EP0915886A1

EP0915886A1 - Novel homoazaadamantane spirooxazines and use thereof in ophthalmic optics

Info

Publication number: EP0915886A1
Application number: EP97931863A
Authority: EP
Inventors: Karine Chamontin; Vladimir Lokshin; André Samat; Robert Guglielmetti
Original assignee: Transitions Optical Inc
Current assignee: Transitions Optical Inc
Priority date: 1996-07-31
Filing date: 1997-07-03
Publication date: 1999-05-19
Also published as: AU3546697A; JP2000515876A; US6136968A; FR2751971B1; AU719894B2; FR2751971A1; BR9710557A; WO1998004563A1

Abstract

Novel homoazaadamantane spirooxazines of general formula (I), wherein R1 is an optionally substituted alkyl, vinyl, allyl, optionally substituted phenyl, aralkyl, optionally substituted alicyclic or aliphatic hydrocarbon group comprising one or more heteroatoms selected from O, N and S; R2 and R3 are H, an alkyl radical, aryl, -(CH2)mOR, -SR, -COR or -COOR, where R is H, alkyl or aryl and m is an integer from 0 to 10, -NR4R5, where R4 and R5 are H, alkyl, cycloalkyl, aryl, or R4 and R5, taken together with the nitrogen atom, form a heterocyclic ring, halogen, mono- or polyhaloalkyl, -NO2, -CN, -SCN, SO3R', where R' is hydrogen or an alkali metal, SO2R', where R' is a phenyl or tolyl group; a polymerisable group; and H is an aromatic hydrocarbon ring or an aromatic heterocyclic ring, are disclosed. Said compounds are useful as photochromic compounds in ophthalmic optics.

Description

New homoazaadamantane spirooxazines and their use in the field of ophthalmic optics.

The subject of the invention is new photochromic compounds, more particularly photochromic compounds from the family of homoazaadamantane spirooxazines, their use in the field of ophthalmic optics, in particular in and / or on ophthalmic lenses, and contact lenses. optical devices.

Photochromism has been known for many years. A compound is said to be photochromic when this compound, irradiated by a light beam, certain wavelengths of which lie in the ultraviolet range, changes color and returns to its original color as soon as the irradiation ceases.

The applications of this phenomenon are multiple, but one of the known applications which is more particularly interesting relates to the field of ophthalmic optics.

Such compounds can be used in the manufacture of lenses or glasses for glasses, with a view to filtering light radiation as a function of their intensity.

The incorporation of photochromic compounds in an organic material constituting an ophthalmic lens, makes it possible to obtain a glass whose weight is considerably reduced compared to conventional lenses made of mineral glass which comprise silver halides as photochromic agent. Their incorporation into organic materials has always posed technical difficulties.

However, not all photochromic compounds can be used in the field of ophthalmic optics. Indeed, the photochromic compound must meet a certain number of criteria, including among others:

- a strong colorability which is the measure of the capacity for a photochromic compound to present an intense color after isomerization; - coloration after absorption of light making the photochromic compound suitable, alone or in combination with other photochromic compounds, for use in glasses or lenses ophthalmic;

- an absence of coloring or very weak coloring in the initial form;

- rapid kinetics of coloring or discoloration; - a photochromism manifesting itself in the widest possible temperature range, and in particular preferably between 0 and 40 ° C.

The organic photochromic compounds known and currently used generally exhibit a decreasing photochromism when the temperature increases, so that the photochromism is particularly marked at temperatures close to 0 ° C., while it is much weaker, even nonexistent, at temperatures of the order of 40 ° C which are temperatures that glasses can reach during exposure to the sun in particular. Another problem encountered for the photochromic compounds of the state of the art is their lifetime. In fact, for certain products of the state of the art, there is a relatively short life. In fact, after a certain number of coloring and discoloration cycles, the photochromic compound undergoes chemical degradation and no longer exhibits reversible photochromic properties.

The document EP-A-0338660 describes photochromic compounds of the spiro family [3H-1,4-oxazines] comprising a ring of the piperidine type grafted on spiranic carbon. These compounds have satisfactory photochromic characteristics with in particular a hypsochromic displacement of the wavelength of absorption in the visible compared to the standard reference series spiro [indoline-naphthoxazine]. On the other hand, the synthesis of compounds of document EP-A-033 660 proves to be difficult, in particular at the level of the piperidine precursor.

