MXPA01002559A - Naphthopyrans annelated in c6 - Google Patents

Abstract

The invention relates to novel naphthopyrans having a cyclic group annelated in position 6, 7. These naphthopyrans have formula (I). These compounds (I) have advantageous photochromic properties. The invention also covers the method of preparing these naphthopyrans, as well as their applications as photochromes:compositions and (co)polymers matrices comprising them.

Description

/ NAFTOPIRANS ANELATED IN CARBON 6 AND 7. YOUR PREPARATION. AND COMPOSITIONS AND MATRICES OF POLYMERS AND / OR COPOLYMERS THAT CONTAIN THEM • DESCRIPTIVE MEMORY The present invention relates to novel compounds of the naphthopyran type having, in particular, photochromic properties. The invention also relates to photochromic compositions and photochromic ophthalmic articles (lenses, for example) containing naphthopyrans. The invention also covers the preparation of these novel naphthopyrans. The photochromic compounds are capable of changing color under the influence of a poly- or monochromatic light (UV for example) and of to return to its initial color when the light irradiation ceases, under the influence of temperature and / or a poly- or monochromatic light different from the first. • Photochromic compounds find applications in several fields, for example for the manufacture of ophthalmic lenses, lenses of contact, sun protection glasses, filters, optical elements of cameras or optical elements of photographic or other optical devices and observation devices, glassware, decorative objects, elements of tihA? A? .tr < tiAJ. - * * * ticket or even for storage of information by optical registration (coding). In the field of ophthalmic optics and in particular in the field of eyeglasses, a photochromic lens comprising one or more photochromic compounds must have: - high transmission in the absence of ultraviolet radiation, - low transmission (high coloring capacity) in the solar irradiation, - kinetics adapted from coloring and discoloration, a dye acceptable to the consumer (preferably gray or brown) preferably with maintenance of the chosen dye during the coloring and the discoloration of the lens, - maintenance of the performances, the properties, inside from a temperature range of 0-40 ° C, - significant durability, since these projected objectives are corrective lenses and therefore costly. These lens characteristics are actually determined by the active photochromic compounds they contain; compounds that must also be perfectly compatible with the organic or inorganic support that constitutes the lens. In addition, it should be noted that obtaining a gray or brown dye may require the use of at least two photochromies of different colors, that is to say that they have certain absorption wavelengths . --- Ji t, maximum in the visible spectrum. This combination also imposes requirements of the photochromic compounds. In particular, the kinetics of coloration and decoloration of the combined (two or more) active photochromic compounds must be essentially identical. The same applies for your • stability over time and also for compatibility with a plastic or inorganic support. Among the numerous photochromic compounds described in the prior art, there may be mentioned the benzopyrans or naphthopyrans which are described in the patents or patent applications US-A-3,567,605, US-A-10 3,627,690, US-A-4,826,977, US-A -5,200,116, US-A-5,238,981, US-A- # 5,411, 679, US-A-5,429,744, US-A-5,451, 344, US-A-5,651, 923, US-A-5,645,767, US-A- 5,698,141, WO-A-95 05382, FR-A-2,718,447, WO-A-96 14596, WO-A-97 21698 which are of the following reduced formula: The patents of E.U.A. US-A-5,645,767 and US-A-5,651,923-20 describe more specifically naphthopyrans which have, respectively, first indeno groups and secondly bento or naphthofuran side / naphthopyran groups (general structures below). i- i «., A J __ & _____ *., -. -? - It appears that some of the naphthopyrans disclosed in US-A-5,651,923 comprise aneclic carbocycles of the type of indene that are fused with the carbons 9 and 10 of the unit • Naphthopyran or comprise anetrocylated heterocycles of the benzo or naphthofuran type which are fused with coals 5 and 6 of the naphthopyran unit. The photochromic compounds are obtained, according to the US-A-5,645,767, from substituted or unsubstituted benzophenones which it is desired to react with an ester of succinic acid, such as dimethyl ester, in the presence of toluene potassium tert-butoxide. HE • thus produces a half ester that is successively converted to acetoxynaphthalene and carboxinaphthol which is used to give a molten naphthol with a residue of indenone. The reaction of this latter compound with a propargyl alcohol, in the presence of DBSA, gives rise to a naphthopyran fused with an indenone ring. You can get the indene counterpart of this naphthopyran ..,,. ^^^. ^^? X wmiA • _Afa, a ,, 4._M. < _-.-__ starting with the precursor that has a reduced acetone function. This indenone carbon can be substituted in several ways. As for the naphthopyrans fused with the benzo or naphthofuran residues according to US Pat. No. 5,651,923, they are prepared by reacting a fused naphthol with an indenone ring or a naphthofuran ring, on the one hand, and with a propargyl alcohol on the other hand. Naphthol is melted with an indedone ring, for example as described in US-A-5,645,767; while the naphthol fused with a naphthofuran ring originates from the reaction between a naphthoquinone and 1,3-dihydroxynaphthalene, with or without subsequent methylation at least one hydroxy. These compounds seem to meet the specifications defined above. In fact, if these compounds actually have one or more of the basic properties procured, such as high transmission in the absence of ultraviolet irradiations of this coloration ability in solar irradiation, none of the compounds described so far has the full combination of the properties which are necessary for the production of satisfactory articles. In particular, none of these compounds is essentially gray or brown and there remains a need to use an additional photochromia in order to obtain one of these two dyes. In this context, it is for the credit of the inventors to have been interested in this type of naphthopyran as a basis for developing novel photochromies and to have proposed a novel family of molecules that have particularly vectored photochromic properties. Thus, according to the first of its aspects, the present invention relates to naphthopyran compounds of the following formula (I): wherein: • L corresponds to a direct bond or divalent residue: O, S, NRT (Re represents a linear or branched alkyl group comprising from 1 to 6 carbon atoms), CR7R8. (CR7R8) 2, (representing R7 and Rβ, which are identical or different, independently an H, an OH, or a linear or branched alkyl or alkoxy group comprising from 1 to 6 carbon atoms) or a carbocycle selected from the following: • • R1 and R2 independently represent: - a hydrogen, ]?You?' I? ÉÍÍtilÍffif «ÍM --t - * - - * * fc > ., **. ** & ^ ga ^ g - 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 of 6 to 24 carbon atoms or from 4 to 24 carbon atoms respectively and at least one heteroatom selected from sulfur, oxygen and nitrogen; said basic structure being optionally substituted by at least one substituent selected from: + a halogen, and notably fluorine, chlorine and bromine, + a hydroxy group, + a linear or branched alkyl group comprising from 1 to 12 carbon atoms, + a straight or branched linear or branched alkoxy group comprising from 1 to 12 carbon atoms, + a halogenoalkyl or halogenoalkoxy group corresponding to the above C-pC? 2 alkyl or alkoxy groups respectively which are substituted by at least one atom of halogen and notably such a fluoroalkyl group, + a linear or branched alkenyl group comprising from 2 to 12 carbon atoms, and notably a vinyl group or an allyl group, + a -NH2 group, t-áfc-á ------ ¡-Kj-t -.__ ^ i.,. j-.i. . ... . . »,. __ • t-t-, - - a »- .. -iv." «,», * .. + a -NHR group, R representing a linear or branched alkyl group comprising from 1 to 6 carbon atoms, + a group representing R 'and R ", which are identical or different, independently a linear or branched alkyl group comprising from 1 to 6 carbon atoms, or representing, together with the nitrogen atom to which they are attached, a ring of 5 or 7 members which may comprise at least one other hetero atom selected from oxygen, sulfur and nitrogen, said nitrogen being optionally substituted by a group R "\ which is a linear or branched alkyl group comprising from 1 to 6 carbon atoms, + a methacryloyl group or an acryloyl group, - an alkyl or heteroalkyl group, the alkyl group comprising, which is linear or branched, of 1 to 4 carbon atoms and the aryl and heteroaryl groups having the definitions given above, or substituents Ri and R2 together form an adamantyl, norbonyl, fluorenylidene, dialkyl (C6-6) anthracenylidene or spiro-cycloalkyl (C5-C6) anthracenylidene group; said group being optionally substituted by at least one of the substituents listed above for R-i, R2: an aryl or heteroaryl group; _ ---- --fc-i¿-¿ l - ?. i. _-• ...-., .-. .

