MXPA01008319A - Naphthopyrans and phenanthropyrans annelated in c5-c6 with a bicyclic group, and compositions and (co)polymer matrices containing them - Google Patents

Abstract

The invention relates to novel naphthopyran- and phenanthropyran-type compounds having a carbobicycle annelated in 5,6- position. These compounds have formula (I). These compounds (I) have interesting photochromic properties. The invention also relates to their preparation, to their applications as photochromes, as well as to the compositions and (co)polymer matrices containing them.

Description

NAFTOPIRANOS AND FENANTROPIRANOS RUBBED AT C5-C6 WITH A BICICLICO GROUP, AND COMPOSITIONS AND MATRIXES OF COPOLYMERS THAT CONTAIN THEM.

The present invention relates to novel compounds of the type naphthopyrans or ringed phenanthropyres which have, in particular, photochromic properties. The invention also discloses photochromic compositions and photochromic ophthalmic articles (for example lenses) which contain said naphthopyrans or phenanthropyrans. The invention also covers the preparation of these new compounds. The photochromic compounds are able to change color under the influence of poly or monochromatic light (UV for example) and to return to their initial color when the light irradiation ceases, or under the influence of the temperature and / or light poly or monochromatic different from the first. It has been found that photochromic compounds have application in various fields, for example for the manufacture of ophthalmic lenses, contact lenses, lenses for sun protection, filters, optical cameras or photographic optical devices or other optical devices and observation devices, works in glass, decorative objects, signs or for the conservation of information by optical inscriptions (codes). In the field of ophthalmic optics, and in particular in the eyeglass business, a photochromic lens comprises one or more photochromic compounds that must have: a high transmission in the absence of ultraviolet, - a low transmission (high colorability) under irradiation solar, -'- accommodated coloration and kinetics of discoloration, - a dye acceptable to the consumer (preferably gray or brown) with a maintenance of the dye preferably chosen during the coloring and the discoloration of the lenses, the maintenance of the performance, the properties, within a temperature range of 0-40aC, - a significant durability, because these objectives seen a posteriori are sophisticated corrective lenses, and therefore of high cost. The characteristics of these lenses are actually determined by the active photochromic compounds they contain; the compounds can be further refined to make them compatible with the organic or inorganic supports (or even with inorganic-organic hybrids) which constitute the lenses. Moreover, it should be noted that obtaining gray or brown tints may require the use of at least two photochromes of different colors, for example, having a different maximum absorption of wavelengths in the visible. This combination also imposes other requirements of the photochromic compounds. In particular, the coloration and decolorization kinetics of (two or more) combined active photochromic compounds must be essentially identical. The same applies for its stability over time and also for its compatibility with plastic or inorganic or hybrid supports. Among the "numerous photochromic compounds described in the prior art, mention may be made of benzopyrans and naphthopyrans, which have been described in patent applications US-A-3,567,605, US-A-3,627,690, US-A No. 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-5,698.1 1, US-A-5,783,116, WO-A-95 05382, "FR-A-2.718 .447, OA-96 14596, OA-97 21698 which are of the reduced formula shown below: Benzopyrans Naftopyrans The patent US-A-5. 51,923 claims the general structure below: US-A-5651923 wherein ring A, annealed with side f, is a benzothieno-, benzofuran-, or heterocycle of the indole type. US-A-5,783,116 describes more specifically the naphthopyrans of the following general structure These compounds are claimed to meet the specifications defined above. Actually, if these compounds actually had one or more of the basic properties that will be seen later, such as high light transmission in the absence of ultraviolet and high colorability under solar irradiation, none of these compsbscribed here have the full combination of the properties that will be seen later, which are necessary for the production of satisfactory articles. In particular, none of these compounds is intrinsically gray or brown and therefore the need to use additional photochromes in order to obtain one of these two dyes remains. In this context, the credit of the inventors was to have interest in this type of derivatives as a basis for the development of new photochromes, and to propose a novel family of molecules which have particularly advantageous photochromic properties. Thus, according to a first aspect, the present invention relates to compounds of the formula (I): wherein: Ri and R2 are identical or different, independently represent: hydrogen, branched or linear alkyl group comprising 1 to 12 carbon atoms, cycloalkyl group comprising 3 to 12 carbon atoms, aryl or heteroaryl group, which comprises in its basic structure 6 to 24 carbon atoms or 4 to 24 carbon atoms respectively and at least one heteroatom selected from sulfur, oxygen and nitrogen, said basic structure being optionally substituted with minus one substituent selected from the total of the substituents given below: + a halogen, and notably fluorine, chlorine and bromine, + a branched or linear alkyl group comprising 1 to 12 carbon atoms, + a branched or linear alkoxy group which it comprises one to 12 carbon atoms, + a haloalkyl or haloalkoxy group corresponding to the alkyl or alkoxy (C? -C? 2) groups above respectively which are their bituted with at least one halogen atom and notably such a fluoroalkyl group, + a branched or linear alkenyl group comprising 2 to 12 carbon atoms and notably a vinyl group or an allyl group, + a -NH2, + group a group -NHR, where R represents a branched or linear alkyl group comprising from 1 to 6 carbon atoms, + a group RJ -N R ".

