components selected from at least a polymer, a solvent an additive, and a mixture thereof.

13. The cosmetic or pharmaceutical composition, or a personal care composition according to claim 12, wherein the effective amount ranges from 0.5 to 20 wt.% based on the total weight of the composition.

14. The cosmetic or pharmaceutical composition, or a personal care composition according to any of the claims 12-13, wherein the composition is selected from the group consisting of creams, ointments, oils, lotions, gels, sticks, foams, milks, suspensions, powders, emulsions, dispersions, sprays, aerosols, lipsticks, foundations, makeup, loose or press powders, eye blushes, eye shadows, mascaras, nail varnishes, nail lacquers and non-permanent dyeing composition for the hair.

15. A process for preparing a compound as defined in any of the claims 6-9, which comprises: a) hydrolysing a compound of formula (I) as defined in any of the claims 1-5, including the compound of formula (I) where Ri is H, X is O, Y is NH, n is 1, o is 1 , m is 3, R2, R3, R4are OEt, and Z is in para position; and b) polycondensating the compound obtained in step a).

16. The process according to claim 15, further comprising a previous step which comprises:reacting a compound of formula (II),whereinRi is independently selected from the group consisting of H and (Ci-Ce)-alkoxy; p is equal to 3; andA is selected from the group consisting of NH2, COCI, COOH, OH with a compound of formula (III),wherein: m is an integer from 1 to 5;R2, R3, and R4 are selected from the group consisting of linear or branched (Ci-Ce)-alkyl, linear or branched (C2-Ce)-alkenyl, (C3-C6)-cycloalkyl, and phenyl; andB is selected from the group consisting -NCO, NH2, COOH, COCI, and OH; and wherein:a) when A is NH2, B is NCO; b) when A is either COCI or COOH, B is either OH or NH2; and c) when A is OH, B is selected from the group consisting of NCO, COOH, and COCI.

Images