R3 and R4, which are identical or different, independently represent: a hydrogen, a halogen, and notably fluorine, chlorine or bromine, a linear or branched alkyl group comprising from 1 to 12 carbon atoms (advantageously from 1 to 6 carbon atoms), - a cycloalkyl group comprising from 3 to 12 carbon atoms, - a linear or branched alkoxy group comprising from 1 to 12 carbon atoms (advantageously from 1 to 6 carbon atoms), wW - a halogenoalkyl, halogenocycloalkyl or halogenoalkoxy group corresponding to the above alkyl, cycloalkyl or alkoxy groups, respectively, which are substituted by at least one halogen atom, selected notably from fluorine, chlorine and bromine, an aryl or heteroaryl group has the same definition as that given above for R1, R2, - an aralkyl or heteroalkyl group, the alkyl group F comprising, which is linear or branched, from 1 to 4 carbon atoms, and the aryl and heteroaryl groups having the same definitions as those given above - an amine or amide group: -NH2, -NHR, -CONH2, -CONHR, »Jr__ / R - N \ o -CON. R "R"; having R, R ', R "their respective definitions given above for the • 5 amine substituents of the Ri, R2: aryl or heteroaryl values, - a group -OCORβ or -COORβ, R representing a straight or branched alkyl group comprising 1 to 6 carbon atoms, or a cycloalkyl group of comprising 3 to 6 carbon atoms, or a phenyl group, optionally substituted minus one of the substituents listed above for the values of R-i, R2: aryl or heteroaryl; • • m and n are, independently, integers from 0 to 4 and from 0 to 3 respectively, • R5 represents: - a nitrogen, - a linear or branched alkyl group comprising from 1 to 12 carbon atoms (advantageously from 1 to 6 carbon atoms), - a cycloalkyl group comprising from 3 to 12 carbon atoms • carbon, - a linear or branched alkenyl group comprising from 2 to 12 carbon atoms, and notably a vinyl group or an allyl group, - a phenyl or benzyl group, optionally substituted by less with one of the substituents listed above for the values of R1, R2: aryl or heteroaryl, m * ^^^ gte * "MeMg &__ ___-___ j --- t.«; »- _..« -_,. -. »._ .-.",. - - ^. .., __ 1. -. * - a group -COR, -COOR7 or CONHR7, R7 representing a linear or branched alkyl group comprising from 1 to 6 carbon atoms, or a cycloalkyl group comprising from 3 to 6 carbon atoms, or a phenyl or benzyl group optionally substituted with at least one of the • 5 substituents listed above in the definition of the radicals R1, R2 in the formula (I), in which case these radicals correspond independently or an aryl or heteroaryl group. The compounds of the invention - naphthopyrans of the formula (I) - possess particularly advantageous photochromic properties. Plus specifically, these novel compounds have a high capacity for • coloration (even at 40 ° C), high sensitivity to UV irradiation with? Max greater than known naphthopyrans of analogous structure. Among said compounds of the formula (I) above, those having the formula (I) are preferred, as follows: in which: • L represents a direct bond, an oxygen, a radical -CH2- (CH3) 2C, • R-i and / or R2, independently represent optionally substituted aryl or heteroaryl groups whose basic structure is selected from the group phenyl, naphthyl, biphenyl, pyridyl, furyl, benzofuryl, dibenzofuryl, N-aiqui (CrC6) carbazole, thienyl, benzothienyl, dibenzothienyl, julodidinyl; • Ri and / or R2 advantageously representing a para-substituted phenyl group or R-i and R2 together form an adamantyl or norbonyl group; • R5 represents a hydrogen, a linear or branched alkyl group comprising from 1 to 6 carbon atoms, an optionally substituted phenyl or benzyl group, a -COR group, -COOR7 or CONHR7, wherein R7 represents a linear or branched alkyl group which comprises from 1 to 6 carbon atoms, or an optionally substituted phenyl or benzyl group. • Among the above compounds of the formulas (I) and (II) are particularly preferred different from those having L corresponding to a direct link and being R5 COOR7 or CONHR7 (subfamily I 'oi 1') and more generally those of said formulas (I) and (II) wherein L (does not correspond to a direct bond) corresponds to a divalent residue: O, S, NRe, CR7R8, (CR7R8) 2, or a carbocycle (subfamily I "or 11"). * lBáÍt? ^ tKm M? ^ AJí Á A ai? -.- fa-tna-, »- ... - - ~. - "- ,. _, --- • -. _t «M» - ». "Y. _. * - », -, .. t 5 The inventors also take the credit in the sense that they have proposed, in this field of photochromies, a novel synthetic route to the aneflated naphthopyrans that gives access to novel compounds that have at least one carbocycle or heterocycle fused with coals 6 and 7 of the naphthopyran unit, using this synthetic route of a precursor of the naphthol type which obtains at least one ketone: - comprising at least one carbocycle or heterocycle; and which is reacted with at least one alkyl cyanoacetate; the product obtained being then cyclized. According to the second of its aspects, the invention also relates to a method of preparation, notably to a method of preparing the compounds of the formula (I) as defined above. This method consists essentially in carrying out a condensation: - at least one compound of the following formula (II): wherein R3, R, R5, L, m and n are as defined above with reference to formula (I); 10 at least one propargyl alcohol derivative, • the following formula (III): Wherein R1 and R2 are as defined above with reference to formula (I); the condensation (ll) / (III) being advantageously carried out in the presence of a catalyst, this catalyst being preferably selected from the group comprising: para-toluenesulfonic acid, dodecyl sulfonic acid and acid Bromoacetic acid, - or with an aldehyde derivative of the following formula (III1): ? XX X. < ? -I.-7ÍÍÍ in which Ri and R2 are as defined above with reference to formula 5 (I); the condensation (ll) / (IH ') being carried out in the presence of a metal complex, preferably a titanium complex, with the 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, to which optionally appropriate catalysts are added. For more details on the condensation of the compounds (II '), (I II') reference is made to the patent application EP-A-0 562 915. Said compounds of the formula (III) are known to those skilled in the art. the technique and are obtained from the corresponding ketone according to a method notably described in patent application WO-A-96 14596. The ketone is itself commercial and is prepared according to known methods such as the Friedel method Crafts (see WO-A-96 14596 and references cited). The aldehydes derived from (III) are obtained by rearrangement in an acid medium (see J. Org Chem., 1977, 42, 3403). .t ..-- -: ^ «:. ^ ,. á.;. t »- < > .