R 'and R ", which are identical or different, independently represent a branched or linear alkyl group comprising from 1 to 6 carbon atoms or representing together with the nitrogen atom to which they are attached to a ring of 5 to 7 members which may comprise at least any one of another heteroatom selected from oxygen, sulfur and nitrogen, said nitrogen being optionally substituted with a group R '' ', which is a branched or linear alkyl group comprising from 1 to 6 atoms of carbon. + a methacryloyl group, or an acryloyl group, - an aralkyl or heteroaralkyl group, the alkyl group, which is branched or linear, comprising from 1 to 4 carbon atoms and the aryl part which has the same definition as the given above for the aryl and heteroaryl group; or said two substituents Rx and R2 together form an adamantyl, norbonyl, fluorenylidene, di (C? -C6) alkylatratracenylidene or a. spiro group (C5-C6) alkylatratracenylidene cycle; said group being optionally substituted with at least one of the substituents listed above for Ri, R2: an aryl or heteroaryl group; • R3, which are identical or different, independently represent: a halogen, and notably fluorine, chlorine or bromine, a branched or linear alkyl group comprising 1 to 12 carbon atoms (more advantageously 1 to 6 carbon atoms) , - a cycloalkyl group comprising from 3 to 12 carbon atoms, - a branched or linear alkoxy group comprising from 1 to 12 carbon atoms (more advantageously from 1 to 6 carbon atoms), a haloalkyl, halocycloalkyl group, or haloalkoxy corresponding to the alkyl, cycloalkyl and alkoxy groups above respectively, which are substituted with at least one halogen atom, particularly selected from the group of fluorine, chlorine and bromine, - an aryl or heteroaryl group having the same definition given above for Ri and R2, - an aralkyl or heteroaralkyl group, an alkyl group, which is linear or branched, comprising one to 4 carbon atoms, and the groups a ryl or heteroaryl having the same definition given above for Ri, R2. - an amine or amide group: -NH2, NHR, -CONH2, CONHR, R, R ', R ", which have their respective definitions given above for the amine substituents of the RX / R2 values: aryl or heteroaryl, - a group-OCOR6 or -COOR6, Re representing a branched or straight alkyl group comprising from 1 to 6 carbon atoms, or a cycloalkyl group comprising from 3 to 6 carbon atoms, or a phenyl group, optionally substituted with at least one of the substituents listed above for the values of Ri, R2: aryl or heteroaryl; or at least two of the groups R3, which are adjacent, forming an aromatic ring of 5 to 6 members or a non-aromatic ring which may comprise at least one heteroatom selected from the group consisting of: oxygen, sulfur or nitrogen and / or at least one substituent selected from a Cj.-C6 alkyl group, which is linear or branched, a Ci-Ce alkoxy group, which is linear or branched, and an amine group of the formula -NH2, -NHR or R \ -N R "' defined above as substituents, of the basic structure of the aryl group, or heteroaryl representing Ri or R2; • m is an integer from 0 to 4; • R which is identical or different independently represented: a halogen preferably selected from the group consisting of fluorine, chlorine and bromine, an alkyl group, or a C? -C6 alkyl group which is linear or branched; n is an integer from 0 to 4. Those skilled in the art will obviously be able to understand that the branched alkyl, alkoxy and alkenyl groups as described above comprise a sufficient number of carbons as a function of being branched (more than 3, more than 3, and more than 4 carbon atoms respectively). The compounds of the invention - naphthopyrans or phenanthropyrans of the formula (I) have a high colorability even at 40 ° C, combined with a decolorization kinetics which is adapted for the application of a posterior vision. The colors which can be easily achieved vary from red to blue. Among said compounds of the invention, they are preferably those which have the formula (I), in which: Ri, R2 are identical or different and independently represented optionally substituted by heteroaryl groups or aryls of basic structure which are selected from the group comprising phenyl, naphthyl, biphenyl,. pyridyl, furyl, benzofuryl, dibenzofuryl, alkyl carbazole N- (C? -C6), thienyl, benzothienyl, dibenzothienyl, and julolidinyl groups; Ri and / or R2 advantageously representing a para-substituted phenyl group; or Ri and R2 together form an adamantyl or norbonyl group. According to a first embodiment of the invention, the compounds (I) are such that at least two of their adjacent substituents R3 do not together form a ring. According to a second embodiment of the invention, the compounds (I) are such that they comprise at least two adjacent R3 groups, which together form a heterocycle or ring carbocycle, which is optionally substituted (with an alkyl or alkoxy group) C? -C6 or with an amine group). According to a variant of this second embodiment, the invention discloses the following phenanthrene structures of formulas (1.1) and (1.2): (iD (I-2) In which Rj, R2, and R4 are as defined above, R3? and R32 independently represent a group having the same definition given above for R in the generic formula (I), which includes the two embodiments described above: R5 represents an alkyl, alkoxy, or amine group as defined above and m = 0, 1, 2, n = 0 to 4 and I = 0 to 4. According to the invention, notably according to the two above-mentioned embodiments, n = 0 in the formulas (I), (1.1) or (1.2). In accordance with the second of these aspects, the present invention discloses a method for preparing the compounds, (I ), characterized in that it consists essentially of a condensation being carried out: • of an intermediate product of formula (II.1), (II.2) or (II.3) given below: (11.1) (II.2) (H.3) wherein R3, R31, R32, 'R4, R5,, n, and o are as defined above with reference to formulas (I), (1.1), (1.2); with a propargyl alcohol derivative having the formula (III) below: wherein Ri and R2 are as defined above with reference to formula (I); the condensation (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 or bromoacetic acid; or • with an aldehyde derivative, having, the formula (III ') below: wherein Ri and R2 are as defined above with reference to formula (I): condensation (11) / (III ') being advantageously carried out in the presence of a metal complex, preferably a complex of titanium, with titanium (IV) ethoxide being particularly preferred.

