MXPA98001904A - Photocromatic espiroxazinas with asymmetric monociclico substitute, compositions and articles chelas contie - Google Patents

Abstract

The invention relates to photochromic compounds having the formula (I), wherein R 1 is an asymmetric aliphatic monocyclic group with the formula (II), wherein 1 = 1-12, R 9 is H or an alkyl, alkoxy, dialkylamino group , alkyl ester or CN, with the proviso that at least one of the groups R9 is not H, R2-R7 can have a variety of meanings, A represents a heteroaromatic ring that can be substituted and n is a whole number; production of photochromic articles made of organic polymer, notably lent

Description

PHOTOCROMIC ESPIROXAZINAS WITH ASYMMETRIC MONOCICLIC SUBSTITUTE. COMPOSITIONS AND ARTICLES THAT CONTAIN THEM DESCRIPTIVE MEMORY The present invention relates to novel compounds of the spiroxazine type which has, in particular, photochromic properties. It also relates to photochromic compositions and ophthalmic articles (eg, lenses) containing spiroxazines. Photochromic compounds have the ability to change color due to the influence of a poly- or monochromatic light (eg, UV) and are able to recover their initial color when radiation or light is stopped, or due to the influence of a poly- or monochromatic light that is different from the first light, or due to the influence of temperature and / or of a poly or monochromatic light that is different from the first. These photochromic compounds are applied in various fields, for example, for the manufacture of ophthalmic lenses, contact lenses, some shades for the sun, filters, optics for cameras such as photographic or other optical or observation devices, glass partitions, objects decorative, exhibition elements or training storage by optical registration (coding).