Said compounds of the formula (II) are obtained according to a synthetic scheme whose several steps are adaptations of known methods. The preferred general synthetic scheme is given below: This synthetic route is inspired by the work of Sepiol et al. (Synthesis 1979, 290). From which it follows that the invention also encompasses a method of preparing the naphthols of the formula (II), characterized in that it comprises the following essential steps: 1- Reaction of the precursor (Ip-i) of the formula: ? Jt -I A -¡¡ < - ^ & , & and at least one alkyl cyanoacetate of the formula NC-CH 2 -COORa with Ra = alkyl, preferably ethyl, in order to obtain the intermediate compound (Ipi): 2- thermal cyclization of (lp2) that gives rise to the intermediate compound 3- High temperature deciation of (Ip3> to produce the intermediate compound (II): .i k General details of this method are given in the following examples. It really is a matter of a novel synthetic route in the field of photochromies; and this route offers undeniable advantages in terms of ease of application and in economic terms. • According to the third of its aspects, the object of the invention is a (co) polymer and / or crosslinked which is obtained by polymerizing and / or interlacing at least one monomer comprising a naphthopyran as defined above. In addition, the naphthopyran according to the invention can themselves be comonomers and / or be comprised between copolymerizable and / or crosslinkable comonomers. The (co) polymers and / or crosslinks thus obtained can be photochromic matrices. According to the fourth of its aspects, the present invention relates to the use of said compounds of the formula (I) of the invention, as photochromic agents. The object of the invention is therefore: firstly, novel photochromic compounds which are constituted by the naphthopyran derivatives, such as defined above, taken alone or as a mixture of themselves and / or at least • any other non-photochromic compound of another type and / or at least one non-photochromic coloring agent; 20 - secondly, novel photochromic compositions comprising at least one naphthopyran derivative (I) and one of its derivatives as defined above, and / or at least one linear or interlaced (co) polymer containing at least a compound (I) in agreement .'-. v S. I __-- i.-a- - *, i *. j¿ka »- > ._.-. , -. _. "_. with the invention in its structure. Such photochromic compositions may contain at least some other photochromic compound of another type and / or a non-photochromic coloring agent and / or at least one stabilizing agent. Photochromic compounds of another type, non-photochromic coloring agents and stabilizing agents are prior art products known to the person skilled in the art. Within the context of the present invention, combinations of photochromic compounds of the invention and / or combinations of photochromic compounds of the invention and photochromic compounds of another type according to the prior art are particularly recommended; such combinations being interesting because they are suitable for generating gray or brown dyes, which are desired by the public in applications, such as ophthalmic goggles or solar glasses. These additional photochromic compounds may be those known to those skilled in the art and described in the literature, for example, cromenos (US-A-3,567,6045, US-A-5,238,981, WO-A94 22850, EP-A-0 562). 915), spiropyrans or naphtho sires (US-A_5,238,981) and esiroxazines (Crano et al., "Applied Photochromic Polymer Systems", Ed. Blackie &Sons Ltd., 1992, Chapter 2). Said compositions according to the invention may also comprise: non-photochromic coloring agents which make it possible to adjust the dye, * .A & pM '- and / or one or more stabilizing agents, such as an antioxidant agent for example, - and / or one or more anti-UV agents, - and / or one or more antiradical agents, 5 - and / or one or more photochemical excited state deactivators, These additives can make possible remarkably the improvement of the durability of said compositions. The compounds of the invention contemplated within the context of their photochromic applications 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 obtained solutions are in general 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 the sun's rays, or in other words, when they are no longer subjected to UV irradiation. In general, a very low concentration of the product (of the order of 0.01 to 5% by weight) is sufficient to obtain a • intense coloration. The compounds according to the invention are also compatible with support matrices of organic polymer or inorganic material, in a form included in said matrices as well as the form of a coating of said matrices.