It would be desirable to produce photochromic compounds having higher spectrokinetic constants and therefore better photochromic properties and which are easily synthesizable. The applicant company has discovered a new family of spirooxazines with particularly interesting photochromic properties. The compounds according to the invention indeed have a high colorability, in particular in the field of pink or gray / green which is particularly useful for ophthalmic optics, these compounds then being able to be used with photochromic compounds giving a yellow or red color. such as chromenes, in order to obtain a natural final coloration when exposed to light.

The compounds in accordance with the invention moreover exhibit an absence of coloration or a very weak coloration in the initial state and rapid kinetics of coloration and discoloration in a very wide temperature range, in particular between 0 and 40 ° C.

On the other hand, the compounds according to the invention are more easily synthesizable than the compounds of document EP-A-0338660.

The Applicant has also found that these compounds have a particularly long lifespan.

All these properties mean that these new photochromic compounds are particularly advantageous in their use in ophthalmic optics and in particular for their use in and / or on ophthalmic lenses and optical devices.

In the sense of the invention, ophthalmic lenses are called spectacle lenses, in particular sunglasses, contact lenses.

An object of the invention therefore consists of the new photochromic compounds.

Another object of the invention is constituted by their use in ophthalmic optics. The invention also relates to compositions intended to be used for coating ophthalmic lenses or their incorporation into these lenses and the lenses of optical devices.

Other objects of the invention will appear on reading the description and the examples which follow. The photochromic compounds according to the invention are essentially characterized by the fact that they correspond to the general formula:

in which :

Ri represents a Cι-C ₁₆ alkyl group optionally substituted by one or more hydroxy, halogen, aryl, aroxy, alkoxy, acyloxy, acryloxy, methacryloxy or vinyl substituents; vinyl, allyl, phenyl, arylalkyl, phenyl mono- or disubstituted by alkyl or alkoxy substituents C _j -C ₆ alkyl or halogen, an optionally substituted alicyclic group, or an aliphatic hydrocarbon group having in its chain one or more heteroatoms from O, N and S;

R ₂ and R ₃ denote, independently of one another, a hydrogen atom; an alkyl group; an aryl group; a group - (CH ₂ ) _m OR, -SR, -COR or -COOR, in which R denotes a hydrogen atom, an alkyl group or an aryl group and m is an integer from 0 to 10; an amino group of formula NR ₄ R ₅ in which R and R ₅ denote, independently of one another, a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, R ₄ and R ₅ can forming with the nitrogen atom, a heterocycle comprising 4 to 7 members and which may additionally contain one or more intracyclic heteroatoms chosen from nitrogen, oxygen and sulfur; a halogen atom; a mono- or polyhaloalkyl group; a group -N0 ₂ , -CN, -SCN, S0 ₃ R 'where R' denotes hydrogen or an alkali metal, S0 ₂ "where R" is a phenyl or tolyl group; or an acrylic, methacrylic, vinyl or allylic polymerizable group optionally long-chain, for example an alkyl group in C _j -C, ₂ linear or branched, optionally interrupted by one or more oxygen atoms or carboxyl groups comprising at least one acrylic group, methacrylic, vinyl or allyl, preferably at the end of the chain; H is an aromatic hydrocarbon ring or an aromatic heterocycle having 4 to 7 members and preferably 5 or 6 members, the heterocyle comprising one or more intracyclic heteroatoms chosen from nitrogen, oxygen and sulfur, these rings and heterocycles being able to be substituted by one or more groups as defined for R ₂ and R ₃ or condensed with an aromatic or cycloalkyl ring.

In the above formula, an alkyl group preferably denotes a group having 1 to 6 carbon atoms, a cycloalkyl group preferably denotes a group having 3 to 7 carbon atoms, the aryl group preferably denotes a phenyl group, halogen denotes preferably chlorine, bromine, fluorine, the polyhaloalkyl group preferably designates the group CF ₃ .

Among the alkyl groups represented by R _j , mention may be made of methyl, ethyl, n-propyl, isopropyl and n-butyl groups.