In the field of ophthalmic optics, and in particular in the spectacle field, a photochromic lens, comprising one or more photochromic compounds, must have: - a high transmission in the dark or in the absence of sunlight, a low transmission ( high color capacity) when exposed to sunlight irradiation, an appropriate kinetics of coloring and discoloration, - a dye that is acceptable to the consumer (preferably gray or brown), preferably with maintenance of the selected dye during the course of the coloration and the discoloration of the lens, a maintenance of the performances of the characteristics in a scale of temperature of 0 to 0 ° C, - a high durability, because the intended objectives are sophisticated corrective lenses and therefore expensive. These lens characteristics are in fact determined by the active photochromic compounds which, moreover, must be perfectly compatible with the organic or mineral support constituting the lens. In addition, it should be noted that obtaining a gray or brown-brown dye may require the use of at least two photochromes of different colors, that is, having different wavelengths of maximum absorption on the visible scale (wavelength). maximum). In this way, the association imposes other requirements more on the photochromic compounds. In particular, the kinetics of coloration and discoloration of the two or more associated active photochromic compounds must be essentially identical. The same applies to its stability over time and also to its compatibility with a plastic or mineral support. Among the numerous photochromic compounds described in the prior art, mention may be made of the indolino-spiro-naphthoxazines described in the U.S. Patents. Nos. 3,578,602; 3,562,172; 4,215,010; European Patent Nos. 0,171,909; 0,313,941; French Patent No. 2,647,789; and European Patent No. 0,600,669: The Ri group of these molecules represents straight or branched alkyl, alkylaryl or alicyclic. It is considered that these compounds meet the previously defined specifications. In fact, although these compounds do have one or more of the basic properties that are sought, such as high transmission in the dark, a high color capacity when exposed to solar radiation, absorption in blue or violet [spectrum] (570) -630 nm), rapid kinetics of coloration and desloration, all the compounds described to date do not have the complete combination of the desired properties required for the production of satisfactory articles that can be industrially manufactured. Although the prior art teaches how to modify the absorption band by adding substituents to the different positions of the rings and also teaches how to modify the kinetics of discoloration, on the contrary, it does not teach how to increase the color capacity of these molecules without increasing the residual coloration in the inactivated state and, above all, how to make them photochemically stable to allow their use on an industrial scale. In fact, without high stability, you can not use those expensive molecules, introduced into a sophisticated lens. A merit of the applicant is to have unexpectedly found that the presence of an asymmetric monocyclic substituent group on the nitrogen atom of the indoline or portion of certain indolinoespiroxazines allows the solution of the problem of residual coloration and color capacity, which is essential for the indicated applications. The originality of the invention lies in the surprising effect of the asymmetric monocyclic group, which increases the color capacity of the spiroxazines without increasing their residual coloration, while ensuring a good pH value. Therefore, the present invention relates to a compound, in particular to a -otochromic compound, having the following general formula (I): wherein - R1 is an asymmetric aliphatic monocyclic group that is directly connected to the nitrogen atom, having 5 to 7 members, and possibly comprising at least one heterogeneous atom having the formula & (R ») l wherein 1 = 1-12, R9 represents H or an alkyl, alkoxy, dialkylamino, alkyl or CN alkyl group, provided that at least one of R9 is not H. - R2, R3 are identical or different and represent an alkyl group, straight or branched chain, from 1 to 12 carbon atoms, an alkenyl group, alkynyl, aryl, alkylaryl, cycloalkyl, R2 and R3 optionally To combine to form a heterocyclic or heterocyclic group having 5 to 10 atoms, R 4, R 5, R 6 and R 7 are identical or different and represent: g hydrogen, | an alkyl, cycloalkyl, alkenyl, alkynyl, aryl (preferably phenyl, mono-, di- or trisubstituted naphthyl by donor or electron acceptor groups), heteroaryl, aryloxy or aralkyl, said group being optionally halogenated, | a halogen, preferably F, Br, Cl, | OR, SR, -0C0R, -C00R, with R = H, alkyl and / or cycloalkyl and / or aryl, g a (poly) ether, (poly) amide, a (poly) carbonate, a (poly) carbamate, a (poly) urea or a (poly) ester. | * an amino radical that gives rise, once it is bound in (I), to a primary, secondary or tertiary amine, said amine being alkyl, aryl or aralkyl, mono- or disubstituted, depending on its nature, * or a radical aminoalkyl optionally containing one or more heterogeneous atoms, or an electron acceptor group preferably selected from the group comprising CF3, CN, NO2, SCN, - wherein at least two of the radicals R *, R5, R6, R? , preferably carried by the adjacent carbon atoms, can be combined to form at least one aromatic ring having 5 or 6 members or an aliphatic ring having 5 to 7 members, preferably 5 to 6 members, said ring (s) optionally comprising at least one heterogeneous atom to form at least one heterocyclic ring, the latter being optionally substituted by one or more radicals which may be identical or different, and having the same definition as given above for R * to R7, - A represents a heteroaromatic ring (containing, for example, at least one nitrogen atom) and possibly replaced by one or more radicals R8, which may be identical or different, and which have the same definition as given above for R * to R7, - n is an integer and when n > 2, two of the R8 radicals may possibly be combined to form at least one aromatic or heteroaromatic ring. The term "asymmetric" in the expression "asymmetric aliphatic monocyclic group" means that the plane that is perpendicular to ring B of group R1 and that includes the segment of a straight line representing the bond between ring B and the nitrogen atom is not it is a plane of symmetry for the group R1, it being understood that the -ping is based on the formula developed on a plane of the g-upo R1. Specific examples of groups 1 are the following: among many others . Preferred compounds of the invention have the following formula (I '): wherein A, and R1 and R7 are as defined above, and D is an aromatic or aliphatic ring having from 5 to 7 members, optionally comprising a heterogeneous atom which may or may not be substituted by one or more radicals which may be identical or different, and has the same definition as was given for 4 to R7. In accordance with a particularly preferred embodiment of the invention, ring A is a phenyl ring and R * and R5 combine to form a ring to a romat. This corresponds to the following formula (I "): wherein R1 to R4 and R6 to R8 are as defined above, and n and assume the values 0 to 4. Among the substituents that can be considered for the compounds with the formulas (I), (I ') and (I ") according to the invention, the groups R * to R9 must be considered, which comprise and / or form at least one reactive function for polymerization and / or entanglement, preferably selected from the Following list: preferably alkenyl vinyl-methacryloyl, acryloyl, acryloxy-alkyl, ethacryloxyalkyl or epoxy In this way, the photochromic compounds according to the invention can be designed as monomers, of different types or not, which can react between themselves or with other comonomers, to form homopolymers and / or copolymers carrying a photochromic functionality and having the mechanical properties of macromolecules It is clear that one of the objects of the present invention consists of these homopolymers or copolymers composed of the comonomers and / or of interlacing, at least in part constituted by photochromic compounds (I), (! ') and (I ") according to the invention. In the same order of ideas, the compounds (I), (! ') And (I ") mentioned above can be considered as interlacing agents having reactive functions capable of allowing the formation of bridges between the polymer chains that can be or non-photochromic type The interlaced compounds obtainable in this way also constitute another object of the present invention In a general manner, in the above formulas, the following designations according to the invention are used: - "alkyl" , which preferably refers to a straight or branched chain hydrocarbon group having from 1 to 12 carbon atoms; - "alkoxy", which refers to a group of the O-alkyl type preferably having from 1 to 10 carbon atoms, - "aryl", which refers to an aromatic hydrocarbon group containing at least 6 carbon atoms , "heteroaryl", which refers to an aromatic hydrocarbon group comprising at least 5 atoms, of which at least one is a heterogeneous atom, - "aralkyl", a group comprising at least one alkyl and therefore minus one aryl, as defined above, - "heterogeneous atom", an atom other than C and H, which preferably belongs to the following group: N, 0 and S. The photochromic compounds which are particularly preferably used in the context of the invention, as can be concluded from the foregoing, are therefore indolinospironaf toxazines or indolinoespi robenzoxazines. The most advantageous indolinoespi roxazines include those that have the formula: where R1 n = 0.1 or 2 and R2, R3 = Ci-Cs alkyl, R * = H, OMe, R6 = H, OMe or amino. Rß = H, Me, OMe or CF3.