Also, within the context of the fourth aspect of the invention in relation to photochromic applications, the object of the invention is a matrix comprising: - at least one compound (I), as defined above; - and / or at least one (co) polymer and / or crosslinked material, as defined above; - and / or at least one composition, as previously presented. The most interesting applications of the compounds of the invention are in fact those in which the photochromia is dispersed uniformly within or on the surface of a matrix formed by a polymer, a copolymer and / or mixtures of (co) polymers. Following the example of their behavior in solution or in a polymer 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 under a source of light of the solar type.

Finally, they recover their initial coloration once irradiation ceases. The methods of execution that can be contemplated in order to obtain such a matrix are very varied. Among those known to the person skilled in the art, mention may be made, for example, of diffusion in the (co) polymer, from a suspension or solution of the photochromy, in a silicone oil, in an aliphatic or aromatic hydrocarbon, or in a glycol, or from another polymer matrix. Diffusion is commonly carried out at a temperature of 50 to & -. : _. * 200 ° C for a time interval of 15 minutes to several hours, according to the nature of the polymer matrix. Another execution technique consists of mixing the photochromy in a formulation of polymerizable matrices, depositing the mixture on a surface or a mold, and then carrying out the polymerization. These execution techniques and others are described in the article by Crano et al., "Spiroxazines and their use in photochromic lenses" published in Applied Photochromic Polymer Systems, Ed. Blackie and Son Ltd - 1992. The following products can be mentioned as examples 0 of preferred polymeric materials for forming matrices which are useful in optical applications of photochromic compounds according to the invention: alkyl, cycloalkyl, (poly or oligo) ethylene glycol, ary or arylalkyl, mono-, di-, tri- or tetraacrylate , or mono-, di-, tri- or tetramethacrylate, 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 group and / or amide, polystyrene, polyether, polyester, polycarbonate (for example bisphenol-A polycarbonate, diallyldiethylene glycol polycarbonate), polycarbamate, polyepoxy, polyurea, polyurethane, polythiourethane, polysiloxane, polyacrylonitrile, polyamide, or polyester aliphatic or aromatic r, vinyl polymers, cellulose acetate, cellulose triacetate, cellulose acetate propionate or polyvinyl butyral, - difunctional monomers having the following formula: tálSi .. i JL ...-..-. .-, ..- -. -,,. »- ..:».,. _ __ _. ft -._ - - -_? .- .. .-, "-» UB ÍJ in which: 5? River, R'10, Rn and R'11 are identical or different and independently represent a hydrogen or a methyl group; ? mi and n-i are, independently, integers between 0 and 4 (inclusive); and are advantageously independently equal to 1 or 2; ? X and X ', which are identical or different, are a halogen and preferably represent a chlorine and / or a bromine; ? pi and q-i are, independently, integers between 0 and 4 (inclusive); - copolymers of at least two types of copolymerizable monomers selected from the monomers precursors of the Polymers listed above (notably those belonging to the group comprising: (meth) acrylic monomers, vinyl monomers, átk allilic monomers and mixtures thereof). In a particularly preferred manner, the photochromies of the invention are used with resins having a nanobiphasic structure and which are obtained copolymerizing monomers two different specific difunctional monomers. Such resins have been described in the French patent application FR-A-2 762 845.