Among the arylalkyl groups, R _j preferably represents the benzyl group.

The aromatic heterocycle H is more particularly represented by formula (II):. () _n (X) _p

C - R ₇ (II)

(Z) _q in which:

X, Y and Z, independently of each other, CR ₆ wherein R ₆ is hydrogen, alkyl C _j -C ₆ alkyl or a phenyl group, the carbon atom being linked to the one of the neighboring atoms by a double bond; a nitrogen atom linked to one of the neighboring atoms by a double bond; an oxygen atom or sulfur; n, p and q being integers equal to O or 1;

R ₇ denotes hydrogen, a C 1 -C ₆ alkyl group, a phenyl group, or R and X or R ₇ and Z may jointly form a 5 or 6-membered ring, aromatic or not, preferably benzene, or a naphthalene nucleus, optionally substituted by one or more groups (Rg) _r , R _g having the meaning of any of the groups R,, R ₂ , R ₃ , as defined above and r having an integer value of 1 to 4 when we have a benzene cycle or from 1 to 6 when we have a naphthalene cycle; X, Y, Z and CR ₇ being chosen so as to ensure the aromaticity of the heterocycle condensed on the naphthoxazine nucleus.

The particularly preferred heterocyclic rings are chosen from the groups of formula (II), in which n is equal to 0, X denotes O, S or N and Z denotes CR ₇ or X denotes CR ₇ and Z denotes O, S or N, R ₆ and R ₇ having the meanings indicated above. X preferably denotes O or S.

Other preferred compounds are those for which n + p + q = 3, and at least one of the groups X, Y or Z denotes N.

Among the aromatic rings that H can represent, there may be mentioned benzene, hydroxybenzenes, alkoxybenzenes such as methoxybenzene and halobenzenes such as bromobenzene. Among the aromatic heterocycles which H may represent, there may be mentioned thiophene, benzothiophene, naphthothiophene, furan, pyran, isobenzofuran, pyrrole, imidazole, pyrazole, isothiazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, isoindole, indole, indazole, isoquinoline, quinoline, phthalazine, quinoxaline, quinazoline, cinnaline, these cycles can possibly include one or more substituents. The more particularly preferred heterocyclic rings H are chosen from pyridine, pyrimidine, pyrazine and furan rings, optionally condensed with an aromatic ring to form an optionally substituted benzofuran, thiazole ring.

Preferred photochromic compounds according to the invention correspond to the formulas: where R _j , R ₂ , R ₃ and R _g have the same meaning as above, R ₉ is a group as defined for R ₂ and R ₃ , X _j represents -S- or -O-, r is an integer of 0 to 4, s is an integer from 0 to 3 and t is 0, 1 or 2.

The new compounds according to the invention can be easily synthesized using the method described in J. Org. Chem. 43, 20, The reaction scheme is indicated below.

Ri

(d) 80%

A substituted nitrosonaphthol or a substituted aminonaphthol is reacted on the quaternary base c), in the presence of triethylamine, or on the methylene base d) according to the reaction scheme below.

The photochromic compounds according to the invention can be used to make photochromic ophthalmic lenses. The compounds according to the invention can be introduced into a composition intended to be applied to or be introduced into a transparent organic polymer material to obtain a photochromic transparent article. They can also be introduced into solid compositions such as plastic films, plates and lenses for producing usable materials, in particular as ophthalmic lenses, sunglasses, viewfinders, camera optics and filters. The liquid compositions which constitute an object of the invention are essentially characterized in that they contain, in dissolved or dispersed form, the compounds according to the invention in a medium based on solvents suitable for being applied or introduced into a polymer material transparent. More particularly useful solvents are organic solvents chosen from benzene, toluene, chloroform, ethyl acetate, methyl ethyl ketone, acetone, ethyl alcohol, methyl alcohol, acetonitrile, tetrahydrofuran , dioxane, ethylene glycol methyl ether, dimethylformamide, dimethyl sulfoxide, methylcellosolve, morpholine, and ethylene glycol.

When the compounds according to the invention are dispersed, the medium can also contain water.

According to another embodiment, the compounds according to the invention can be introduced and preferably dissolved in colorless or transparent solutions prepared from polymers, copolymers or mixtures of transparent polymers in an appropriate organic solvent.