In practice, the condensation reaction between the compounds (II) and (III ') can take place in solvents such as toluene, xylene, or tetrahydrofuran, in which the appropriate catalyst is optionally added. For more details on the condensation of the compounds (11) / (III '), it can be referred to the patent application EP-A-0 562 915. The compounds of the formula (III) are known to those skilled in the art. the art and are obtained from the corresponding ketone according to the method described in patent application WO-A-96 14596. The ketone is commercially available or is prepared according to known methods such as the Friedel Crafts method (WO- A-96 14596 and the references cited). The aldehydes (III ') which are derivatives of (III) are obtained by rearrangements in an acid medium (cited J. Org. Chem., 1977, 42, 3403). The compounds of the formula (II) are obtained according to a synthesis scheme of several stages, which are adaptations of known methods. The preferred general synthetic scheme is given below, for the compound (II.1). The compounds of formula (II.2) and (II.3) can be obtained by the same routes starting from organomagnesium reagents of 2-bromo- or 1-bro onaphthalene respectively.

Scheme 1: Route A Stage 1 and Scheme 2: Route B Regarding route A: stage 1 is carried out according to the method described by Basavaiaiah et al (Tetrahedron Symm, 1994, 5, 223-234), stage 2 by Corey et al. (Tetrahedron Lett, 1975, 2647) and stage 3 by Sepiol et al. (Synthesis 1979, 290). Regarding route B: stage 1 is carried out according to the method described by Schoenleber et al. (O-A-96 38435) and stages 2 and 3 according to Lin (US-A-5,783,116). According to a third aspect, the invention also discloses new intermediate products of formula (II.1), (II.2), (II.3) shown below (11.1) (11-2) (11.3) in which R3, R31, R32, R4, R5, m, n and o are defined above with reference to formulas (I), (1.1), (1.2). The naphthopyrans or phenanthropyrans of the invention are obtained by condensation of at least one compound having a formula of type (II), (with a compound of formula III or III '). According to the fourth aspect, the object of the invention is a (co) polymer / s and / or crosslinked / s obtained by polymerization and / or crosslinking and / or by grafting at least one monomer consisting of a compound (I) as define above. In this way, the compounds (I) according to the invention can be (co) monomers per se and be comprised in crosslinkable (co) monomers and / or (co) polymerizable monomers. The (co) polymers and / or crosslinks thus obtained may constitute photochromic matrices such as those presented below. According to a fifth aspect, the present invention discloses the use of said compounds of the formula (I) of the invention as photochromic agents. Another object of the invention is also: New photochromic compounds which are constituted by derivatives of naphthopyrans or phenanthropyrans as defined above, taken alone or in a mixture thereof and / or with at least some of the photochromic compounds of another type and / or with at least one non-photochromic coloring agent; Novel photochromic compositions which comprise at least one compound (I) as described above and / or one of its derivatives and / or at least one linear or crosslinked copolymer containing in its structure at least one compound (I) according to 'the invention. Such photochromic compositions may contain at least one other photochromic compound of another type and / or at least one non-photochromic coloring agent and at least one stabilizing agent. These photochromic compounds of another type, non-photochromic coloring agents and stabilizing agents are products already known in the art by the skilled person. Within the context of the present invention, the combinations of photochromic compounds of the invention and combinations <are particularly recommended.; of photochromic compounds of another type according to the prior art being such combinations of interest in that they are capable of generating gray or brown tints, which are desired by the public in applications such as ophthalmic goggles or solar glasses. These additional photochromic compounds may be those known to the person skilled in the art and described in the literature, for example chrome (US-A-3,567,605, US-A-5,238,981, WO-A-94 22850, EP- A-0 562 915), spiropyrans or naphthospiropyrans (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 coloring agents which facilitate the adjustment of the dye, and one or more stabilizing agents such as an antioxidant agent such as, for example, and / or one or more anti-UV. , - and / or one or more antiradicals, - and / or one or more photochemical deactivators of excited states. These