MXPA01002566A - Naphthopyrans annelated in c5 - Google Patents

Abstract

The invention relates to novel compounds of the naphthopyran type which have an annelated carbocycle in position 5, 6. These compounds are of formula (I) in which A is an alicyclic ring which is optionally annelated with an aromatic ring and in which two adjacent R3 can together form at least one ring, for example a benzo group. These compounds (I) possess interesting photochromic properties. The invention also relates to the method of preparing these compounds (I), as well as their applications as photochromes:compositions and (co)polymer matrices comprising them.

Description

NAFTOPIRANOS RUBBED IN THE POSITIONS C5-Cp. YOUR PREPARATION AND POLYMERIC COMPOSITIONS AND MATRIXES (CO) THAT CONTAIN THEM DESCRIPTIVE MEMORY The present invention relates to novel ringed naphthopyran-type compounds, which have, in particular, photochromic properties.

The invention also relates to photochromic compositions and photochromic ophthalmic articles (eg lenses) containing said naphthopyrans. The invention also encompasses the preparation of these novel naphthopyrans. The photochromic compounds have the ability to change the color under the influence of a polychromatic or monochromatic light (UV for example) and to return to their initial color when the light irradiation ceases, or under the influence of temperature and / or a polychromatic or monochromatic light different from the first. The photochromic compounds find applications in various fields, for example in the manufacture of ophthalmic lenses, contact lenses, sun protection goggles, filters, optical systems for cameras or optical systems for photographic or other optical devices and observation devices, glazing, decorative objects, elements of bills or even for storage of information by optical registration (coding). In the field of ophthalmic optical systems, and in particular the branch of eyeglasses, a photochromic lens comprising one or more 5 photochromic compounds must have: - a high transmission in the absence of ultraviolet, - a low transmission (high color capacity) when under solar irradiation, - adapted kinetics of coloration and discoloration, 10 - a dye acceptable to the consumer (preferably gray or brown) that preferably maintains the dye chosen during coloring and discoloration of the lenses, - a preservation of the yields, properties, within a temperature range of 0-40 ° C, 15 - a significant durability, because these sought-after objectives are sophisticated corrective lenses and therefore costly. These characteristics of the lenses are in fact determined by the active photochromic compounds they contain: compounds that must also be perfectly compatible with the organic or inorganic support constituting the lenses. In addition, it should be mentioned that it may be necessary to use at least two photochromic compounds of different colors, that is to say they have different maximum absorption wavelengths in the range visible, to obtain a gray or brown tint. This imp > There are also other requirements for photochromic compounds. In particular, the coloring and decolorization kinetics of the combined active (photochromic) two or more compounds must be essentially identical. The same applies in terms of its stability over time and also for its compatibility with a plastic or inorganic support. Among the numerous photochromic compounds described in the prior art, mention may be made of the benzopyrans or naphthopyrans described in the patents or patent applications: US-A-3,567,605, US-A-3,627,690, US-A-4,826,977, US-A-5,200,116, US-A-5,238,981, US-A-5,411, 679, US-A-5,429,744, US-A-5,451, 344, US-A-5,458,814, US-A-5,651, 923, US- A-5,645,767, US-A-5,698,141, WO-A-95 05382, FR-A-2,718,447, WO-A-96 14596, and WO-A-97 21698 which have the following condensed formula: The patent E.U.A. US-A-6,645,767 discloses naphthopyrans having an indene group bonded to carbons 5 and 6 of the naphtho base structure: The patent E.U.A. US-A-5,651,923 describes naphthopyrans having a naphthofuran or benzo group bonded to carbons 5 and 6 of the naphtho base structure.

The patent E.U.A. US-A-5,783,116 describes naphthopyrans having an unsubstituted alicyclic group.