Examples of such solutions are inter alia solutions of nitrocellulose in acetonitrile, polyvinylacetate in acetone, polyvinyl chloride in methyl ethyl ketone, polymethyl methacrylate in acetone, cellulose acetate in dimethylformamide, polyvinylpyrrolidone in acetonitrile, polystyrene in benzene, ethylcellulose in methylene chloride. These compositions can be applied to transparent supports such as polyethylene glycol terephthalate, boryl paper, cellulose triacetate and dried to obtain a photochromic material which can be colored in the presence of ultraviolet radiation, and which returns to the colorless and transparent state in the absence of the radiation source.

The photochromic compounds of the present invention or the compositions containing them defined above can be applied or incorporated in a solid transparent polymerized organic material suitable for ophthalmic elements such as ophthalmic lenses or materials useful for use in sunglasses , viewfinders, camera optics and filters.

As transparent solid materials which can be used to produce ophthalmic lenses in accordance with the invention, mention may be made of polyol (allylcarbonate) polymers, polyacrylates, poly (alkylacrylate) such as polymethylmethacrylates, cellulose acetate , cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly (vinyl acetate), poly (vinyl alcohol), polyurethanes, polycarbonates, polyethyleneterephthalates, polystyrenes, (polystyrene-methylmethacrylate) , copolymers of styrene and acrylonitrile, polyvinylbutyrates.

Transparent copolymers or mixtures of transparent polymers are also suitable for producing such materials. Mention may be made in this connection of materials prepared from polycarbonates such as poly (4,4'-dioxydiphenol-2,2 propane), polymethylmethacrylate, polyol (allylcarbonate) such as in particular diethylene glycol bis (allylcarbonate) and its copolymers such as for example with vinyl acetate. Mention may in particular be made of the copolymers of diethylene glycol bis (allylcarbonate) and of vinyl acetate (80-90 / 10-20) and also the copolymer of diethylene glycol bis (allylcarbonate) with vinyl acetate, of cellulose acetate. and cellulose propionate, cellulose butyrate (80-85 / 15-20). Polyols (allylcarbonate) are prepared using allyl carbonates of aliphatic or aromatic, linear or branched liquid polyols such as aliphatic glycols of bis-allylcarbonate or alkylene bis (allylcarbonate). Among the polyols (allylcarbonatc) which can be used to prepare the transparent solid materials which can be used in accordance with the invention, mention may be made of ethylene glycol bis (allylcarbonatc), diethylene glycol bis (2-methallylcarbonate), diethylene glycol bis (allylcarbonate), ethylene glycol bis (2-chloroallylcarbonate), triethylene glycol bis (allylcarbonate). 1,3-propanediol bis (allylcarbonate), propylene glycol bis (2-ethylallyl carbonate), 1,3-butanediol bis (allylcarbonate), 1,4-butanediol bis (2-bromoallylcarbonate), dipropylene glycol bis ( allylcarbonate). trimethylene glycol bis (2-ethylallylcarbonate), pentamethylene glycol bis (allylcarbonate), isopropylene bisphenol bis (allyl carbonate). The most important product is constituted by diethylene glycol bis (allylcarbonate) still known under the name CR39.

The quantity of photochromic compounds to be used in accordance with the invention, either in the composition or at the time of its introduction into the solid support, is not critical and generally depends on the intensity of the color which the composition can impart to the material after exposure to radiation. In general, the more photochromic compounds are added. the more the coloring under iiτadiation will be important.

In accordance with the invention, a sufficient amount is used to give the treated material the property of changing color when exposed to radiation. This quantity of photochromic compounds is generally between 0.01 and 2 () 7 <- by weight and preferably between 0.05 and 107c by weight relative to the total weight of the optical material or of the composition.

The photochromic compounds according to the invention can also be introduced into a temporary transfer support (such as a varnish forming a coating on a substrate) and then be transferred thermally into the substrate as described in particular in US Pat. No. 4,286. 957 or US-4,880,667.

Thus, the invention also relates to a transfer varnish which contains at least one photochromic compound according to the invention.

These compounds can be used with other photochromic compounds, such as photochromic compounds giving give rise to different colors such as yellow or red, known in the state of the art. This is how chromenes well known in the art can be used.