additives can remarkably be able to improve the durability of said compositions. The compounds of the invention contemplate within the context of their photochromic applications that can be used in solution. Thus, 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 generally colorless and transparent. When they are exposed to sunlight, they develop a strong coloration and recover the 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. In general, a very low concentration of the product (in the order of 0.01 to 5% by weight) is sufficient to obtain an intense coloration. The compounds according to the invention are furthermore compatible with support matrices of organic polymers or inorganic material, in a form in which they are included in said matrices' and. also as in the way in which they cover such matrices. Also, within the context of a fourth aspect of the invention in relation to photochromic applications, the object of the invention is a matrix which comprises: at least one compound (I), as defined above; - and / or at least one (co) polymer and / or crosslinked, as defined above, and at least one composition as presented above. The most interesting application of the compounds of the invention are in fact those in which the photochrome is uniformly dispersed within and on a surface of a matrix formed by a polymer or (co) polymer and / or mixture of (co) polymers. Continuing with the example of its behavior in solution, the compounds (I), included in a polymer matrix are, in an initial stage, colorless or slightly colored and rapidly develop an intense coloration under UV light (365 nm) or under a source of solar type light. Finally they recover their initial coloration once the irradiation has ceased. The methods of implementation that can be considered in order to obtain such a matrix are very varied.

Among these are those known to those skilled in the art, "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 other polymer matrices, can be cited as an example.Diffusion is commonly carried out at a temperature of 50 to 200 ° C for a period of time from 15 minutes to several hours, according to the nature of the matrix Another implementation technique consists of mixing the photochrome in a formulation of polymerizable matrices, depositing the mixture on a surface or in a mold and then carrying out the polymerization.These implementation techniques and others are described in Crano's article. and collaborators "Spiroxazines and their use in photochromic lenses" published in Applied Photocrhor ic Polymer Systems, Ed. Blackie and Son Ltd -1992 The following products can be mentioned These are exemplary of preferred polymer materials for forming matrices which are useful in optical applications of photochromic compounds in accordance with. invention: Alkyl, cycloalkyl, (poly or oligo) ethylene glycol, aryl or arylalkyl poly [mono-, di-, tri- or tetra-] acrylate or poly [mono-, di-, tri-, or tetra-J-methacrylate, which are optionally halogenated or which comprise at least one ether and / or ester and / or carbonate and / or carbamate and / or thiocarbamate and / or urea and / or amide group, - polystyrene, polyether, polyester, polycarbonate (e.g. polycarbonate biphenol-A, polycarbonate diallyl diethylene glycol), polycarbamate, polyepoxy, polyurea, polyurethane, polyurethane, polysiloxane, polyacrylonitrile, polyamide, aliphatic or aromatic polyester, vinyl polymers, cellulose acetate, cellulose triacetate, polyvinyl butyral or acetate-propionate cellulose, Those obtained from difunctional monomers that have the formula below: .in which: ? Rio, R'IOÍ Rn and R 'n are identical or different and independently represent a hydrogen group or a methyl group; ? mi and ni are independently integers between 0 and 4, (inclusive); and are conveniently and independently equal to 1 or 2; ? X and X ', which are identical or different, are a halogen and preferably represent a chlorine and / or a bromine; ? Pi and qi are, independently, integers between 0 and 4 (inclusive); Copolymers of at least two types of copolymerizable monomers selected from precursor monomers from the above polymer list, and preferably those belonging to the group comprising: or (I) is carried out in accordance with the route A described higher. In a preferred embodiment, the photochromes of the invention are used with the resins which have nanobiphasic structures and which are obtained by copolymerization, at least two different difunctional specific monomers. Said resins have been described in French Patent Application FR-A-2,762,845. The amount of photochrome used in the (co) polymer matrix depends on the desired degree of darkness. Generally, between 0.001 and 20% of weight is used.