A merit of the applicant is to have described these compounds, since they present particularly advantageous photochromic properties. Very specifically, they have a high color capacity, particularly in the blue region of the spectrum. In this way, they are well adapted to combine - observing the compatibility and complementarity requirements - with photochromes that absorb in the yellow, orange, red and violet of the show, to obtain a wide coverage of the visible absorbance spectrum and in this way Coloring dyes that are brown or dark gray in color. The sensitivity, as well as the height and the area of its maximum wavelength reaches a peak in the visible region, achieving satisfactory values. These compounds are also perfectly stable and compatible with support matrices made of organic polymer or mineral material, in a form included in the matrix and in the form of a coating. In solution or in a polymeric matrix, the compounds according to the invention are colorless or slightly colored in the initial state and rapidly develop an intense coloration under UV light (365 nm) or a light source of the solar type. Finally, they quickly recover their initial color when irradiation is stopped. The compounds of the invention can be obtained by condensation of an indolira derivative substituted with an asymmetric aliphatic monocyclic group Ri and an aromatic nitroso alcohol derivative such as those described, for example, in the U.S. Patents. us. 3,578,602; 4,634,767; 4,913,544 and European Patent No. 600,669. This reaction can take place in solvents such as ethanol, toluene or dichloroethane.

The indoline derivatives are obtained by methods that are adapted from the literature: (3) UA! H4 Step 1 is carried out for a process described in Katritzky et al., Tetrahedron, 1991, Vol. 47, 2683. The nitrosation of the amine (step 2) is carried out by reaction with sodium nitrite-hydrochloric acid and the reduction of the nitrous derivative (step 3) is carried out by the reaction of LiAIH; in THF (Fridman et al., Russian Chemical Reviews, 1971, 40 (1), 34. The last step of synthesis (4) is carried out by reacting hydrazine with the appropriate ketone in an acidic medium, for example, hydrochloric acid. / ethanol or acetic acid (for a general review of this reaction see Robinson, "Fischer Nature synthesis," Wiley-Interscience, 1982.) In the case of applications of compounds in accordance with the present invention, it should be noted that they can be used as a photochromic material that is dispersed in the surface part or in the composition of a polymeric or mineral matrix, and can also be used in solution.A photochromic solution can be obtained by dissolving the compound in an organic solvent such as toluene, dichloromethane, Tetrahydrofuran or ethanol The solutions obtained are generally colorless and transparent.When exposed to sunlight, they develop a strong coloration and their colorless state returns when They place in an area with exposure to sunlight or, in other words, when they are no longer exposed to UV radiation. In general it is sufficient to use a very small concentration of product (of the order of 0.01-5%) to obtain an intense coloration.