Once applied to ophthalmic materials or introduced into such materials, we observe after exposure to UV irradiation, the appearance of a coloration and the return to the original color or transparency when the exposure to UV radiation is interrupted. .

The compounds in accordance with the invention have the advantage of allowing this change in coloration a large number of times and this at very variable temperatures of between 0 and 40 ° C.

The following examples are intended to illustrate the invention without, however, being limiting in nature.

EXAMPLE 1

Compound preparation:

To a mixture containing 0.30 g (1 mmol) of compound c) for which R _j = CH ₃ , 0.22 g (1.1 mmol) of aminonaphthol hydrochloride

0.4 g of sodium hydrogen carbonate, 0.15 g (1.25 mmol) of dimethyl sulfoxide and 0.25 g (2.5 mmol) of triethylamine, 10 ml of toluene are added and the mixture is left for 5 hours at 50 ° C. It is filtered, washed with hot toluene (5 ml) and the filtrate is evaporated. The product is then purified by flash chromatography (95 hexane / 5 ethyl acetate).

The expected product is obtained having a melting point of 108 ° C with a yield of 26%.

EXAMPLE 2

Compound preparation

To a mixture of 0.17 g (1 mmol) of compound of formula (d) in which R _j = CH ₃ , 0.22 g (1.1 mmol) of amino-naphthol hydrochloride, 0.4 g d sodium hydrogen carbonate, 0.15 g (1.25 mmol) of dimethylsulfoxide, and 0.15 g (1.5 mmol) of triethylamine, 10 ml of toluene are added and the mixture is left at 50 ° C. for 5 hours. It is filtered, washed with hot toluene (5 ml) and the filtrate is evaporated. The product is then purified by flash chromatography (95 pentane / 5 ethyl acetate).

The expected product is obtained having a melting point of 159 ° C with a yield of 32%.

EXAMPLE 3

Compound preparation:

To a mixture of 0.30 g (1 mmol) of compound (c) in which R _] = CH ₃ , 0.19 g (1 mmol) of l-nitroso-2,7-dihydroxynaphthalene, 0.12 g (1 , 2 mmol) of triethylamine, 15 ml of ethanol are added and the mixture is heated at reflux for 4 hours. The solvent is evaporated. The product is purified by flash chromatography (80 pentane / 20 ethyl acetate).

The expected product is obtained having a melting point of 188 ° C with a yield of 29%.

EXAMPLE 4 Preparation of the compound:

To a mixture of 0.17 g (1 mmol) of compound (d) for which R _j = CH ₃ , 0.17 g (1 mmol) of 6-hydroxy-5-nitrosoquinoline, 0.12 g

(1.2 mmol) of triethylamine, 15 ml of trichlorethylene are added and the mixture is left to reflux for 3 hours. The solvent is evaporated. The product is then purified by flash chromatography (90 dichloromethane / 10 ethyl acetate). The expected product is obtained having a melting point of 101 ° C with a yield of 24%.

EXAMPLE 5

Compound preparation

This compound is obtained as in Example 3, from compound (c) (R _j = CH ₃ ) and 3-hydroxy-4-nitrosodibenzofurane.

The expected product is obtained having a melting point of 122 ° C with a yield of 12%.

EXAMPLE 6

Compound preparation

This compound is obtained as in Example 3, from compound (c) (R _j = CH ₃ ) and 5-hydroxy-4-nitroso-2,3-pentamethylene benzofuran.

The expected product is obtained having a melting point of 81 ° C with a yield of 22%. EXAMPLE 7

Compound preparation

This compound is obtained as in Example 3, from compound (c) (R _j = CH ₃ ) and 3-hydroxymethyl-1-nitroso-2-naphthol.

The expected product is obtained having a melting point of 128 ° C with a yield of 28%.

EXAMPLE 8

Compound preparation:

This compound is obtained as in Example 3, from compound (c) (R _j = CH ₃ ) and 3-methoxycarbonyl-1-nitroso-2-naphthol.

The expected product is obtained having a melting point of 92 ° C with a yield of 16%. EXAMPLE 9 Preparation of the compound:

This compound is obtained as in Example 3, from compound (c) (R _j = CH ₃ ) and 6-bromo-1-nitroso-2-naphthol.