Examples Example 1: Synthesis of Compound (I) The synthesis of compound (1) was carried out according to the route A described above Step 1: In a 250 ml conical flask, the following products are placed in order: 40 ml of THF, 33.5 ml of PhMgBr (3M ether) and 3.4 g. of Cul. The mixture is cooled to -30 ° C and then a solution of 10 g is placed. of epoxynorbornane in 50 ml of THF. After 30 minutes at -30 °, the temperature is allowed to reach 2.5 ° C and after 16 hours the medium is placed inside a solution of ammonium chloride. The organic phase is recovered, washing with 150 ml of 3x of an ammonium chloride solution, and then dried over magnesium sulfate. 12.5 g are recovered. of an oil which contains the desired product.

Stage 2 : . In a 500 ml conical flask, the following products are added in order: 11.5 g.- of the product from the previous step, 200 ml of dichloromethane, 60 g. of Celite and 39 g. of pyridinium chlorochromate. After 1.5 hours at room temperature, 200 ml of diisopropyl ether is placed in the medium and the suspension is filtered. After evaporation to dryness, 12 grams of a brown liquid are recovered and purified by chromatography on silica eluting with a toluene / dichloromethane 80/20 mixture. 5.84 g are recovered. of the desired product in the form of an oil.

Stage 3: In a 250 ml conical flask equipped with a Dean-Stark trap, the following mixture is heated under reflux for 24 hours: 5.85 g of the product from the preceding stage, 3.55 g of ethyl acetate, 2, 7 g of ammonium acetate, 2.2 g of acetic acid and 100 ml of toluene. Then 10 g of acetamide are added and the toluene is distilled. After 6 hours at 200-220 ° C, the medium is placed into 300 ml of water, and the product is then extracted with a mixture of THF / ethyl acetate. The product is then purified by chromatography on silica eluting with a mixture of toluene / dichloromethane 60/40. 1.37 g of the desired intermediate product are isolated after recrystallization. The following mixture is heated at about 200-220 ° C for 6 hours in an acid digestion pump of 125 ml: 1.37 g of the product from the preceding step, 2.7 g of KOH in 15 ml of n-butanol . After cooling, the mixture is transferred to a flask and then reduced to dryness. The paste is then dissolved in 50 ml of water and then neutralized by the slow and progressive addition of concentrated hydrochloric acid. The product is extracted with 60 ml of diisopropyl ether, washed with 2 x 100 ml of water and then dried over magnesium sulfate. After evaporation to dryness, 1.3 g (98%) of a brown oil is recovered.

Step 4: The following mixture is heated under reflux in the presence of a catalytic amount of bromoacetic acid in a 100 ml reactor for 5 hours: 0.5 g of the product of the preceding step, 0.78 g of 1, 1- bis (para -methoxyphenyl) propine-1-ol in 10 ml of dichloromethane. The product is then purified by chromatography on silica eluting with toluene. The purified fractions are combined which are reduced to dryness. About 50 ml of the desired photochrome is obtained. Its structure is confirmed by NMR spectroscopy.

Example 2: Synthesis of the compounds (2) The synthesis of the compound (2) is carried out according to the route A described above: The method is analogous to that described for the compound of Example 1. It is started from the Grignard 1-bromo naphthalene reagent instead of the Grignard bromobenzene reagent. In step 4, the following mixture is heated under reflux in the presence of a catalytic amount of bromoacetic acid for 4 hours: 0.3 g of fenantrol originating from step 3-and 1.2 g of 1.1-bis (for methoxyphenyl) propin-1-ol in 15 ml of toluene. The product is then purified by chromatography on silica eluting with a toluene / heptane 80/20 mixture. The pure fractions are combined and reduced to dryness. A recrystallization in a toluene / heptane mixture at 0 ° C makes it possible to isolate around 50 ml of the desired photochrome. Its structure is confirmed by NMR spectroscopy.