These known compounds A, B, C, D, E claim to meet the specifications defined above. Actually, sitíS ós compounds really have one or more of the basic properties sought, such as a high transmission in the absence of ultraviolet and a high capacity of coloration under solar irradiation, none of the compounds described to date have the full combination of properties sought which are necessary for the production of satisfactory articles. In particular, none of these compounds is gray or brown in an intrinsic manner and the need to use an additional photochromic in order to obtain one of these two dyes persists. The photochromic compounds according to US-A-5,645,767 are obtained from substituted or unsubstituted benzophenones, which are allowed to react with an ester of succinic acid, such as the dimethyl ester, in the presence of toluene and tert-butoxide of potassium In this way a hemiester is produced which is successively converted to acetoxinaphthalene and then to carboxinaphthol which is cyclized to obtain a naphthol fused to a benzofuranone residue. The reaction of this latter compound with a propargyl alcohol in the presence of DBSA leads to a naphthopyran fused with an indenone ring. The homophenone of this naphthopyran can be obtained starting from a precursor having a reduced ketone functional group. This indene carbon can be substituted in several ways.As for the naphthopyrans fused with benzo or naphthofuran residues according to US-A-5,657,923, these are prepared by reacting a naphthol fused with an indenone ring or a naphthofuran ring on the one hand, and with a propargyl alcohol on the other hand. other. Naphthol fused to an indenone ring is obtained, for example, as described in US-A-5, 645,767; while naphthol fused to a naphthofuran ring originates from the reaction between a naphthoquinone and a 1,3-dihydroxynaphthalene, with or without subsequent methylation of at least one hydroxy group. In this context, the inventors should be given credit for having had an interest in the aforementioned naphthopyrans and for having selected, within this family of naphthopyrans fused at the Cs-Cß positions with at least one carbocycle, a group of molecules specific ones that have particularly advantageous photochromic properties. Therefore, the present invention relates, according to a first aspect, to the compounds of the formula (I): in which: ^ '\' * &A? ^^^^^ - 'Á. ^^ i? M¿ ^ 3t i'a i * a_tfe »• Ri and R2 are identical or different and represent independently: - hydrogen, - a linear or branched alkyl group comprising from 1 to 5 12 carbon atoms, - a cycloalkyl group comprising from 3 to 12 carbon atoms, - an aryl or heteroaryl group which comprises in its basic structure of 6 to 24 atoms carbon or from 4 to 24 carbon atoms respectively and at least one heteroatom selected from sulfur, oxygen and nitrogen; said basic structure optionally being substituted with the at least one substituent selected from the total of the substituents mentioned below: + a halogen and specifically fluorine, chlorine and bromine, + a hydroxy group, + a linear or branched alkyl group which comprises from 1 to 12 carbon atoms, + a linear or branched alkoxy group comprising from 1 to 12 carbon atoms, 20 + a halogenoalkyl or halogenoalkoxy group corresponding respectively to the above C C-d2 alkyl or alkoxy groups which are substituted with at least one halogen atom, and specifically such a fluoroalkyl group, * -n? T £ ¡& & amp; and ^ Zz * 'i * ^: 3s ^ eJk¡ + a phenoxy or naphthoxy group optionally substituted with at least one linear or branched alkyl or alkoxy group comprising from 1 to 6 carbon atoms, + a linear alkenyl group or branched comprising from 2 to 12 carbon atoms and specifically a vinyl group or an allyl group, + an -NH2 group, + a -NHR group, wherein R represents a linear or branched alkyl group comprising from 1 to 6 atoms carbon, + a group: R 'and R "which are identical or different, independently represent a linear or branched alkyl group comprising from 1 to 6 carbon atoms, a phenyl group optionally substituted with at least one linear or branched alkyl or alkoxy group which comprises from 1 to 6 carbon atoms, or which together with the nitrogen atom to which a 5 to 7 membered ring is attached, which may comprise at least some other heteroatom selected from oxygen, sulfur and nitrogen, said nitrogen optionally substituted with a group R '", which is a linear or branched alkyl group comprising from 1 to 6 carbon atoms, + a methacryloyl group or an acryloyl group, - an aralkyl or heteroaralkyl group, the alkyl group comprising , which is linear or branched, of 1 to 4 carbon atoms, and the aryl and heteroaryl groups having the definitions given above, or said two substituents Ri and R2 together form n an adamantyl group, norbornyl, fluorenylidene, dialkyl (C? -C6) -antracenylidene or a spirocycloalkyl (C5-C6) -anthracenylidene group; said group being optionally substituted with at least one of the substituents listed above for Ri, R2 corresponding to an aryl or heteroaryl group; • R3, which is identical or different, represents, independently: - a halogen and preferably fluorine, chlorine or bromine, - a linear or branched alkyl group comprising 1 to 12 carbon atoms (advantageously 1 to 6 carbon atoms), a cycloalkyl group comprising from 3 to 12 carbon atoms, a linear or branched alkoxy group comprising from 1 to 12 carbon atoms (advantageously from 1 to 6 carbon atoms), - a halogenoalkyl, halogenocycloalkyl, halogenoalkoxy group corresponding respectively to the above alkyl, cycloalkyl, alkoxy groups, which are substituted with at least one halogen atom, which is specifically selected from fluorine, chlorine and bromine, - an aryl group or heteroaryl having the same definition as that given above for Ri, R2, - an aralkyl or heteroaralkyl group, the alkyl group comprising, which is linear or branched, from 1 to 4 carbon atoms; and the aryl and heteroaryl groups having the same definitions as those given above for Ri, R2, - a phenoxy or naphthoxy group optionally substituted with at least one linear or branched alkyl or alkoxy group comprising from 1 to 6 carbon atoms, - an amine or amide group: -NH2, -NHR, -CONH2 > -CONHR, R "" R "" / ^ / ^ - N 0 -CON \ \ R "- - 'R" - -' having R, R ', R "the respective definitions given above for the amine substituents of the Ri, R2: aryl or heteroaryl, - a -OCORß or -COORs, in which Rs represents a linear or branched alkyl group comprising from 1 to 6 carbon atoms or a cycloalkyl group comprising from 3 to 6 carbon atoms or a phenyl group which is optionally substituted with at least one of the substituents listed above for the values of Ri, R2: aryl or heteroaryl or at least two adjacent R3 groups together form at least one aromatic or non-aromatic cyclic group having a single ring or having two fused rings, optionally comprising at least one heteroatom selected from the group consisting of: oxygen , sulfur and nitrogen, being this, or these rings fused, optionally substituted with at least one substituent selected from those having the definitions given above for the aryl or heteroaryl groups which can form Ri and / or R2; • m is an integer from 0 to 4; A represents: (A.,) (A2) (A,) in these fused rings (A-i) to (A5):? the dotted line represents the bond of the C5 carbon to the carbon Ce of the naphthopyran ring of the formula (I); ? the fused ring bond (A4) or (A5) may be bonded differently to the C5 carbon or the Ce carbon of the naphthopyran ring of the formula (I); ? R4, which is identical or different, represents, so independently, an OH group, an alkyl group or an alkoxy group which are linear or branched and comprising from 1 to 6 carbon atoms or two of the R4 form a carbonyl (CO); ? R5, Re and R7 represent, independently: - a halogen and specifically fluorine, chlorine or bromine, - a linear or branched alkyl group comprising from 1 to 12 carbon atoms (advantageously from 1 to 6 carbon atoms), - a halogenoalkyl group corresponding to the linear alkyl group or branched above, which is substituted with at least one halogen atom, specifically a fluoroalkyl group, - a cycloalkyl group comprising from 3 to 12 carbon atoms, - a linear or branched alkoxy group comprising from 1 to 6. carbon atoms, - a phenyl or benzyl group, optionally substituted with at least one of the substituents listed above in the definitions of the radicals Ri, R 2 of the formula (I) in the case in which the radicals correspond independently to an aryl or heteroaryl group, an amino group -NH2, -NHR, R'- - N R "- - ' having R, R 'R "their respective definitions given above for the amino substituents of the Ri, R2: aryl or heteroaryl, - a phenoxy or naphthoxy group optionally substituted with at least one linear or branched alkyl or alkoxy group which comprises from 1 to 6 carbon atoms, - a group -CORg, -COORg or -CONHRg, in which Rg represents a linear or branched alkyl group comprising from 1 to 6 carbon atoms or a cycloalkyl group comprising from 3 to 6 carbon atoms or a phenyl or benzyl group which is optionally substituted with at least one of the substituents listed above in the definitions of the radicals Ri, R 2 of the formula (I) in the case in which the radicals correspond in the form independent to an aryl or heteroaryl group, - it being possible for two groups R5 adjacent together to form an aromatic or non-aromatic ring of 5 to 6 links which may comprise at least one heteroatom which is selected from the group comprising: oxygen, sulfur and nitrogen; ? n is an integer from 0 to 6, or is an integer from 0 to 2, p is an integer from 0 to 4 and q is an integer from 0 to 3; with the conformance condition to which in (Ai) and (A2) n is zero only in the case where at least two of the adjacent substituents R3 form at least one aromatic or non-aromatic cyclic group having a ring individual or two fused rings, optionally comprising at least one heteroatom which is selected from the group comprises: oxygen, sulfur and nitrogen, this ring or these fused rings being optionally substituted with at least one substituent selected from those having the definition given above for the aryl groups which can form R-i and / or R2. The compounds of the invention - naphthopyrans of the formula (I) - possess a high coloring capacity, even at 40 ° C, combined with the decolorization kinetics which are adapted for the applications sought. The colors, which can be accessed easily, vary from orange to blue. In accordance with a first embodiment of the invention, the compounds considered are of the formula (I) in which A corresponds to one of the fused rings (Ai) or (A2) as defined above. According to a second embodiment of the invention, the compounds considered correspond to those of the formula (I) in the Wherein A is one of the fused rings (A3), (A4) or (A5) as defined above. It goes without saying that the invention also encompasses mixtures of compounds (I) which belong to at least two different types which are selected from the group comprising compounds (I) in the which A = (A-?), Those in which A = (A2), those in which A = (A3), those in which A = (A4) and those in which A = (A5). According to a third embodiment of the invention, the compounds encompassed are those belonging to the family in which the iÉ < The compounds are of the formula (I) with at least two adjacent R3 groups together forming an aromatic or non-aromatic cyclic group having a single ring (for example a phenyl group) or two rings fused (for example a benzofuran group), optionally comprising at least one heterogeneous atom that is selected from the group comprising: oxygen, sulfur and nitrogen, this ring or these fused rings being optionally substituted with at least one substituent that it is selected from those having the definition given above for the aryl or heteroaryl groups which can form R1 and / or R2. The family according to this third embodiment comprises, among others, the compounds (I) in which two adjacent R3 groups form at least one fused ring, for example, a benzo group and in which the carbons 5 and 6 of the The phenanthrene base structure is linked to at least one alicyclic and / or aromatic cycle A corresponding to (Ai), (A2), (A3), (A4) or (A5). The compounds according to this third embodiment are, specifically, naphthopyrans (I) in which two adjacent R3 groups form at least one fused ring, for example a benzo group, and in which the carbons 5 and 6 of the base structure of phenanthropyran are linked to at least one substituted or unsubstituted alicyclic or aromatic ring. According to a fourth embodiment of the invention, the compounds contemplated are those of the formula (I) indicated ? _ftM8wta8_ < fc «« B «" i above, excluding compounds in which A corresponds to (Ai) * or (A2) having at least one of the substituents R4 other than hydrogen and in which at least two adjacent R3 groups do not together form at least one aromatic or non-aromatic cyclic group having a single ring or having two fused rings, optionally comprising at least one heterogeneous atom which is selected from the group comprising oxygen, sulfur and nitrogen, being this ring or these fused rings optionally substituted with at least one substituent selected from those having the above definition for aryl or heteroaryl groups which can form R1 and / or The compounds according to this fourth embodiment are, specifically, naphthopyran (I) in which two R3 groups do not form a fused ring, for example, m = 1 and R3 = -Ome, and in which the carbons 5 and 6 of the naphtho base structure are linked to at least one alicyclic ring A which is different from (Ai) and different from (A2 ). Preferably, the compounds according to the invention are of the formula (I) in which: - R1, R2 are identical or different and independently represent optionally substituted aryl or heteroaryl groups whose basic structure is selected from those of phenyl, naphthyl, biphenyl, pyridyl, furyl, benzofuryl, dibenzofuryl, N-alkyl (CrC6) -carbazole thienyl, benzothienyl, dibenzothienyl, julolidinyl, represented Rt and / or R2 >; advantageously, a phenyl group substituted in the para position; ¿. - or R1 and R2 together form an adamantyl or norbonyl group. The inventors also accept that they have proposed, in this field of photochromes, a novel route of synthesis of the naphthopyrans fused with at least one carbocycle blended in carbons 5 and 6, in which route a naphthol type precursor is obtained. starting from at least one ketone comprising at least one carbocycle and which is allowed to react with at least one alkyl cyanoacetate, subjecting the obtained product to cyclization. The invention also relates, according to a second aspect, to a method of preparation, specifically of the compounds of the formula (I) as defined above. This method consists essentially in carrying out the condensation:? of at least one compound having the following formula (II): wherein R3, A and m are as defined above with reference to formula (I); -g & ßsgaz - _fc_a5 _ ugly? S3 ^^ - with at least one propargyl alcohol derivative having the following formula (lll): ^ _ wherein Ri and R2 are as defined above with reference to formula (I); the condensation of (11) / (III) being advantageously carried out in the presence of a catalyst, this catalyst being preferably selected from the group comprising para-toluenesulfonic acid, dodecyl sulfonic acid and bromoacetic acid, or with at least one derivative thereof. aldehyde having the following formula (lir): wherein Ri and R2 are as defined above with reference to formula (I); performing, advantageously, the condensation of (II) / (III) in the presence of a metal complex, preferably a titanium complex, with titanium (IV) ethoxide being particularly preferred. In practice, the condensation reaction between the compounds (II) and (III) can be carried out in solvents such as toluene, xylene or tetrahydrofuran, to which He can optionally add the appropriate catalysts / With respect to the condensation of the compounds (II) and (III '), reference could be made to the patent application EP 0 562 915 for older people. details Said compounds of the formula (III) are known to those skilled in the art and can be obtained from the corresponding ketone in accordance with a method specifically described in the patent application WO-A-96 14596. The ketone by itself It can Obtained in commercial form or prepared in accordance with known methods such as the Friedel-Crafts method (see WO-A-96 14596 and cited references). The aldehydes obtained from (III) are obtained by transposition in an acid medium (see J. Org Chem., 1997, 42, 3403). Said compounds of the formula (II) are obtained according to a synthesis scheme whose various steps are adaptations of known methods. The general synthesis scheme that is preferred is given below.