The expected product is obtained having a melting point of 11 ° C. with a yield of 14%.

EXAMPLE 10

Compound preparation

This compound is obtained as in Example 3, from compound (c) (R _j ≈nPr) and 7-methoxy-1-nitroso-2-naphthol.

The expected product is obtained having a melting point of 106 ° C with a yield of 18%.

COMPARATIVE EXAMPLES 1 1 and 12

The compounds of Comparative Examples 11 and 12 were synthesized according to the references below in order to compare them with the products of the present invention.

The reaction scheme is as follows:

12

The synthesis of compound 11 is more particularly described in Bull. Chem. Soc. Jpn, 63, 267-268, 1990 and that of compound 12 in patent EP-A-0388660.

The syntheses of product A described in patents EP-A-0358774 and US-A-4287337 (R. Guglielmetti), testify to the difficulty of access of this compound.

The spectrokinetic parameters of the products of Examples 1-10 and of comparison products 11 and 12 (A ₀ , K and λ _maχ ) (K denotes the rate of thermal discoloration rate and A _Q the "colorability" determined by the value of l absorbance measured immediately after the irradiation flash) were obtained by flash photolysis coupled to a fast spectrometer of the Warner and Swasey type. The experimental conditions are as described in patent application WO-96/04590, using in particular concentrations of 2.5 × 10 ^"5 Ml ^"! in photochromes in toluene and a temperature of 25 ° C.

The results are shown in Table I below.

* The underlined values correspond to the bands of greatest intensity

The underlined values correspond to the bands of greatest intensity Due to the relatively low colorability and the rapid discoloration rate, the photochromism of the products of Comparative Examples 1 1 and 12 is not observable at room temperature in toluene.

EXAMPLE 13

Compounds 1, 2, 1 1 and 12 were tested in a polymer matrix, prepared as follows:

A solution is prepared at 10% by weight of polymethyl methacrylate (PMMA) obtained from the company ALDRICH and 3% by weight in photochrome in chloroform. The solution is deposited in a thin layer in a crystallizer. The solvent is allowed to evaporate and then the plastic film is peeled off.

The photochromism of the films thus obtained was observed under UV irradiation (Flash).

Products 1 and 2 give good coloring. Product 1 1 shows no coloration. However, product 12 is photochromic under these conditions with lower colorability.

It appears from the preceding examples that the colorability values A _Q of the compounds according to the invention are higher than those of the compounds of Comparative Examples 1 1 and 12 and the values of the kinetic constants are lower.

In addition, the synthesis of the homoazaadamantane part of the compounds according to the invention is much easier than the synthesis of the piperidine part of Comparative Examples 1 1 and 12 and the formation of the corresponding spirooxazines of the invention therefore proves to be more effective. .

Claims

1. Photochromic compound, characterized in that it corresponds to the general formula:

in which :

R _j represents a C _j -C ₁₆ alkyl group optionally substituted by one or more hydroxy, halogen, aryl, aroxy, alkoxy, acyloxy, acryloxy, methacryloxy, vinyl substituents; a vinyl, allyl, phenyl, arylalkyl, phenyl group mono- or disubstituted by alkyl or alkoxy substituents in CC ₆ or halogen, an alicyclic group optionally substituted, or an aliphatic hydrocarbon group comprising in its chain one or more heteroatoms chosen from O, N and S;

R ₂ and R ₃ denote, independently of one another, a hydrogen atom; an alkyl group; an aryl group; a group - (CH ₂ ) _m OR, -SR, -COR or -COOR, in which R denotes a hydrogen atom, an alkyl group or an aryl group and m is an integer from 0 to 10; an amino group of formula NR ₄ R ₅ in which R ₄ and R ₅ denote, independently of one another, a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, R ₄ and R ₅ which can form, with the nitrogen atom, a heterocycle comprising 4 to 7 members and which can additionally contain one or more intracyclic heteroatoms chosen from nitrogen, oxygen and sulfur; a halogen atom; a mono- or polyhaloalkyl group; a group -N0 ₂ , -CN, -SCN, S0 ₃ R 'where R' denotes hydrogen or an alkali metal, S0 ₂ R "where R" is a phenyl or tolyl group; or a group polymerizable acrylic, methacrylic, vinyl or allylic optionally long chain; H is an aromatic hydrocarbon ring or an aromatic heterocycle having 4 to 7 members and preferably 5 or 6 members, the heterocycle comprising one or more intracyclic heteroatoms chosen from nitrogen, oxygen and sulfur, these cycles and heterocycles being able to be substituted by one or more groups as defined for R ₂ and R ^ condensed with an aromatic or cycloalkyl ring.