The most intense applications are those in which the photochrome is dispersed uniformly within the surface of a polymer, copolymer or mixture of polymers or on it. A great variety of implementation methods can be considered. Those known to those skilled in the art include, for example, diffusion in the copolymer, from a suspension or solution of the -otocrome, in a silicone oil, in an aliphatic or aromatic hydrocarbon, in a glycol, or from another poly-rich matrix. The diffusion is carried out routinely at a temperature of 50-200 ° C for a duration of 15 minutes to several hours, depending on the nature of the polymer matrix. Another implementation technique consists of mixing the photochrome in a formulation of polymerizable substances, in the deposition of this mixture on a surface or in a mold and then in the conduction of the polymerization. These implementation techniques and others are described in the article by Crano et al, "Spi roxazines and their use in photocrhromic lenses" published by Photochromic Polymer Systems, Published by Blackie and Son Ltd., 1992. In accordance with a variant of the invention , it is also possible to consider the grafting of the photochromes on the copolymers. In this way, another object of the invention consists of copolymers to which at least one of the photochromes described above has been grafted. Examples of preferred polymeric materials for the optical applications of the photochromic comps according to the invention include the following products: (mono, di, tri or tetra) polyacrylate or alkyl, cycloalkyl, aryl or arylalkyl polymethacrylate, optionally halogenated or comprising at least one ether and / or ester and / or carbonate and / or carbamate and / or thiocarbamate / or urea and / or amide, polystyrene, polycarbonate (eg, bisenol-A polycarbonate, allyleethylene glycol polycarbonate), polyepoxy, polyurethane , polythiourethane, polysiloxane, polyacrylonitrile, polyamide, aliphatic or aromatic polyester, vinyl polymers, cellulose acetate, cellulose triacetate, cellulose acetate propionate or polyvinyl butyral, copolymers of two or more types of monomers or polymer blends mentioned above, preferably polycarbonate-polyurethane, polymethacrylate-polyurethane, polystyrene-polymethacrylate or polystyrene-polyacrylate trilo, advantageously a mixture of polyester and polycarbonate or polymethacrylate. The amount of photochrome used depends on the desired degree of darkening. Generally, an amount of 0.001-20% by weight is used. The photochromic compounds according to the invention can be used alone or in admixture with other products to form a composition which can be in solid or liquid form, for example, in a solution or in a dispersion, as already indicated above. These compositions, which constitute another object of the invention, can thus comprise the compounds (I), (I ') and (I ") of the invention and other complementary photochromic compounds that allow obtaining dark colorations, for example, gray or coffee, which are desired by the public in applications such as ophthalmic goggles or for protection from sun rays.These complementary photochromic compounds have a maximum wavelength and an absorbance spectrum in the visible region such that, after association with The compounds of the invention impart the desired dye to the mixture of activated photochromes.The photochrome (or photochromes), which can be associated with the compounds of the invention is that known to a person skilled in the art and described in the literature. , for example, cromenos (U.S. Patent Nos. 3,567,605; 5,238,981; World Patent No. 9,422,850; European Patent No. 0,562,915), spiro pyrapids or naprospiropans [sic]; (U.S. Patent No. 5,238,981) and Spiroxazines (J. C. Crano et al. "Applied Photochromic Polymer Systems," Publisher, Blackie &Son Ltd., 1992, Chapter 2). The compositions according to the invention may also comprise: non-photochromic dyes that allow an adjustment of the dye, and / or one or more stabilizers, such as, for example, an antioxidant, and / or one or more anti-UV agents, and / or one or more anti-radical compounds, and / or one or more deactivators of photochemically excited states. These additives may allow an improvement in the durability of said compositions. In accordance with another of its aspects in relation to the application of the photochromic compounds (I), (I ') and (I "), the present invention also refers to ophthalmic articles, such as eyeglasses or articles for protection of lightning solar cells, comprising at least one compound according to the invention and / or at least one (co) polymer formed, at least in part from recurring units of type (I), (I ') or (I ") and / or at least one composition comprising the compounds (I), (I ') or (I ") according to the invention, as defined above, and / or at least one matrix, as defined above, made of an organic polymer material or a mineral material or a mineral-organic hybrid material incorporating at least one compound of the invention In practice, the articles to which the present invention is very particularly concerned are ophthalmic photochromic lenses or lenses for protection from the sun's rays, window as (windows for buildings, for locomotives, automobiles), optical devices, decorative items, articles for protection against the sun, data storage, etc. The present invention will be better understood in the light of the following examples of photocromic synthesis and the validation of the compounds (I), (I ') and (I "), to which it refers.