? A ...? Ii- -__, _._. . _-_-, ..,, -a_fe__tta_ «< "The amount of photochromic used in the (co) polymer matrix will repair the desired degree of darkening. Usually, it is used between 0.001 and 20% by weight. Still with the fourth of its aspects in relation to the applications of the naphthopyrans (I) as photochromies, another object of the present invention are the ophthalmic articles, such as ophthalmic or solar eyeglass articles, comprising: - at least one compound according to the invention and / or at least one polymer and / or a crosslinked material formed, at least in part from compounds of the invention, - and / or at least one photochromic composition as defined above, - and / or at least one matrix, as defined above, of an organic polymeric material or an inorganic material, or even of a hybrid organic-inorganic material, said matrix optionally comprising at least one compound of the invention. In practice, articles that more particularly cover the present invention are ophthalmic lenses or photochromic solar lenses, glazing (windows for buildings, for locomotion machines, motor vehicles), optical devices, decorative articles, sunscreen articles, storage of information, ... The present invention is illustrated by the following examples of synthesis and photochromic validation, of the naphthopyrans of the invention. Those compounds of the invention are compared with a prior art compound of C1.

EXAMPLE 1 Synthesis of compound (1) Step 1 The following mixture of 10 g of 9-acetyl fluororen (Brown et al, tetrahedron Asymmetry 1996, 7, 2029), 5.47 g of ethyl cyanoacetate, 4 g of ammonium acetate, 2 g of acetic acid in 60 ml is heated. of toluene, under reflux for 4 hours in a 100 ml conical flask equipped with a Dean-Stark trap. The reaction mixture is diluted with 50 ml of toluene and then washed with 200 ml of water and then 100 grams of saturated sodium bicarbonate solution. The solution is dried over magnesium sulphate and then evaporated to dryness. 15 grams of a yellowish oil are obtained. A yield of 80% is estimated according to the proton NMR.

Step 2 The following mixture was heated at 200 ° C for 3 hours: 14 grams of the product from the previous step in 15 grams of acetamide. The mixture was then poured while it was hot to 300 ml of water with stirring. Two extractions were carried out with dichloromethane (200 + 100 ml). The organic phase was then washed with 2 x 100 ml of water dried over sodium sulfate. i i- < »L- - Ms. _ .. magnesium and then reduced to dry. The product is purified by chromatography on silica elution with toluene and then toluene / chloroform (1/1). The purest fractions containing product are recovered and reduced until dry. 1.1 grams (10%) of yellow powder are isolated.

Step 3 Heat, about 200-220 ° C for 6 hours in a 125 ml reactor (the developed pressure is about 30 bars) the following mixture: 1.0 grams of the product from the previous step, 2 grams of sodium hydroxide in 10 ml of ethanol. 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 with slow and progressive addition of concentrated hydrochloric acid. The precipitate is recovered by filtration, washed with 2 x 20 ml of water and then dried under vacuum at 40 ° C overnight. Yield of 0.9 grams (99%).

Step 4 The following mixture of 0.6 grams of the product from the previous step (2.58 mmol), 0.98 g of 1,1-bis (para-methoxyphenyl) pripin-1-ol (3.66 mmol), in the presence of an amount, is heated under reflux. catalytic bromoacetic acid in 10 ml of xylene, for 3 hours in a 100 ml reactor. The mixture is then washed with 3 x 30 ml of potassium hydroxide at 3N and then with 50 ml of water containing 2 grams of NaCl. The product is then purified by chromatography on silica elution with toluene. The purest fractions are combined and then reduced to dryness. After recrystallization from a toluene / diisopropyl ether mixture, 140 milligrams of the compound (1) are recovered in the form of a clear yellow solid. • 5 Its structure is confirmed by NMR spectroscopy.

EXAMPLE 2 Synthesis of the compound (2) Steps 1 to 3 • The naphthol derivative is synthesized, in the same manner as the compound of Example 1, from methyl-9-xanthenyl ketone. (Rochlin et al., J. Amer. Chem. Soc, 1992, 114, 230): Step 4: The following mixture of 1.0 grams of the product from the previous step (4 mmol), 1.3 grams of 1,1-bis (para- • methoxyphenyl) propin-1-ol (4.8 mmol), under the presence of a catalytic amount of bromoacetic acid in 15 ml of xylene, for 2.5 hours. Then the mix with 2 x 25 ml of potassium hydroxide at 3N and then with 25 ml of water. The photochromic product is then isolated after 2 successive purifications by chromatography on a column of silica (eluent heptane / toluene 70/30 and then ethyl acetate / heptane 20/80), followed by recrystallization of .-..-- »" ¿___-- lj > ., - »-__-- > ", -» - »-. . ' - - - - - O »_-. - Á- «__B-Í- THF / ethanol. 150 milligrams of a transparent yellow product are obtained. 7.5% yield. Its structure is confirmed by proton NMR.