This synthetic route is inspired by the work of Sepiol ef al. 10 (Synthesis 1979, 290). From which it follows that the invention also encompasses a method for preparing the naphthol precursors of the formula (II), characterized in that it comprises the following essential steps: 1. reaction of a precursor (lp?) Of the formula: with at least one alkyl cyanoacetate of the formula CN-CH2-COORa in which Ra = alkyl, preferably ethyl, so that the intermediate product (lp2) is obtained: • x-- z,. », Z-F - ^ .. * ^^ ¡ü 2. thermal cyclization of (IP2) leading to the intermediary (lp3): 3. elimination of the cyano group at high temperature from (Ip3> to produce intermediate (II).) Details on the complete method are given in the following examples 15. In any case, it is really a subject of a novel synthetic route in the field of photochromes, and this route offers advantages in terms of ease of implementation and in terms of economy In accordance with a third aspect, the objective of the invention is (co) polymer (s) and / or crosslinked material (s) (s) that is obtained by polymerizing and / or crosslinking at least one monomer comprising at least one compound (I) as defined above, Therefore, the compounds (I) according to the invention can be themselves (co) monomers and / or may be included in (co) polymers (co) polymerisable and / or crosslinkable. The (co) polymers and / or crosslinked materials obtained in this way can constitute photochromic matrices such as those presented below. According to a fourth aspect, the present invention relates to the use of said compounds of the formula (I) of the invention as photochromic agents. The object of the invention is, therefore: firstly, novel photochromic compounds which are constituted by the naphthopyran derivatives such as those defined above taken alone or as a mixture thereof and / or with at least some other photochromic compound of another type and / or with at least one non-photochromic coloring agent; in second, novel photochromic compositions comprising at least one naphthopyran derivative (I) as defined above and / or one of its derivatives, and / or at least one linear or crosslinked (co) polymer containing at least one a compound (I) according to the invention in its structure. Such photochromic compositions may contain at least some other photochromic compound, or some other type and / or at least one non-photochromic coloring agent and / or at least one stabilizing agent; these other photochromic compounds, non-photochromic coloring agents and stabilizing agents are prior art products known to those skilled in the art.