2. Compound according to Claim 1, characterized in that the ring or heterocycle H is a 5 or 6-membered ring.

3. Compound according to claim 1 or '2, characterized in that the aromatic heterocycle corresponds to the general formula:

C— R ₇ (II)

- (Z) q in which:

X, Y and Z denote, independently of one another, a group CR ₆ in which R ₆ represents hydrogen, an alkyl group

C _j -C ₆ or a phenyl group, the carbon atom being linked to one of the neighboring atoms by a double bond; a nitrogen atom linked to one of the neighboring atoms by a double bond; an oxygen or sulfur atom; n, p and q being integers equal to 0 or 1; R ₇ denotes hydrogen, a C _j -C ₆ alkyl group, a phenyl group, or R ₇ and X or R and Z which can jointly form a 5 or 6-membered ring, aromatic or not, preferably benzene. or a naphthalene ring, optionally substituted by one or more groups (Rg) _r , Rg having the meaning of any one of the groups R _j , R ₂ , R ₃ , as defined above and r having an integer value of 1 to 4 when we have a benzene cycle or 1 to 6 when we have a naphthalene cycle; X, Y, Z and CR ₇ being chosen so as to ensure the aromaticity of the heterocycle condensed on the naphthoxazine nucleus.

4. Compound according to claim 3, characterized in that in the group of formula (II), n is equal to O, X denotes O, S or N and Z denotes CR ₇ , or else X denotes CR ₇ and Z denotes O, S or N, R and R ₇ having the meanings indicated in claim 3.

5. Compound according to Claim 3, characterized in that n + p + q = 3 and at least one of the groups X, Y, Z denotes N.

6. Compound according to any one of claims 1 to 3. characterized in that the photochromic compounds are chosen from the compounds of formulas:

where R _j , R ₂ , R ₃ and R _g have the same meaning as in claims 1 and 2, R ₉ is a group as defined for R and R ₃ , X _j represents -S- or -O-, r is an integer from 0 to 4, s is an integer from 0 to 3 and t is 0, 1 or 2.

7. Compound according to claim 1 or 2, characterized in that it is chosen from the compounds of formula:

8. Use of the compound according to any one of claims 1 to 7, as a photochromic compound in ophthalmic optics.

9. Composition intended to be applied to or introduced into a transparent organic polymer material, characterized in that it contains at least one photochromic compound as defined in any one of claims 1 to 7, in quantities sufficient to allow the material exposed to ultraviolet radiation to change color.

10. Composition according to Claim 9, characterized in that the composition is in liquid form containing, in dissolved or dispersed form, the photochromic compounds according to any one of Claims 1 to 7, in a medium based on solvents suitable for being applied or introduced into a transparent polymer material.

11. Composition intended to be applied to or introduced into a transparent organic polymer material, characterized in that it consists of a colorless or transparent solution based on polymers, copolymers or mixture of transparent polymers in an appropriate organic solvent , containing at least one photochromic compound as defined in any one of claims 1 to 7, in amounts sufficient to allow the material exposed to ultraviolet radiation to change color.

12. Transparent solid material suitable for producing ophthalmic lenses, characterized in that it comprises on the surface and / or inside at least one photochromic compound as defined in any one of claims 1 to 7, in sufficient quantities to allow the material exposed to ultraviolet radiation to change color.

13. Transparent solid material according to claim 12, characterized in that it contains 0.01 to 20% by weight of photochromic compounds.

14. Composition or transparent solid material according to any one of claims 8 to 12, characterized in that the photochromic compound as defined in any one of claims 1 to 7, is used in conjunction with other photochromic compounds giving rise to different colorings.

15. Transfer varnish, characterized in that it contains at least one compound as defined in any one of claims 1 to 7.