EXAMPLES 3 • 5 Synthesis of the compound (3) The following mixture of 0.95 grams of reflux was heated under reflux.

Naphthol from step 3 of the preceding synthesis (3.8 mmol), 1.25 grams of 1-p-dimethylamino-phenyl-propin-1-ol (5.0 mmol), in the presence of an amount catalytic bromoacetic acid in 15 ml of toluene, for 1.5 hours. HE • then diluted the mixture with 15 ml of THF and then neutralized with 1 gram of sodium bicarbonate. The solution was then filtered and then reduced to dryness. The product was subjected to purification by chromatography on an eluted silica column with a 70/30 toluene / heptane mixture. The recoveries are photochromic fractions, evaporate until dry and are then heated in a mixture of 5 ml of THF and 20 ml of heptane. After 2 hours of stirring at room temperature, the crystallized product of the product is recovered by filtration. • green tint. Yield: 400 mg (32%). Its structure is confirmed by NMR of protons. --------- ^ l-Í --- _-- .. .i- -v EXAMPLES 4 Synthesis of the compound (4) Step 9 9.9-Sp.rocyclopentyl-10-acetyl-9,10-dihydroanthracene was prepared according to the following sequence: (1) reduction of the spiromocyclopentylantrone (WO 96/30357) with sodium borohydride in trifluoroacetic acid ( W. Gribble et al., Synthesis, 172, 1977); (2) condensation of the lithium organ reagent formed by the action of t-BuLi on acetaldehyde (W. f. Adam et al., Chem. Ver., (126), 2697, 1993), which results in alcohol; (3) oxidation of the hydroxyl function to a carbonyl function with the help of pyridinium chlorochromate (E. J. Crey et al., Tetrahedron Lett., 2647, 1975).

Step 2: 15 The following mixture of 5.05 grams of water is heated under reflux 9,9-SpO cyclopentyl-10-acetyl-9,10-dihydro-anthracene, 2.22 grams of ethyl cyanoacetate, 1.1 ml of acetic acid, 6 grams of ammonium acetate (1.5 grams added every 4 hours) in 50 ml of toluene, for 12 hours in a 100 ml conical flask equipped with a Dean-Stark connector. 20 After 5 grams of acetamide are added to the medium and the control temperature is raised to 250 ° C. After all the solvent has been distilled off, the reflux is maintained for 5 hours. The mixture is then poured, while hot, into 100 ml of water with stirring. HE --- 4 -, -_ - _ fa _-- fc_. * -_ ----- _ __ ^ - i.a - _ _ ». ^ fe ^ at .. ._ __ .- _ ^ j.- _ -, .i., - t-. ? make two extractions with toluene THF 1/1 (2 x 50 ml). The organic phase is then washed with 30 ml of water and then 30 ml of a saturated solution of sodium chloride, dried over magnesium sulfate and then reduced to dryness. A brown oil is obtained. The product is purified by chromatography on silica elution with a mixture of toluene / diisopropyl ether (1/1). The purest fractions containing the product are recovered, which are reduced to dryness before recrystallization of the desired product from toluene. 2.4 g (40%) of a yellow powder are isolated.

Step 3 # The following mixture of 2.3 grams of product from the previous step, 2.6 grams of sodium hydroxide in 30 ml of ethanol, is heated to approximately 200-220 ° C for 5 hours in a 125 ml reactor (the pressure developed it is approximately 30 bars). After cooling, it transfer the mixture to a flask and then reduce until dry. The paste is then dissolved in 100 ml of water and then neutralized by the slow and progressive addition of concentrated hydrochloric acid. It recovers by filtration • the precipitate is elevated with 2 x 20 ml and then dried under vacuum at 40 ° C overnight. A brown solid is collected with quantitative yield. Step 4 The following mixture of 750 mg of the product from the previous step, 670 mg of 1,1-bis (para-methoxyphenyl) propin-1-ol, was heated under reflux in presence of a catalytic amount of bromoacetic acid in 20 ml of xylene, for 4 hours in a 50 ml reactor. After evaporation of the solvent, the product is purified directly, first by chromatography on silica gel eluting with toluene and then by filtration on alumina gel. The purest fractions are combined and reduced until dry. 79 mg of the sub-compound (4) are recovered in the form of a violet-colored oil. Its structure is confirmed by NMR spectroscopy.

EXAMPLE 5 10 Compound C1 • C1 was considered C1 compound of the prior art of the formula: This compound is commercially obtainable. - "aA> aBMMa''Mi EXAMPLE 6 The photochromic properties of said compounds (1) to (4) and C1 were evaluated. 5 These compounds are dissolved at a rate of 5 mg in 50 ml of THF. The visible UV absorptions are then measured (optical path of 1 cm), before and after exposure to a UV irradiation source of 365 nm. The observation of the dyes and the intensities developed is done by placing the solutions in the sun or before a solar simulator. The properties of these compounds are given in the following table. • _-- il ---------- ÍÍÍ ^^ -_- É &_; > -, -. . . . I composed before your exposure - > This is demonstrated with these measurements that the naphthopyrans of the invention have greater than the analogous compound without ring annealed at positions 6, 7, 7, 7 and 7. of the naphthopyran and this improves its sensitivity to solar radiation. The? 2 of the compounds are also larger (batochromic change) and the intensities developed in the presence of UV rays or solar rays are much greater for the analogous compound. • l ------------ Í -------- i --- a ^ ____ l-iJ- - --- • «- * '.? í-.t,. »-» -.;. ? . __.-.- -. -. - « - «..-, -«. . ..- -. ', ... ¿ i ...-- -

