FR2738570A1 - Photochromic spiro-oxazine type cpd., used to mfr. ophthalmic lenses - Google Patents

Abstract

A photochromic spiro-oxazine type cpd. of formula (I) is new. In (I), R1 = asymmetric aliphatic monocyclic gp. directly connected to the N atom, having 5-7 members and opt. comprising a heteroatom(s), and of formula (i); l = 1-12; R9 = H, alkyl, alkoxy, dialkylamino, alkyl ester or CN, provided at least one R9 is not H; R2, R3 = 1-12C alkyl, alkenyl, alkynyl, aryl, alkylaryl or cycloalkyl, or R2 and R3 can form a 5-10 membered carbocyclic or heterocyclic gp.; R4-R7 = H, an opt. halogenated alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, aryloxy or aralkyl gp., halogen, OR, SR, -OCOR, -COOR, polyether, polyamide, polycarbonate, polycarbamate, polyurea, polyester, an amino radical which gives rise, once it is bound in (I), to a prim., sec. or tert. amine which is alkyl, aryl or aralkyl mono- or disubstd., an amino-cyclic radical opt. contg. a heteroatom(s), or an electron withdrawing gp., pref. CF3, CN, NO2 or SCN, where at least two of R4-R7, pref. borne by two adjacent C atoms, can combine to form an aromatic 5-6 membered ring(s) or an aliphatic 5-7, pref. 5-6 membered ring(s), which opt. comprises a heteroatom(s), so as to form a heterocyclic ring(s) opt. substd. by a radical(s) defined as for R4-R7; R = H, alkyl and/or cycloalkyl and/or aryl; A = (hetero)aromatic ring, opt. substd. by a radical(s) R8, defined as for R4-R7; and n = integer, where when n \- 2, two R8 may combine to form a (hetero)aromatic ring(s). Also claimed are: (1) a co(polymer) and/or crosslinkage obtd. by polymerisation and/or crosslinking of a monomer(s) comprising (I); (2) a (co)polymer which is grafted to a cpd(s) (I); (3) a photochromic compsn. comprising a cpd(s). (I) and/or a (co)polymer(s) as in (1) or (2), and opt. a further photochromic cpd(s). and/or a dye(s) and/or a stabiliser(s); (4) a (co)polymer matrix comprising a cpd(s). (I) and/or a (co)polymer(s) as in (1) or (2) and/or a compsn(s). as in (3); (5) an ophthalmic or sun-protection device comprising such cpd(s), (co)polymer(s) and/or compsn(s).; and (6) a glass partition and/or optical device comprising such cpd(s)., (co)polymer(s), compsn(s). and/or matrix(es).

Description

 The present invention relates to novel spiroxazine compounds having, in particular, photochromic properties. It also relates to photochromic compositions and ophthalmic articles (e.g., lenses) containing these spiroxazines.

 The photochromic compounds are capable of changing color under the influence of a poly- or monochromatic light (eg W) and recovering their initial color, when the light irradiation ceases, or under the influence of a poly- or monochromatic different from the first, or under the influence of temperature and / or a poly- or monochromatic light different from the first.

 These photochromic compounds have applications in various fields, for example, for the manufacture of ophthalmic lenses, contact lenses, sunglasses, filters, camera optics or cameras or other optical and observation devices, glazing, decorative objects, display elements or even for the storage of information by optical inscription (coding).

In the field of ophthalmic optics, and in particular eyewear, a photochromic lens, comprising one or more photochromic compounds, must exhibit - high transmission in the dark or in the absence of sunlight, - low transmission ( strong colorability) under solar irradiation, - appropriate coloring and discoloration kinetics, - a color acceptable by the consumer (gray or brown)
preferably) with, preferably, a maintenance of the
shade chosen during the coloring and
discoloration of the lens, - a maintenance of the performances of the properties in a range
temperature of 0-400C, - significant durability, because the objectives are
corrective lenses that are sophisticated and therefore expensive.

 These lens characteristics are, in fact, determined by the active photochromic compounds, which must, in addition, be perfectly compatible with the organic or inorganic support constituting the lens.

 It should also be noted that obtaining a gray or brown hue may require the use of at least two photochromics of different colors, that is to say having wavelengths of maximum absorption. in the visible (X,) distinct. This association imposes other requirements on photochromic compounds. In particular, the staining and fading kinetics of the two or more associated active photochromic compounds must be substantially identical. It is the same for their stability over time and, also, for their compatibility with a plastic or mineral support.

Among the numerous photochromic compounds described in the prior art, mention may be made of the indolinospironaphthoxazines described in the patents
US 3,578,602, US 3,562,172, US 4,215,010, EP 0 171 909,
EP 0 313 941, FR 2 647 789 and EP 0 600 669

 The R1 group of these molecules being linear or branched alkyls, alkylaryls or alicyclic.

These compounds claim to meet the specifications defined above.

 In fact, if these compounds do have one or more of the desired basic properties, such as high transmission in the dark, high colorability under solar irradiation, absorption in blue or violet (570-630nm), kinetics rapid coloring and discoloration, all the compounds described to date do not have the complete combination of desired properties, necessary for the production of satisfactory articles, susceptible of industrial manufacture.

 If the prior art teaches how to modify the absorption band by adding substituents on the different positions of the rings and also how to modify the kinetics of discoloration, on the other hand, it does not teach how to increase the colorability of these molecules without to increase the residual staining in the inactivated state and, above all, to make them photochemically stable in order to allow their use on an industrial scale. Indeed, without good stability, these expensive molecules, introduced into a sophisticated lens, can not be used.