Example 3: Synthesis of the compound (3) The method is analogous to that described for the preceding product. In step 4, the following mixture: 0.35 g of fenantrol originating from step 3 and 1.2 g of 1-phenyl-1- (for dimethyl inophenyl) -propin-1-ol in 15 ml of toluene they are heated under reflux in the presence of a catalytic amount of bromoacetic acid for 14 hours. The product is then purified by chromatography on silica eluting with a mixture of toluene / heptane 80/20.

The pure fractions are then combined and reduced to dryness. Recrystallization from toluene / heptane in a toluene / heptane mixture at 0 ° C makes it possible to isolate about 50 ml of the desired photochrome. Its structure is confirmed by NMR spectroscopy.

Example 4: Synthesis of the compound (4) The synthesis of the compound (4) is carried out according to the route A described above. stage : The method is analogous to that described for compound 1 starting from the Grignard 2-bromonaphthalene reagent instead of the Grignard bromobenzene reagent. In step 4, the following mixture: 0.7 g of the fenantrol originating from step 3 and 1.0 g of 1- (para-methoxyphenyl) -1- (para-dimethylaminophenyl) propin-1-ol in 15 ml of toluene, is heated under reflux in the presence of catalytic amounts of bromoacetic acid for 7 hours. The product is then purified by chromatography on silica eluting it with a 70/30 toluene / heptane mixture. The purified fractions are combined and reduced to dryness. Recrystallization from toluene / heptane in a toluene / heptane mixture at 0 ° C makes it possible to isolate around 140 mg of the desired photochrome. Its structure is confirmed by NMR spectroscopy.

Example 5: Compounds Cl, C2 and C3 Compound Ci is commercially available. Compounds Ci, C2 and C3 are described in US-A-5,783,116.

Example 6: The photochromic properties of said compounds (1), (2), (3), (4), Cl, C2, C3 were evaluated, said compounds were dissolved at a range of 5 ml in 50 ml of THF. The UV-visible absorption (optical path of 1 cm) was then measured before and after exposure to a source of 365 nm UV. The observation of the dyes and the intensity developed was done by placing the solution in the sun or before a solar simulator. The properties of these compounds are given in the following table *? L is the maximum band of the longest wavelength of the compound before exposure. **? 2 is the maximum band of the longest wavelength of the compound after exposure.

The observation of the solutions in the presence of solar or UV rays shows that the compounds of the invention have α1 and β2 which are translational towards the greatest wavelengths (batochromic change). This observation is especially evident when you compare the? maximum of the compound (1) with the analogous compounds Cl, C2 and C3.

Claims (15)

CLAIMS Having thus specially described and determined the nature of the present invention and the way it has to be put into practice, it is claimed to claim as property and exclusive right:

1. Compounds of the following formula (I) in which: - • Ri and R2 which are identical or different, represent. independently: - hydrogen,. A linear or branched alkyl group comprising from 1 to 12 carbon atoms, - a cycloalkyl group comprising from 3 to 12 carbon atoms, - an aryl or heteroaryl group, comprising in its basic structure 6 to 24 carbon atoms or 4 to 24 carbon atoms respectively and at least one heteroatom selected from sulfur, oxygen and nitrogen, said basic structure being optionally substituted with at least one substituent selected from all substituents given below: + a halogen , notably fluorine, chlorine and bromine, + a linear or branched alkyl group comprising 1 to 12 carbon atoms, + a branched or linear alkoxy group comprising 1 to 12 carbon atoms, + a haloalkyl or haloalkoxy group corresponding to the alkyl or alkoxy groups (C? C 2) above respectively which are substituted with at least one halogen atom and notably such a fluoroalkyl group, + a branched or linear alkenyl group comprising from 2 to 12 carbon atoms and notably a group vinyl or an allyl group, + a group -NH2, + a -NHR group, where R represents a branched or linear 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 branched or linear alkyl group comprising from 1 to 6 carbon atoms or represented together with the nitrogen atom to which they are attached to a ring of 5 to 7 members which may comprise at least any one of a heteroatom selected from oxygen, sulfur and nitrogen, said nitrogen being optionally substituted with a group R '' ', which is a branched or linear alkyl group comprising from 1 to 6 carbon atoms. + a methacryloyl group, or an acryloyl group, an aralkyl or heteroaralkyl group, the alkyl group, which is branched or linear, comprising from 1 to 4 carbon atoms and the aryl part which has the same definition given above for the aryl and heteroaryl group; or said two substituents Rx and R2 together form an adamantyl, norbonyl, fluorenylidene, di (Ci-C6) alkylatratracenylidene or a spiro group (C5-C6) alkylaryltracenylidene cycle; said group being optionally substituted with at least one of the substituents listed above for Rx, R2: an aryl (or heteroaryl) group; R3, which are identical or different and independently represent: a halogen, and notably fluorine, chlorine or bromine, a linear or branched alkyl group comprising 1 to 12 carbon atoms (more 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 (more advantageously from 1 to 6 carbon atoms), a haloalkyl, halocycloalkyl, or haloalkoxy group corresponding to the alkyl, cycloalkyl and alkoxy groups above respectively, which are substituted with at least one halogen atom, particularly selected from the group of fluorine, chlorine and bromine, an aryl or heteroaryl group having the same definition as that given above up Ri and R2, an aralkyl or heteroaralkyl group, the alkyl group, which is linear or branched, comprising one to 4 carbon atoms, and the aryl or heteroaryl groups that have the same definition given above for Ri, R2. an amine or amide group: -NH2, NHR, -CONH2, -CONHR, R 'R' -N or CON R "R" R, R ', R ", which have their respective definitions given above for the amine substituents of the Ri, R2: aryl or heteroaryl, a -OCOR6 or -COOR6, Re represents a branched or straight alkyl group comprising from 1 to 6 carbon atoms, or a cycloalkyl group comprising from 3 to 6 carbon atoms, or a phenyl group, optionally substituted with at least one of the substituents listed above for the values of Ri, R2: aryl or heteroaryl; or at least two of the groups R3, which are adjacent, forming an aromatic ring of 5 to 6 members or a non-aromatic ring which may comprise at least one heteroatom selected from the group consisting of: oxygen, sulfur or nitrogen and / or at least one substituent selected from a CL-C6 alkyl group which is linear or branched, a Ci-Cβ alkoxy group which is linear or branched, and an amine group of the formula -NH2, -NHR or R * -NR "- defined above as substituents, of the basic structure of the aryl or heteroaryl group which represents Ri or R2; m is an integer from 0 to 4; R 4 which is identical or different independently represented: a halogen preferably selected from the group consisting of fluorine, chlorine and bromine, an alkyl group, or a C 1 -C 6 alkyl group which is linear or branched; n is an integer from 0 to 4.

2. The compounds according to claim 1, characterized in that they have a formula (I) in which: Ri, R2 are identical or different and independently represent and optionally substituted aryl or heteroaryl groups of basic structure which is selected from the group comprising phenyl, naphthyl, biphenyl, pyridyl, furyl, benzofuryl, and dibenzofuryl, N- (C? -C6) alkylcarbazole, thienyl, benzothienyl, dibenzothienyl, and julolidinyl groups; Rx and / or R2 advantageously representing a para-substituted phenyl group; or Ri and R-2 together form an adamantyl or norbornyl group.

3. The compounds according to one of claims 1 or 2, characterized in that they are such that at least two of their substituents, adjacent R3 do not jointly form a ring.

4. The compounds according to claims 1 or 2, characterized in that they comprise at least two adjacent R3 groups which together form aromatic or non-aromatic groups of 5 to 6 members which may comprise at least one heteroatom selected from the group comprising: oxygen, sulfur or nitrogen and / or at least one substituent selected from a C?-C6 alkyl group which is linear or branched, a Ci-Cg alkoxy group, which is linear or branched and an amine group of the formula -NH2, -NHR or R '• N R- as defined in claim 1, as substituents, of the basic structure of the aryl or heteroaryl group which represent Ri or R2.