Within the context of the present invention, combinations of photochromic compounds of the invention and / or combinations of photochromic compounds of the invention and photochromic compounds of another type according to the prior art are recommended; such combinations being interesting in the sense that they are suitable for generating gray or brown dyes which are desired by the public in applications such as eyeglasses or solar glasses. These additional photochromic compounds may be those known to those skilled in the art and described in the literature, for example, crores (US-A-3,567,605, US-A-5,238,981, WO-A-94 22850, EP-A-0 562 915 ), spiropyrans or naptospiropyrans (US-A-5,238,981) and spiroxazines (Crano et al., "Applied Photochromic Polymer Systems", Ed. Blackie &Son Ltd, 1992, Chapter 2). Said compositions according to the invention may also comprise: non-photochromic agents that allow to adjust the dye, and / or one or more stabilizing agents, such as an antioxidant agent for example, and / or one or more anti-UV agents. , - and / or one more antiradical agents, - and / or one or more photochemical deactivators in the excited state. These additives can significantly improve the durability of said compositions.

V._Il? 5 a «S_lÉi5fe-Lt The compounds of the invention contemplated within the contexts of their photochromic applications can be used in solution. Therefore, a photochromic solution can be obtained by dissolving at least one of said compounds in an organic solvent such as toluene, dichloromethane, tetrahydrofuran or ethanol. The solutions obtained are usually colorless and transparent. When they are exposed to sunlight, they develop a strong color and regain their colorless state when they are placed in an area of less exposure to sunlight or, in other words, when they are not subjected to UV radiation. In general, a very low concentration of product (of the order of 0.01% to 5% by weight) is sufficient to obtain an intense coloration. The compounds according to the invention are also compatible with support matrices of organic polymer or an inorganic material, in a form included in said matrices as well as in the form of a coating of said matrices. Also, within the context of the fourth aspect of the invention in relation to photochromic applications, the objective of the invention is a matrix comprising: - at least one compound (I), as defined above; - and / or at least one (co) polymer and / or crosslinked material, as defined above; - and / or at least one composition as presented above. The most interesting applications of the compounds of the invention are in fact those in which the photochrome is dispersed uniformly within or on the surface of a matrix formed by a polymer, and / or (co) polymer and / or mixture of ( co) polymers. Following the example of their behavior in solution, the compounds (I) included in a polymeric matrix are colorless or slightly colorful in the initial state and rapidly develop an intense coloration under a UV light (365 nm) or under a solar-type light source . Finally, they regain their initial coloration once the irradiation ceases. The methods of implementation that can be contemplated in order to obtain such a matrix are very varied. Among those known to those skilled in the art, mention may be made, for example, of diffusion in the (co) polymer, from a suspension or solution of the photochrome in a silicone oil, in an aliphatic or aromatic hydrocarbon, or in a glycol , or from another polymer matrix. The diffusion is generally carried out at a temperature of 50 and 200 ° C for a period of 15 minutes up to several hours, in accordance with the nature of a polymeric matrix. Another implementation technique consists of mixing the photochrome in a formulation of polymerizable matrices, deposit this mixture on a surface or in a mold, and then perform the copolymerization. These implementation techniques, and others, are described in the article by Crano et al. "Spiroxazines and their use in photochromic lenses" published in Applied Photochromic Polymer Systems, Ed. Blackie and Son Ltd-1992. The following products can be mentioned as examples of preferred polymeric materials for forming matrices which are useful in optical applications of the photochromic compounds according to the invention: alkyl, cycloalkyl, (poly- or oligo) ethylene glycol, monoacrylate, diacrylate, triacrylate or aryl tetraacylate or aryl alkyl or monomethacrylate, dimethacrylate, trimetacrylate or aryl tetrametacrylate or arylalkyl, which are optionally halogenated or comprise at least one ether and / or ether and / or carbonate and / or carbamate and / or thiocarbamate group and / or or urea and / or amide, - polystyrene, polyether, polyester, polycarbonate (for example bisphenol-A polycarbonate, diallyl diethylene glycol polycarbonate), polycarbamate, polyepoxy, polyurea, polyurethane, polythiourethane, polysiloxane, polyacrylonitrile, polyamide, aliphatic or aromatic polyester, vinyl polymers, cellulose acetate, cellulose triacetate, cellulose acetopropionate or polyvinylbutyl ral, - difunctional monomers having the following formula: in which: ! ^ ^ ^ ^^^ if s - ^ .. ^ ^ ^ ^ ^ ^ ^ Me ^ ^? ? River, R'10. R11 and R'11 are identical or different and independently represent a hydrogen or a methyl group; ? my and nor are, independently, whole numbers between 0 and 4 (inclusive); and they are advantageously indefinitely equal to 1 or 2; ? X and X ', which are identical or different, are a halogen and represent, preferably a chlorine and / or a bromine; ? pi and qi are, independently, whole numbers between 0 and 4 (inclusive); - (co) polymers of at least two types of copolymerizable monomers which are selected from the precursor monomers of the polymers listed above, and preferably those belonging to the group comprising: methacrylic monomers, vinyl monomers, allylic monomers and mixtures thereof. In a particularly preferred mode, the photochromes of the invention are used with resins having a nanobiphasic structure and which are obtained by co-polymerizing at least two different specific difunctional monomers. Such resins have been described in French application FR-A-2 762 845. The amount of photochrome used in the copolymer matrix depends on the degree of darkening desired. Normally, it is used between 0. 001 and 20% by weight of this one.