EXAMPLES Synthesis and properties of photochromic compounds (I) - (4) according to the invention (Examples 1-4) The formulas of the compounds (1) - (4) are given below (see Table 1).

EXAMPLE 1 Synthesis of compound 1 Step 1 Synthesis of 2-methylcyclohexylphenylamine In a 100 ml flask, the following mixture is refluxed for 30 hr: 9.3 g aniline, 11.2 g 2-methylcyclohexanone and 12 g benzotriazole. Then, 200 ml of methanol and 5 g of NaBH * in portions are added to the mixture, which is then heated to reflux for 30 minutes. The solution is allowed to cool and 100 ml of water are added to the mixture, which is extracted with 2 x 100 ml of diisopropyl ether. The organic phase is recovered, and dried over magnesium sulfate and reduced to dryness. In this way, 7 g of the desired amine is produced.

Step 2 Synthesis of l- (2-methylcyclohexyl) -l-phenylhydrazine The amine from the previous step (7 g) is suspended in 100 ml of hydrochloric acid (IN), and after the mixture is kept at 0 ° C with stirring. Then add to the aqueous solution of NaN02 (2 g in 20 ml of water) to the mixture in small portions. The temperature is then allowed to rise to room temperature, and the nitrous derivative is extracted with 2 x 100 ml of diisopropyl ether. After evaporation of the solvent, 8 g of product are recovered. This product after adding slowly and in small portions to tetrahydrofuran (80 ml) containing 7 g of LiAlH * and then the mixture is heated for 1 hour. Subsequently, the mixture is cooled to 0 ° C, and then the excess hydride is neutralized with an aqueous solution of sodium hydroxide. Then, 30 g of Na 2 SO 0 are added, and the organic phase is recovered by filtration and reduced to dryness. In this way, 7 g of the desired hydrazine are produced.

Step 3 Synthesis of the 2-methylene derivative In a 100 ml mat, react with 7 g of hydrofluorine of the step before r and r 3 g of 3-methyl-2-butanone in 30 ml of ethanol containing 1 ml of acetic acid at 50 ° C. Then 5 ml of concentrated hydrochloric acid are added and the mixture is heated to reflux for 10 minutes. The medium is then neutralized with sodium hydroxide and the indcl derivative is extracted with 100 ml of diisopropyl ether. After evaporation of the solvent, 3 g of the desired product are prepared.

Step 4 Synthesis of spiroxazine (1) The product of the anteric step (3 g) and 1.8 g of 1-nitroso-2-naphthol are dissolved in 30 n of absolute ethanol and then the mixture is heated to 70 ° C for 30 minutes . The solvent is then evaporated under vacuum and the product is isolated by chromatography on a silica column with toluene as eluent. The product obtained (1 g) is then crystallized from heptane. 450 mg of the slightly green product are isolated. Its structure is confirmed by NMR spectroscopy.

EXAMPLE 2 Synthesis of the compound (2) Step 1: In a 100 ml flask, the following mixture is heated at 12 ° C for 24 hr: 12 g of 3,4-dimethylaniline, 11 g of 2-methylcyclohexanone and 12 g of benzotriazole. The 2-methylcyclohexyl-2,4-dimethylphenylamine is isolated after reduction, as in step 1 of example 1. 18 g of an oily product is isolated.

Steps 2. 3 and 4: These steps are conducive as before. Spiroxazine (2) is synthesized from 3.5 g of the indoline derivative and 2.2 g of 1-ni throso-2-na tol in ethanol at 60 ° C for 2 hours. 1.5 g of product are isolated after chromatography. Its structure is confirmed by NMR spectroscopy. The latter shows the existence of several isomers, due to the position of the two methyls on the phenyl of indole (4,5-dimethyl and 5,6-dimethyl derivative) and due to the position of the nitrogen on the ring (cis and trans with respect to the 2-methyl group).