5. The compounds according to claim, of formula (1.1) or (1.2) in which: • R5 represents a C6-C6 alkyl group which is linear or branched, a C6-C6 alkoxy group which is linear or branched, or an amide group of the formula NH2, NHR or R '-NR "- as defined in claim 1, as a substituent of the basic structure of the aryl or heteroaryl group, which represents Ri, R2, • myo are integers from 0 to 2 and from 0 to 4 respectively, - Ri and R2 and R4 and n are as defined in claim 1 and, - R31 and • R32 which independently represent a group having the same definition as the same definition given above for R3 in the generic formula (I) of Claim 1

6. The compound according to any of claims 1 to 5, characterized in that n = 0 in the formulas (I), (1.1) or (1.2).

7. A method for preparing the compounds according to any of claims 1 to 6, characterized in that it consists essentially of a condensation being carried out: - of an intermediate product of formula (1.1), (1.2) or (1.3) given below: (11.1) (H.2) (I1.3) in which R3, R3 ?, R3, R, R5, m, n, I are as defined in claim 1 to 5 above with reference to the formulas (I), (1.1), (1.2); - with a propargyl alcohol derivative having the formula (III) below: wherein Rx and R2 are as defined above with reference to formula (I); the condensation (11) / (III) being advantageously carried out in the presence of a catalyst, this catalyst preferably being selected from the group comprising para-toluenesulfonic acid, dodecyl sulfonic acid or bromoacetic acid; with an aldehyde derivative, having the formula (III ') below: wherein Ri and R2 are as defined above with reference to the formula, (I): condensation (11) / (III ') being advantageously carried out in the presence of a metal complex, preferably a complex of titanium, with titanium (IV) ethoxide being particularly preferred.

8. Intermediary products, notably useful for preparing the compounds according to any of claims 1 to 6, characterized in that they have the following formulas (II.1), (II.2), (II.3): in which R3, R31, R32, R4, R5, n, m and o are as defined above in claims 1 to 5 with reference to formulas (I), (1.1) and (1.2).

9. A (co) polymer and / or a crosslinking obtained by the polymerization and / or crosslinking and / or by grafting at least one monomer consisting of a compound according to any of claims 1 to 6.

10. A photochromic compound characterized in that it is constituted by a compound according to any of claims 1 to 6 or by the mixture of at least two compounds according to any of claims 1 to 6 or by the mixture of at least one compound according to any of claims 1 to 6, with at least one other photochromic compound of another type and / or at least one non-photochromic coloring agent.

11. A photochromic composition, characterized in that it comprises: - at least one compound according to any of claims 1 to 6, - and / or at least one linear (co) polymer or lattice which contains, in its structure, at least minus one compound (I) according to any one of claims 1 to 6, - and optionally at least one of the other photochromic compounds of another type and / or at least one non-photochromic coloring agent and / or at least one stabilizing agent.

12. A matrix of (co) polymer, characterized in that it comprises: - at least one compound (I) according to any of claims 1 to 6, - and / or at least one composition according to claim 11, - and / or at least one (co) polymer and / or crosslinked according to claim 9.

13. The matrix according to claim 11, characterized in that the (co) polymer / s which constitutes it is selected from the following list: - Alkyl, cycloalkyl (poly or oligo) ethylene glycol, aryl or arylalkyl , poly [mono-, di-, tri- or tetra-] acrylate or poly [mono-, di-, tri-, or tetra-] methacrylate, which is optionally halogenated or which comprises at least one ether and / or ester and / or carbonate and / or carbamate and / or thiocarbamate and / or urea and / or amide group, - polystyrene, polyether, polyester, polycarbonate (for example polycarbonate biphenol-A, polycarbonate diallyl diethylene glycol), polycarbamate, polyepoxy, polyurea, polyurethane, polythiourethane, polysiloxane, polyacrylonitrile, polyamide, aliphatic or aromatic polyester, vinyl polymers, acetate, cellulose, cellulose triacetate, polyvinyl butyral or cellulose acetate propionate, - Those obtained from difunctional monomers having the formula below : in which: ? Rio, R'ior Rn and R 'ii are identical or different and independently represent a hydrogen group and a methyl group; ? mi and ni are independently integers between 0 and 4, (inclusive); and are conveniently and independently equal to 1 or 2; ? X and X ', which are identical or different, are a halogen and preferably represent a chlorine and / or a bromine; ? Pi and qi are, independently, integers between 0 and 4 (inclusive); - copolymers of at least two types of copolymerizable monomers selected from precursor monomers from the list of polymers above, and preferably those belonging to the group comprising: (meta) acrylic monomers, vinyl monomers, allylic monomers, and mixtures of the same.

14. An ophthalmic or solar article comprising: - at least one compound (I) according to any of claims 1 to 6, - and / or at least one composition according to claim 11, - and / or minus one (co) polymer and / or crosslinked according to claim 9, - and / or at least one matrix according to any of claims 12 or 13.,

15. The article according to claim 14, characterized in that it is constituted for lenses, for glassware or for optical devices.