Even in accordance with the fourth aspect in relation to the applications of naphthopyrans (I) as photochromes, another objective of the present invention are ophthalmic articles, such as ophthalmic or solar eyeglass articles, comprising: • at least one tax (I) according to the invention; • and / or at least one (co) polymer and / or a crosslinked material formed, at least in part, from compounds of the invention; • and / or at least one photochromic composition as defined above; • and / or at least one matrix (as defined above), an organic polymeric material or an inorganic material, or even of a hybrid inorganic-organic material, said matrix optionally comprising at the start at least one compound of the invention. In practice, the articles that are covered more particularly by the present invention are ophthalmic lenses or photochromic solar lenses, glazing (windows for buildings, for locomotives, for motor vehicles), optical devices, decorative articles, sunscreen articles, for storage, ... The present invention is illustrated by the following examples of synthesis and photochromic validation of compounds of the invention (naphthopyrans). Said compounds according to the invention are compared with the prior art compounds Ci and C2.

EXAMPLES EXAMPLE 1 Synthesis of the compound (1) compound (1) Step 1 The following mixture: 8.0 g of 1-phenyl-3,4-dihydro-. --naftalen-2-one (synthesized in accordance with Mills et al., J. Chem. Soc. 1956, 4213), 3.9 ml of ethyl cyanoacetate, 7 g of ammonium acetate, 3.6 ml of acetic acid in 70 ml of toluene, is heated under reflux in a conical flask of 100 ml equipped with a Dean Stark collector for 16 hours. The toluene is then distilled and the mixture is left for several hours at 220 ° C (cyclization of the lp2-type intermediate). The reaction mixture is then triturated in 50 ml of toluene and then filtered. 7.27 g of a colored solid are obtained ___ ^ 8 ^ «« to _ ~ «? - 3. - .. ^ t ^ a ^ J ^^ T '^^^ S-A ^ i-i iifeaSa yellow corresponding to intermediate compound 2-naphthol-1 Ciay or (IP3 structure).?.

Step 2 5 following mixture: 2.0 g of the previous step, 3 g of potassium hydroxide in 30 ml of n-butanol, is heated to about 200-220 ° C in a 125 ml reactor for 6 hours. After cooling, the mixture is transferred to a flask and then evaporated to dryness. The paste is then dissolved in 100 ml of water and then neutralized with the slow and progressive addition of concentrated hydrochloric acid (4 ml). The precipitate is recovered by filtration, washed with 4x20 ml of water and then dried under vacuum at 40 ° C overnight. Performance 90%.

Step 3 15 The following mixture: 808 mg of the product from the previous step, 1.05 g of 1,1-bis (para-methoxyphenyl) -propin-1-ol is heated under reflux in the presence of a catalytic amount of bromoacetic acid in 45 ml of xylene in a 100 ml reactor for 6 hours. The mixture is then evaporated to dryness and the product is then isolated by chromatography over silica eluting with toluene. The purest photochromic fractions are combined and evaporated to dryness. After recrystallization from THF / heptane, 640 mg of compound (1) is recovered as a solid. Its structure is confirmed by NMR spectroscopy.

S. & , - S_ > jj_8 &fc4.Fx = i ^ &AiftmAa EXAMPLE 2 Synthesis of the compound (2) The following mixture: 7 < || gm of the product from step 2 of the previous example, 930 mg of 1-para-dimethylaminophenyl-1-phenyl-propin-1-ol is heated under reflux in the presence of a catalytic amount of bromoacetic acid in 25 ml of xylene in a 100 ml reactor for 6 hours. The mixture is then evaporated to dryness and the product is then isolated by chromatography on silica gel eluting with toluene. The purest photochromic fractions are combined and evaporated to dryness. 120 mg of the compound (2) are obtained in the form of a solid. Its structure is confirmed by NMR spectroscopy.

EXAMPLE 3 Synthesis of the compound (3) compound (3) * & - * v Step 1 The derivative - < 1- (p-methoxyphenyl) -6-methoxy-3,4-dihydronaphthalene (synthesized in accordance with the method adapted from Org. Synth, Coll. Volll, p 729) is converted to epoxy-reactive by transposition, in basic medium, of the corresponding bromohydrin (according to J. Org Chem. 1986, 3407). The ketone is then obtained by rearrangement of the epoxy derivative in acid medium. The naphthol type II derivative is then synthesized in the same manner as indicated above. Step 2 The compound (3) is obtained by reaction of the derivative of the previous step with 1,1-bis (p-methoxyphenyl) -propin-1-ol as in example 1. The product (3) is obtained after purification. Its structure is confirmed by NMR spectroscopy.

EXAMPLE 4 Synthesis of the compound (4) Compound (4) is obtained by reacting the intermediate derivative of type II of the previous example with 1-para-dimethylaminophenyl-1-p-methoxy-phenyl-propin-1-ol as in example 1. The product (4) is obtained _ ^^ jáiah ^ ai ^^ g ^ WÍÉ £ ^^ fA. ??? "M. < , * «_ _ After purifying it. Its structure is confirmed by NMR spectroscopy.

EXAMPLE 5 Synthesis of. compound (5) compound (5) The compound (5) is obtained by reaction of the above naphthol derivative (500 mg) (obtained according to the method described by Newman et al., J. Amer. Chem. Soc. 1938, 60, 2947) with the 1, 1 bis (p-methoxyphenyl) -propin-1-ol (560 mg) as in Example 1 with a reflux time of 2 hours. 300 mg of the compound (5) is obtained after purification. Its structure is confirmed by NMR spectroscopy.