Claims (10)

NOVELTY OF THE INVENTION CLAIMS

1. - Naftopyrans of the following formula wherein: L corresponds to a direct bond or divalent residue: O, S, NRβ (Re represents a linear or branched alkyl group comprising from 1 to 6 carbon atoms), CR7Rs, (CR Rβ) 2, R7C = CRs ( representing R and Re, which are Identical or different, independently an H, an OH, or a linear or branched alkyl or alkoxy group comprising from 1 to 6 carbon atoms) or a carbocycle selected from the following: R-i and R2 independently represent: a 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 group or _ * -.- • - ^ * ^ ----- ^. < -i J., 4 - »_ * - á__ • _ heteroaryl comprising in its basic structure of 6 to 24 carbon atoms or from 4 to 24 carbon atoms respectively and at least one heteroatom selected from sulfur, oxygen and nitrogen; said basic structure being optionally substituted by at least one substituent selected from: a halogen, and notably fluorine, chlorine and bromine, a hydroxy group, a linear or branched alkyl group comprising from 1 to 12 carbon atoms, a linear alkoxy group or branched linear or branched comprising from 1 to 12 carbon atoms, a halogenoalkyl or halogenoalkoxy group corresponding to the above alkyl or alkoxy groups of CrC? 2 respectively which are substituted by at least one halogen atom and notably a fluoroalkyl group of that type, a linear or branched alkenyl group comprising from 2 to 12 carbon atoms, and notably a vinyl group or an allyl group, a -NH2 group, a -NHR group, R represents a linear or branched alkyl group comprising from 1 to 6 carbon atoms, a group representing R 'and R ", which are identical or different, independently a linear or branched alkyl group comprising from 1 to 6 carbon atoms, or representing, together with the nitrogen atom to which they are attached, a ring of 5 or 7 members which may comprise at least one other heteroatom selected from oxygen, sulfur and nitrogen, being * • ^ I J #, k - > -i-¡& i »* optionally substituted said nitrogen with a group R" \ which is a linear or branched alkyl group comprising from 1 to 6 carbon atoms, a methacryloyl group or an acryloyl group, an alkyl or heteroalkyl group, comprising the alkyl group, which is linear or branched, of 1 to 4 carbon atoms and the aryl and heteroaryl groups having the definitions given above, or said two substituents Ri and R2 together form an adamantyl, norbonyl, fluorenylidene, dialkyl (CrC6) anthracenylidene group or spiro-cycloalkyl (C5-C6) anthracenylidene, said group optionally being substituted by at least one of the substituents listed above for Ri, R2: an aryl or heteroaryl group: R3 and R4, which are identical or different, independently represent: hydrogen, a halogen, and notably fluorine, chlorine or bromine, a linear or branched alkyl group comprising from 1 to 12 carbon atoms (advantageously from 1 to 6 carbon atoms), a group cycloalkyl comprising from 3 to 12 carbon atoms, a linear or branched alkoxy group comprising from 1 to 12 carbon atoms (advantageously from 1 to 6 carbon atoms), a halogenoalkyl, halogenocycloalkyl or halogenoalkoxy group corresponding to alkyl groups, cycloalkyl, alkoxy above respectively, which are substituted by at least one halogen atom, selected notably from fluorine, chlorine and bromine, an aryl or heteroaryl group having the same definition as that given above for Ri, R2, an aralkyl group Heteroalkyl, the alkyl group comprising linear or branched, 1 to 4 carbon atoms, and the aryl and heteroaryl groups having the same definitions as those given above for Ri, R2) an amine or amide group: -NH2, -NHR, -CONH, -CONHR, having R, R ', R "their respective definitions given above for the amine substituents of the Ri, R2: aryl or heteroaryl, an OCORß or -COORß group, representing R & a straight or branched alkyl group comprising from 1 to 6 carbon atoms, or a cycloalkyl group of fe comprises from 3 to 6 carbon atoms, or a phenyl group, optionally substituted by at least one of the substituents listed above for the values of Ri, R2: aryl or heteroaryl; they are, independently, integers from 0 to 4 and from 0 to 3 respectively, R5 represents: a nitrogen, a linear or branched alkyl group comprising from 1 to 12 carbon atoms 15 (advantageously from 1 to 6 carbon atoms), a cycloalkyl group comprising from 3 to 12 carbon atoms, a linear or branched alkenyl group comprising from 2 to 12 carbon atoms, and notably a vinyl group or an allyl group , a phenyl or benzyl group, optionally substituted by at least one of the substituents listed 20 above for the values of R 1, R 2: aryl or heteroaryl, a group -COR 7, -COOR 7 or CONHR 7, R 7 representing a linear or branched alkyl group comprising 1 to 6 carbon atoms, or a cycloalkyl group comprising 3 to 6 carbon atoms, or a phenyl or benzyl group optionally substituted by at least one of the substituents listed above in the definition of the radicals Ri, R 2 in the formula (I), in which case these radicals correspond independently or a aryl or heteroaryl group.