EXAMPLE 3 Synthesis of the compound (3) Step 1: In a 250 ml flask equipped with a Dean-Stark separator, the following mixture is heated to reflux: 12 g of 3,4-dimethylaniline, 20 g of menthone, 14 g of benzotriazole and 200 ml of toluene. After recovery of the theoretical amount of water (16 hr), the mixture is reduced to dryness and then dissolved in 200 ml of methanol, and the product is reduced with NaBH *, as before. 25 g of oily product are isolated.

Steps 2, 3 and 4: These steps were conducted as before, spiroxazine (3) was synthesized from 5 g of the indoline derivative and 3.5 g of l-nitroso-2-naphthol in 60 ml of ethanol at 50 ° C for 1 hr. 2 g of product were isolated after chromatography. Its structure is confirmed by NMR spectroscopy.

EXAMPLE 4 Synthesis of the compound (4) Spiroxazine (4) is synthesized from 6 g of the indoline derivative of Example 3 and 4 g of l-nitroso-2-naphthol in ethanol at 60 ° C for 1 hr. The intermediate product obtained is then methylated with dimethyl sulfate in acetone in the presence of potassium carbonate. 2.2 g of product are isolated after chromatography. Its structure is confirmed by NMR spectroscopy.

APPLICATIONS EXAMPLE 5 Incorporation of compounds (1) to (4) in a polyacrylate General procedure: 10 mg of each of the compounds (1) to (4) are dissolved in dimethacrylate of tetraethoxylated bisphenol A, marketed under the name DIACRYL 121 by the company AKZO) and containing 40 mg of 2 ', 2'- azobis (2-methylbutyronitrile). The solution is then degassed, becomes inert with argon, and is emptied into a glass lens mold having a diameter of 8 cm and a thickness of 2 ml. The mold is then placed in an oven at 70 ° C for 12 hours. After removing the moles, a clear and rigid lens is obtained. When exposed to solar radiation, the glass rapidly develops an intense blue color and becomes colorless again in the dark. The photochromic characteristics are given in Table 1 below. For comparison purposes, the characteristics of the compounds Cl, C2, C3, C4 and C5 of the prior art are also given in Table 1 below.

TABLE 1 \ max measured at D121 in a thickness of 2 mm with exposure to a xenon lamp, 60.00C Ix, at 22 ° C, - TO = initial transmission (inactivated state) measured at a maximum wavelength, - TD15 = transmission after 15 minutes of exposure measured at maximum wavelength, - IOD = induced optical density. { log (T0 / TD15)} , - R5 = percent of recovery of the initial transmission after 5 minutes of discoloration, [In the inserted picture of the original, the commas are replacing the decimal points]. A comparison of the properties of Examples 1 and Comparative Examples Ci and C, on the one hand, and Examples 2 and 3 and Comparative Examples C3 and Ce, on the other hand, show that the prior art compounds with structure similar but without an asymmetric aliphatic monocyclic group according to the invention, do not possess the advantageous combination of the properties sought. In particular, it can be seen that the compounds of the invention have a better compromise between the low initial coloration and the strong induced optical density.

Claims (14)

NOVELTY OF THE INVENTION REÍ INDICACIÓNJES

1. - Photochromic compounds having the following general formula (I): wherein R1 is an asymmetric aliphatic monocyclic group that is directly connected to the nitrogen atom, having 5 to 7 members, and possibly comprising at least one heterogeneous atom having the formula wherein 1 = 1-12, R9 represents H or an alkyl, alkoxy, dialkylamino, alkyl ester or CN group, provided that at least one of R9 is not H; R2, R3 are identical or different and represent an alkyl group, straight or branched chain, of 1 to 12 carbon atoms, an alkenyl, alkynyl, aryl, alkylaryl, cycloalkyl group, R2 and R3 can optionally be combined to form a group carbocyclic or heterocyclic having 5 to 10 atoms, R *, R5, R6 and R7 are identical or different and represent: hydrogen; an alkyl, cycloalkyl, alkenyl, alkynyl, aryl (preferably phenyl, mono-, di- or trisubstituted naphthyl by electron donating or accepting groups), heteroaryl, aryloxy or aralkyl, said group being optionally halogenated; a halogen, preferably F, Br, Cl; OR, SR, -0C0R, -C00R, with R = H, alkyl and / or cycloalkyl and / or aryl; a (poly) ether, (poly) amide, a (poly) carbonate, a (poly) carbamate, a (poly) urea or a (poly) ester; * an amino radical that gives rise, once it is bound in (I), to a primary, secondary or tertiary amine, said amine being alkyl, aryl or aralkyl, mono- or disubstituted, depending on its nature; * or an aminoalkyl radical optionally containing one or more heterogeneous atoms; or an electron acceptor group selected preferably from the group comprising CF3, CN, NO2, SCN; wherein at least two of the radicals R *, R5, R6, R7, preferably carried by two adjacent carbon atoms, can be combined to form at least one aromatic ring having 5 or 6 members or an aliphatic ring having 5 to 7 members, preferably 5 to 6 members, said ring (s) optionally comprising at least one heterogeneous atom to form at least one heterocyclic ring, the latter being optionally substituted by one or more radicals which may be identical or different, and that has the same definition as given above for R * to R7; A represents a heteroaromatic ring (containing, for example, at least one nitrogen atom) and possibly replaced by one or more radicals R8, which may be identical or different, and which have the same definition as given above for R * to R7; n is an integer and when n > 2, two of the R8 radicals may possibly be combined to form at least one aromatic or heteroaromatic ring.