- ~ Z «* aa_aftf» _- EXAMPLE 6 Synthesis of the compound (6) compound (6) Step 1 The 2- (1-naphthyl) cyclohexanone derivative is prepared by reaction of the magnesium derivative of 1-bromonaphthalene with epoxycyclohexane (according to Takahashi et al., Tetrahedron Asym., 1995, 6, 617) by oxidation with chlorochromate of pyridinium (in accordance with Corey et al., Tetrahedron Lett., 1975, 2647). The following mixture: 8.4 of 2- (1-naphthyl) cyclohexanone, 4.3 g of ethyl cyanoacetate, 4 g of ammonium acetate, 4 ml of acetic acid in 40 ml of toluene, is heated to reflux in a 100 ml flask equipped with a Dean Stark collector, for 8 hours. The toluene is then distilled and 15 g of acetamide are added. Then it is kept at a temperature of 200 ° C for 3 hours. The hot medium is then poured into 200 ml of water and the solid precipitate is collected by filtration. Recrystallization with ethanol allows 7.6 g of added naphthol (Ip3 > ss.JHS ~ K.fc Step 2 ** The following mixture: 3.5 g of the product of the previous step, 5 g of potassium hydroxide in 20 ml of n-butanol, is heated to approximately 200-230 ° C in a reactor of 125 8 hours. After cooling, the mixture is transferred to a flask and then evaporated to dryness. The paste is then dissolved in 100 ml of water and then neutralized with the slow and progressive addition of concentrated hydrochloric acid. The precipitate is recovered by filtration, washed with 4x20 ml of water and then dried under vacuum at 40 ° C overnight. Naphthol (type II) is obtained from this way in quantitative performance.

Step 3: The following mixture: 1 g of the product from the previous step, 1.5 g of 1,1-bis (para-methoxyphenyl) -propin-1-ol, is heated to reflux in the presence of a The catalytic amount of bromoacetic acid in 15 ml of xylene in a 100 ml reactor for 5 hours. The product is then purified by chromatography on silica eluting with a toluene / heptane mixture (70/30). The purest photochromic fractions are combined and evaporated to dryness. After recrystallization from toluene / heptane, recover 230 mg of the compound (6). Its structure is confirmed by NMR spectroscopy. compound (7) The compound (7) is synthesized in the same manner as that described for the compound (6). For the last step, 1 g of the naphthol is reacted with 1.1 g of 1,1-bis (para-methoxyphenyl) -propin-1-ol in the presence of a catalytic amount of bromoacetic acid in 20 ml of toluene. The product is then purified by chromatography on silica eluting with a toluene / heptane mixture (80/20). The purest photochromic fractions are combined and evaporated to dryness. After recrystallization with a mixture of toluene / diisopropyl ether, 800 mg of the compound (7). Its structure is confirmed by NMR spectroscopy EXAMPLE 8 Synthesis of the compound (8) The compound (8) is obtained in a manner analogous to that described for example (6) in the sense that the naphthol derivative is allowed to react with 1- (para-dimethylaminophenyl) -1-phenyl-propin-1-ol .

EXAMPLE 9 Synthesis of the compound (9) compound (9) The compound (9) is obtained in a manner analogous to that described for example (6) by starting with 2- (1-naphthyl) cyclopentanone.

EXAMPLE 10 Synthesis of the compound (10) compound (10) The fenantrol intermediate was obtained according to the same method as that described in example 3. The compound (10) is then obtained by coupling with 1- (para-morpholinophenyl) -1-phenyl-propin-1-ol how I know ara1 i < a ____ átt__8_¿a -A-aife. ÍJ¿ - described in Example 1. Its structure is confirmed by NMR spectroscopy.

EXAMPLE 11 Synthesis of the compound (11) compound (11) The naphthol intermediate compound was obtained according to the same method as indicated in Example 3, starting from benzotetralone (obtained according to A. Eirin et al., Arch. Pharm. 1987, 320, 1110) instead of tetralone. The compound (11) is then obtained by coupling with 1- (para-dimethylaminophenyl) -1-phenyl-propin-1-ol as described in example 1, followed by purification by chromatography. Its structure is confirmed by NMR spectroscopy. , _ 4 ^ * - > * EXEMF 12 Synthesis of the compound (12) Compound (12) was obtained by reacting the intermediate naphthol of Example 1 with 1-thien ^ * lenyl-propin-1-ol as described in the last step of example 1, followed by purification by chromatography. Its structure is confirmed by NMR.

EXAMPLE 13 Synthesis of the compound (13) compound (13) Compound (13) was obtained by reaction of the naphthol intermediate (obtained according to Robinson, J. Chem. Soc, 1938, 1390) with 1,1-bis (para-methoxy-phenyl) -propin-1-ol, followed by a purification by chromatography. Its structure is confirmed by NMR. ? rn. ü_5to¿ly ^ M «b ^ ¡» _.

Compounds C1. C2. and C3 Comparative compound O1 is synthesized from 1-naphthol and 1,1-bis (p-methoxyphenyl) -propin-1-ol. E »Ra formula (C1). Compound C2 is of the formula: Compound C2 can be obtained commercially. The compound C3 is described in the patent E.U.A. US-A-5,783,116.

EXAMPLE 15 The photochromic properties of said compounds (1) to (13), C1, C2 and C3 were evaluated. Said compounds are dissolved, in the ratio of 5 mg in 50 ml of THF and the absorptions are then measured in the UV-visible spectrum (optical path of 1 cm) before and after exposure to a UV source at 365 nm. The observation of the dyes and the intensities developed is done by placing the solutions in the sun or before a solar simulator. The properties of these compounds are given in the following table. * ^ j aiawteg faith-faith. __ & & amp; ^ áfeJ t * *? maximum of the longest 4-long strip of the compound before exposure. **? maximum band of the longest wavelength of the compounds after exposure. The visual inspection of the solutions in the presence of solar radiation or UV radiation shows that the compounds of the invention have? 1 and? 2 which are displaced towards longer wavelengths (batochromic displacement) and rapid kinetics of discoloration in comparison with the analogous compounds C1, C2 and C3.

Claims (4)