2. Naphthopyrans according to claim 1, of the formula (I 1): in which: L represents a direct bond, an oxygen, a radical -CH2- 15 o (CH3) 2C, or the next carbocycle • Ri and / or R2, independently represent optionally substituted aryl or heteroaryl groups whose basic structure is selected from the group phenyl, naphthyl, biphenyl, pyridyl, furyl, benzofuryl, dibenzofuryl, N-alkyl (CrC6) carbazole, thienyl, benzothienyl, dibenzothienyl, julodidinyl; R-i and / or R2 representing advantageously a para-substituted phenyl group or Ri and R2 together form an adamantyl or norbonyl group; R5 represents a hydrogen, a linear or branched alkyl group comprising from 1 to 6 carbon atoms, an optionally substituted phenyl or benzyl group, a group -COR7, -COOR7 or CONHR7, wherein R7 represents a linear or branched alkyl group comprising 1 to 6 carbon atoms, or an optionally substituted phenyl or benzyl group.

3. Naphthopyrans according to claim 1, of the 10 formula (I) in which L does not correspond to a direct link.

4. A method of preparing naphthopyrans of the formula (I) according to any of claims 1 to 3, further characterized in that it consists essentially in carrying out a condensation: at least one compound of the formula (II) following: wherein R3, R4, R5, L, m and n are as defined above with reference to formula (I); at least one propargyl alcohol derivative of the following formula (III): 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 catalyst, this catalyst being preferably selected from the group comprising: para-toluenesulfonic acid, dodecyl sulfonic acid and bromoacetic acid, or with an aldehyde derivative of the formula (III ') next: "r A = ^ RT CHO (iir) where Ri and R2 are as defined above with reference to the formula (I); the condensation (ll) / (IH ') being carried out in the presence of a metal complex, preferably a titanium complex, with the titanium (IV) ethoxide being particularly preferred.

5. The method according to claim 4, further characterized in that the starting compound (II) is produced by carrying out the following essential steps: 1) Reaction of the precursor (Ipi) of the formula: ..¿-- j. 1 with at least one alkyl cyanoacetate of the formula NC-CH2-COORa with Ra = alkyl, preferably ethyl, in order to obtain the intermediate compound (Ipi): 2) thermal cyclization of (lp2) that gives rise to the intermediate compound (Ip3): 3) high temperature deciation of (Ip3> to produce the compound

6. - A (co) polymer and / or crosslinked material obtained by polymerizing and / or interlacing at least one monomer comprising at least one naphthopyran according to claim 1 or 2.

7. A photochromic compound further characterized in that it consists of in a compound according to any one of claims 1 to 3, or a mixture of at least two compounds according to any one of claims 1 to 3, or a mixture of at least one compound according to any of the claims 1 to 3, at least with another photochromic compound of another type and / or at least one non-photochromic coloring agent.

8. A photochromic compound further characterized in that it comprises: at least one compound according to any of claims 1 to 3, and / or at least one linear or interlaced (co) polymer containing, in its structure, at least minus one compound (I) according to claim 1 or 2; and, optionally, at least one other photochromic compound of another type and / or a non-photochromic coloring agent and / or at least one stabilizing agent.

9. A polymer (co) matrix, further characterized in that it comprises: at least one compound according to any of claims 1 to 3; and / or at least one (co) polymer and / or crosslinked material according to claim 6; and / or at least one composition according to claim 8.

10. - The matrix according to claim 9, further characterized in that the (co) polymer of the following list is selected: alkyl, cycloalkyl, (poly or oligo) ethylene glycol, aryl or arylalkyl, mono-, di-, tri- or tetraacrylate, or mono-, di-, tri- or tetramethacrylate, 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 group and / or or amide; polystyrene, polyether, polyester, polycarbonate (for example polycarbonate of bisphenol-A, polycarbonate of diallildiethylene glycol), polycarbamate, polyepoxy, polyurea, polyurethane, polythiourethane, polysiloxane, polyacrylonitrile, polyamide, aliphatic or aromatic polyester, vinyl polymers, cellulose acetate, triacetate of cellulose, cellulose acetate-propionate or polyvinyl butyral; difunctional monomers having the following formula: wherein: River, R'10, Rn and R'n are identical or different and independently represent a hydrogen or a methyl group; mi and n-i are, independently, integers between 0 and 4 (inclusive); and are advantageously independently equal to 1 or 2; X and X ', which are identical or different, are a halogen and 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 the precursor monomers of the ií? ^ l. * -, 1 -t »? --- * - L -, .. W-at-a .''-, - »-_- -» ^ - s - ••,. .-----, -_ • «---. .. . J .--- 1.1 polymers listed above (notably those belonging to the group comprising: (meth) acrylic monomers, vinyl monomers, allilic monomers and mixtures thereof). 11.- An ophthalmic or solar article that includes: at least • a compound according to any of claims 1 to 3; and / or at least one composition according to claim 8; and / or at least one (co) polymer and / or crosslinked material according to claim 6; and / or at least one matrix according to one of claims 9 or 10. 10 12. The article according to claim 11, further characterized in that it is constituted by a lens, by a glassware unit or by a device optical. • .-fef-flateT --- | -? a -----, the ^ aVaÍf? «- T.T-. - > »•» * I-- »--__. --AaMa- ». -. . - »-_-. -__---,. < -.- to. . - V ----- Ja.-, > ----------- i