2. Compounds according to claim 1, further characterized in that the group R1 is selected from the following:

3. - Compounds according to claim 1 or 2, further characterized by having the general formula wherein A, and R1 and R7 are as defined above, and D is an aromatic or aliphatic ring having from 5 to 7 members, optionally comprising a heterogeneous atom which may or may not be substituted by one or more radicals which may be identical or different, and has the same definition that was given for R * to R7.

4. Compounds according to any of claims 1 to 3, further characterized in that they have the general formula: wherein R1 to RA and R6 to R8 are as defined above, and y assume the values 0 to 4.

5. Compounds according to any of claims 1 to 4, further characterized in that the Ri-R9 groups of the formulas ( I), (I ') and (I ") according to the invention, comprise and / or form at least one reactive group of polymerization and / or entanglement selected from the following: alkenyl, methacryloyl, acryloyl, acryloxy-alkyl, methacryloxyalkyl and epoxy

6. Compounds according to any of claims 1 to 5, further characterized because they represent the following formula: where R1 = n = 0.1 or 2 and R2, R3 = Ci-Cs alkyl, R * = H, OMe, R «= H, OMe or amino, R8 = H, Me, OMe or CF3. 7.- (Co) polymer and / or interlacing obtained by the polymerization and / or interlacing of at least one monomer consisting of at least one photochromic compound according to claim 5. 8.- (Co) polymer, characterized also because it is grafted by means of at least one of the photochromic compounds according to any of claims 1 to 6. 9. Photochromic composition, characterized in that it comprises: at least one compound according to any of claims 1 to 6 and / or at least one (co) polymer according to claim 7 or 8, and optionally at least one -otochromic compound and / or at least one dye and / or at least one stabilizer. 10. Matrix of (co) polymer, characterized in that it comprises: at least one compound according to any of claims 1 to 6 and / or at least one (co) polymer according to claim 7 or 8, and / or at least one composition according to claim 9. 11.- A matrix according to claim 10, further characterized in that the (co) polymer is selected from the following list: (mono, di, tri or tetra) polyacrylate or polymethacrylate of alkyl, cycloalkyl, aryl or arylalkyl optionally halogenated or comprising at least one ether and / or ester and / or carbonate and / or thiocarbamate and / or urea and / or amide group; polystyrene, polycarbonate, polyepoxy, polyurethane, polythiourethane, polysiloxane, polyacrylonitrile, polyamide, aliphatic or aromatic polyester, polyvinyl acetate, cellulose acetate, cellulose triacetate, cellulose acetate propionate or polyvinyl butyral; L copolymer of two or more types of monomer of monomer mixtures indicated above. 12. Ophthalmic or sun protection device comprising: at least one compound according to any of claims 1 to 6 and / or at least one (co) polymer according to claim 7 or 8, and / or at least one composition according to claim 9. 13. An article according to claim 12, further characterized in that it consists of a lens. 14. Divisions of glass and / or optical device comprising: at least one compound according to any of claims 1 to 6 and / or at least one (co) polymer according to claim 7 or 8, and / or at least one composition according to claim 9, and / or at least one matrix according to claim 10 or 11.