NOVELTY PE_LA «fafeNCIO CLAIMS

1. - Compounds of the following formula (I): wherein: Ri and R2 are identical or different and independently represent: hydrogen, a linear or branched alkyl group comprising from 1 to 12 carbon atoms, a cycloalkyl group comprising from 3 to 12 carbon atoms, a group aryl or heteroaryl which in its basic structure comprises from 6 to 24 carbon atoms or from 4 to 24 carbon atoms respectively and at least one heteroatom selected from sulfur, oxygen and nitrogen; said basic structure optionally being substituted with the at least one substituent selected from the total of the substituents indicated below: a halogen and specifically fluorine, chlorine and bromine, a hydroxy group, a linear or branched alkyl group comprising from 1 to 12 carbon atoms, a linear or branched alkoxy group comprising 1 to 12 carbon atoms, a halogenoalkyl or halogenoalkoxy group corresponding respectively to the above C1-C12 alkyl or alkoxy groups which are substituted with at least one atom of halogen, and specifically such a fluoroalkyl group, a phenoxy or naphthoxy group optionally substituted with at least one linear or branched alkyl or alkoxy group comprising 1 to 6 carbon atoms, a linear or branched alkenyl group comprising 2 to 12 atoms of saloon and specifically a vinyl group or an allyl group, a group -NH, a group -NHR, in which and R represents a linear or branched alkyl group comprising from 1 to 6 carbon atoms, a group R "-, - N \ R '- ~' R 'and R ", which are identical or different, independently represent a linear or branched alkyl group comprising from 1 to 6 carbon atoms, a phenyl group optionally substituted with at least one linear or branched alkyl or alkoxy group comprising from 1 to 6 carbon atoms, or represent together with the nitrogen atom to which a 5 to 7 membered ring is attached, which may comprise at least some other heteroatom selected from oxygen, sulfur and nitrogen, said nitrogen being optionally substituted with a group R '", which is a linear or branched alkyl group comprising from 1 to 6 carbon atoms, a methacryloyl group or an acryloyl group; an aralkyl or heteroaralkyl group, comprising the alkyl group, which is linear or branched, < •% »«. from 1 to 4 carbon atoms, and the aryl and heteroaryl groups the definitions given above, or said two substituents Ri and R2 together form an adamantyl, norbornyl, fluorenylidene, dialkyl CrCß) -anthracenylidene group or a spirocycloalkyl (C5-C6) group ) -antracenilidene; said group being optionally substituted with at least one of the substituents listed above for R2 corresponding to an aryl or heteroaryl group; R3, which is identical or different, represents, independently: a halogen and preferably fluorine, chlorine or bromine, a linear or branched alkyl group comprising from 1 to 12 carbon atoms 10 (advantageously from 1 to 6 carbon atoms), a cycloalkyl group comprising from 3 to 12 carbon atoms, a linear or branched alkoxy group comprising from 1 to 12 carbon atoms (advantageously from 1 to 6) carbon atoms), a halogenoalkyl, halogenocycloalkyl, haloalkoxy group corresponding respectively to alkyl groups, 15 cycloalkyl, alkoxy, which are substituted with at least one halogen atom, which is specifically selected from fluorine, chlorine and bromine, an aryl or heteroaryl group having the same definition as that given above for R1, R2 , an aralkyl or heteroaralkyl group, the alkyl group comprising, which is linear or branched, from 1 to 4 20 carbon atoms and the aryl and heteroaryl groups having the same definitions as those given above for R 1, R 2, a phenoxy or naphthoxy group optionally substituted with at least one alkyl or alkoxy group * 4 * & & amp; & 3 * S! I * M ^ A5 &''% linear or branched comprising from 1 to 6 carbon atoms an amine or amide group: -NH2, -NHR , -CONH2, -CONHR, ** '' ' R "~ R" "- N; or -CON;; 5 R" - '' ^ C - 'having R, R', R "the respective definitions given above for the amine substituents of the Ri, R2: aryl or heteroaryl, a group -OCORs or -COORs, in which Rs represents a linear or branched alkyl group comprising from 1 to 6 carbon atoms or a group Cycloalkyl comprising from 3 to 6 carbon atoms or a phenyl group which is optionally substituted with at least one of the substituents listed above for the values of R1, R2: aryl or heteroaryl; or at least two adjacent R3 groups together form at least one aromatic or non-aromatic cyclic group having a single ring or Having two fused rings, optionally comprising at least one heteroatom which is selected from the group comprising: oxygen, sulfur and nitrogen, this or these fused rings being optionally substituted with at least one substituent selected from those having the definitions given above for the aryl or heteroaryl groups which 20 can form R1 and / or R2; m is an integer from 0 to 4; A represents: a ^ a8 »A« 'i ^ and gfe: .- ¿^ _ > 7 aga ^ a ^ Aj ^ a ^ &, ^ - .., _.._ < < _ & ».« i i? f'ft in these fused rings (A-i) to (A5): the dotted line represents the bond of carbon C5 to carbon Ce of the naphthopyran ring of formula (I); the bond a of the fused ring (A4) or (A5) can be linked indistinctly to the C5 carbon or to the Ce carbon of the naphthopyran ring of the formula (I); R4, which is identical or different, independently represents an OH group, an alkyl group or an alkoxy group which are linear or branched and which comprise from 1 to 6 carbon atoms or two of the R4 form a carbonyl (CO); R5, Re and R7 represent, independently: a halogen and specifically fluorine, chlorine or bromine, a linear or branched alkyl group comprising from 1 to 12 carbon atoms (advantageously from 1 to 6 carbon atoms), a halogenoalkyl group corresponding to the above linear or branched alkyl group, which is substituted with at least one halogen atom, specifically a fluoroalkyl group, a cycloalkyl group comprising from 3 to 12 carbon atoms, a linear or branched alcofi group comprising from 1 to 6 carbon atoms, a phenyl or benzyl group, optionally substituted with at least one of the substituents listed above in the definitions of the radicals Ri, R2 5 of the formula (I) in the case in which the radicals correspond independently to an aryl or heteroaryl group, an amino group -NH2, -NHR, - N R "- - ' Having R, R 'R "their respective definitions given above for the amino substituents of the Ri, R2: aryl or heteroaryl, a phenoxy or naphthoxy group optionally substituted with at least one linear or branched alkyl or alkoxy group which comprises from 1 to 6 carbon atoms, a group -CORg, -COORg or -CONHRg, in which Rg represents a linear alkyl group or Branched comprising from 1 to 6 carbon atoms or a cycloalkyl group comprising from 3 to 6 carbon atoms or a phenyl or benzyl group which is optionally substituted with at least one of the substituents listed above in the definitions of the radicals R1, R2 of the formula (I) in the case in which the radicals correspond independently to 20 an aryl or heteroaryl group, it being possible for two adjacent R5 groups to together form an aromatic or non-aromatic ring of 5 to 6 links which may comprise at least one heteroatom which is selected from the group comprising: oxygen, sulfur and nitrogen; n is an integer from 0 to 6, or is a integer from 0 to 2, p is an integer from 0 to 4 and q is an integer from 0 to »3; with - the condition according to which in (Ai) and (A2) n is zero only in the case where at least two adjacent R3 substituents form at least one aromatic or non-aromatic cyclic group having a ring 5 individual or two fused rings, optionally comprising at least one heteroatom selected from the group comprising: oxygen, sulfur and nitrogen, this ring or these fused rings being optionally substituted with at least one substituent selected from those which have the definition given above for the 10 aryl groups which can form R1 and / or R2. 2. The compounds of the formula (I) according to claim 1, further characterized in that A corresponds to one of the fused rings (Ai) or (A2) as defined in claim 1. 3.- The compounds of formula (I) in accordance with 15 claim 1, further characterized in that A corresponds to one of the fused rings (A3 (A4) or (A5) as defined in claim 1. 4.- The compounds of the formula (I) according to any of the claims 1 to 3, in which at least two of the adjacent R3 groups together form at least one aromatic cyclic group 20 or non-aromatic having a single ring or having two fused rings, optionally comprising at least one heteroatom which is selected from the group comprising: oxygen, sulfur and nitrogen, this ring or these fused rings being optionally substituted with i - ^ S? ^ «aág« = __ fei > = g B ^ EÍtefe &"._ • ..L ^ rf.fe.t. ^ j-s. • * menos menos menos menos menos menos menos menos menos menos??????????????????????????????????????????????????????????????????????. 5. The compounds according to any of claims 1 to 4, further characterized in that they are of the formula (I) in which: Ri, R2 are identical or different and independently represent optionally substituted aryl or heteroaryl groups whose basic structure is selected from those of phenyl, naphthyl, biphenyl, pyridyl, furyl, benzofuryl, dibenzofuryl, N-alkyl (CrC6) -carbazole thienyl, benzothienyl, dibenzothienyl, julolidinyl, represented R1 and / or R2, advantageously , a phenyl group substituted in the para position; or R1 and R2 together form an adamantyl or norbornyl group. 6. A method for preparing the compounds of the formula (I) according to any of claims 1 to 5, further characterized in that it consists essentially of carrying out the condensation: of at least one compound having the following formula (II) : - »_» »¿_ _. in which R3, A and m are as defined previously with reference to formula (I); with at least one propargyl alcohol derivative having the following formula (III): wherein Ri and R2 are as defined above with reference to formula (I); the condensation of (11) / (III) being advantageously carried out in the presence of a catalyst, this catalyst being preferably selected from the group comprising para-toluenesulfonic acid, dodecyl sulfonic acid and bromoacetic acid, or with at least one derivative thereof. aldehyde having the following formula (MI '): wherein R1 and R2 are as defined above with reference to formula (I); performing, advantageously, the condensation of (II) / (III) in the presence of a metal complex, preferably a titanium complex, with titanium (IV) ethoxide being particularly preferred. 7. The method according to claim 6, further characterized in that the starting compound of the formula (II) is produces by performing the essential steps of: 1. reaction of a precursor (lp?) * ^ of the formula: * with at least one alkyl cyanoacetate of the formula CN-CH2-COOR3 in which Ra = alkyl, preferably ethyl, so that the intermediate product (IP2) is obtained:

2. thermal cyclization of (IP2) leading to the intermediary (Ip3):

3. removal of the cyano group at high temperature from (Ip3> to produce the intermediate (II) 8.- A (co) polymer and / or crosslinked material obtained by polymerization and / or crosslinking of at least one monomer * - * »« - ^ constituted by at least one compound according to any of claims 1 to 5. 9.- A photellirical compound characterized in that it is constituted by a compound according to any of claims 1 to 5, or by a mixture of at least two compounds according to any one of claims 1 to 5 or by a mixture of at least one compound according to any of claims 1 to 5 with at least one other photochromic compound of another type and / or at least one non-photochromic coloring agent. 10. A photochromic composition, characterized in that it comprises: at least one compound according to any of claims 1 to 5; and / or at least one linear or crosslinked (co) polymer having in its structure at least one compound (I) according to any one of claims 1 to 5, and optionally, at least some other photochromic compound of another type and / or at least one non-photochromic coloring agent and / or at least one stabilizing agent. 11. A polymer (co) matrix, characterized in that it comprises: at least one compound (I) according to any of claims 1 to 5; and / or at least one composition according to claim 10, and / or at least one (co) polymer and / or crosslinked material according to claim 8. 12. The matrix according to claim 11, characterized in that the constituent (co) polymer (s) is _feto ^ ____ fc_ ^ a8aBBfa selects (n) from the following list: alkyl, cycloalkyl, (poly- or oligo) ethylene glycol, mono- acrylate, diacrylate, triacrylate or aryl tetraacrylate or aryl alkyl or monomethacrylate, dimethacrylate, trimethylacrylate, aryl or arylalkyl rilate or tetramethacrylate, which are optionally halogenated or comprise at least one ether and / or ether and / or carbonate and / or carbamate and / or thiocarbamate and / or urea and / or amide group; polystyrene, polyether, polyester, polycarbonate (for example bisphenol-A polycarbonate, diallyl diethylene glycol polycarbonate), polycarbamate, polyepoxy, polyurea, polyurethane, polythiourethane, polysiloxane, polyacrylonitrile, polyamide, aliphatic or aromatic polyester, vinyl polymers, cellulose acetate, cellulose triacetate, cellulose acetopropionate or polyvinyl butyral; difunctional monomers having the following formula: 15 in which: Rio, R'10. Rn and R'n are identical or different and independently represent a hydrogen or a methyl group; my and nor are, independently, whole numbers between 0 and 4 (inclusive); and are advantageously independently equal to 1 or 2; X and X ', which are identical or different are a halogen and represent, preferably a chlorine 20 and / or a bromine; pi and qi are, independently, whole numbers between 0 and 4 (inclusive); (co) polymers of at least two types of copolymerizable monomers which are selected from the precursor monomers of the polymers listed above, and preferably those which ^^^ £ ^ _M ^ __ iate -. ^? Lte ^ -tefe ^ - Jt &? - á - ^ - J: ^ * belong to the group vinyl monomers, monomers 13.- an ophthalmic or solar article that comprises: minus one compound (I) according to any of claims 1 to 5; and / or at least one composition according to claim 10, and / or at least one (co) polymer and / or crosslinked material according to claim 8; and / or at least one matrix according to one of claims 11 or 12. 1

4. The article according to claim 13, further characterized in that it is constituted by a lens, a glaze or by an optical device. naphthopyran these compounds are of the formula (I) wherein A is an alicyclic ring that is optionally fused to an aromatic ring and in which two adjacent R3 groups can together form at least one ring, for example a benzo group; these compounds (I) possess interesting photochromic properties; the invention also refers 15 to a method for preparing these compounds (I), as well as their application as photochromes; compositions and matrices (co) polymer that contain them. JT / igp * jtr * osu * tpr * kra * mmf * sff. P01 / 69F