 It is to the merit of the Applicant to have found, in a surprising way, that the presence of a monocyclic substituent group dissymmetrical on the nitrogen atom of the indolino portion of certain indolino-spiroxazines made it possible to solve the problem of Residual staining and colorability, essential for the intended applications.

 The originality of the invention lies in the surprising effect of the asymmetric monocyclic group which increases the colorability of spiroxazines, without increasing their residual color, while ensuring good photostability.

dans laquelle, - R1 est un groupe monocyclique aliphatique dissymétrique
directement lié à l'atome d'azote, ayant de 5 à 7
chaînons, pouvant comporter au moins un hétéroatome et
répondant à la formule

où 1 = 1 à 12, et R9 est H ou un groupe alkyle, alcoxy, dialkylamino, alkylester ou CN avec la condition qu'au moins un des R9 n'est pas H.Thus, the present invention relates to a compound, in particular a photochromic compound, of general formula (I) below

in which - R1 is an asymmetric aliphatic monocyclic group
directly linked to the nitrogen atom, having from 5 to 7
which may comprise at least one heteroatom and
answering the formula

where 1 = 1 to 12, and R9 is H or alkyl, alkoxy, dialkylamino, alkyl ester or CN with the proviso that at least one of R9 is not H.

- R2, R3 are identical or different and represent a
alkyl group, linear or branched, from 1 to 12 atoms
carbon, alkenyl, alkynyl, aryl, alkylaryl,
cycloalkyl, R2 and R3 may possibly be taken
together to form a carbocyclic group or
heterocyclic ring of 5 to 10 atoms, - R4, R5, R6, R7 are the same or different and
represent
hydrogen
an alkyl, cycloalkyl, alkenyl or alkynyl group,
aryl (preferably phenyl, mono-naphthyl, -di-or tri
substituted by donor or acceptor groups
of electrons), heteroaryl, aryloxyl or aralkyl,
group being optionally halogenated,
a halogen, preferably F, Br, Cl,
OR, SR, -OCOR, -COOR, with R = H, alkyl and / or
cycloalkyl and / or aryl,
a (poly) ether, a (poly) amide, a (poly) carbonate, a
(poly) carbamate, a (poly) urea or a (poly) ester,
an amino radical giving birth, once bound
in (I), to a primary, secondary or
tertiary, said amine being alkyl, aryl or
aralkyl, mono or disubstituted according to its nature,
* or an aminocyclic radical containing,
optionally, one or more heteroatoms,
or a selected electron-withdrawing group of
preferably, in the group comprising CF3, CN, NO2, SCN, - at least two of the radicals R4, R5, R6, R7, preferably
borne by two vicinal carbon atoms,
possibly together form at least one cycle
5- or 6-membered aromatic or aliphatic having
5 to 7 members, advantageously 5 or 6 members, said (or
said cycle (s) comprising, optionally, at least one
heteroatom, so as to form at least one nucleus
heterocyclic, this (these) last (s) possibly being
substituted by one or more radicals, identical or
different, and meeting the same definition as
above for R4 to R7, - A represents a (hetero) aromatic ring (containing by
example, at least one nitrogen atom) and which can be
substituted with one or more radicals R8, which are identical or
different, and meeting the same definition as
given above for R4 to R7, - n is an integer and when n 2 2, two of the radicals
R8 can possibly be taken together to form at
less an aromatic or heteroaromatic cycle.

The term "asymmetric" in the term "asymmetric aliphatic monocyclic group means that the plane perpendicular to ring B of group R1 and including the line segment representing the ring B bond to the nitrogen atom is not a plane of symmetry for the group
R1, it being understood that one reason on the formula developed in a plane of the group R1.

parmi beaucoup d'autres.Specific examples of groups R1 are as follows

among many others.

où A, et R' à R7 sont tels que définis ci-dessus et D est un cycle aromatique ou aliphatique de 5 à 7 chaînons, comprenant éventuellement un hétéroatome, qui peut être substitué ou non par un ou plusieurs radicaux, identiques ou différents, et répondant à la même définition que celle donnée pour R4 à R7.Preferred compounds of the invention have the following formula (I ')

where A, and R 'to R7 are as defined above and D is an aromatic or aliphatic ring of 5 to 7 members, optionally comprising a heteroatom, which may or may not be substituted by one or more radicals, which may be identical or different, and having the same definition as that given for R4 to R7.

dans laquelle R1 à R4 et R6 à R8 sont tels que définis supra, et n et m prennent les valeurs 0 à 4.According to a particularly preferred embodiment of the invention, the ring A is a phenyl group and R4 and R5 are taken together to form an aromatic ring. This corresponds to the following formula (I ")

wherein R1 to R4 and R6 to R8 are as defined above, and n and m are 0 to 4.

 Among the possible substituents for the compounds of formula (I), (I ') and (I ") according to the invention, it is appropriate to envisage groups R4 to R9 comprising and / or forming at least one reactive function of polymerization and / or crosslinking, preferably selected from the following list: alkenyl - advantageously vinyl methacryloyl, acryloyl, acryloxyalkyl, methacryloxyalkyl or epoxy.

 Thus, the photochromic compounds according to the invention can be conceived as monomers, of different or different natures, capable of reacting with each other or with other comonomers, to form homopolymers and / or copolymers, carrying a photochromic functionality and possessing mechanical properties of macromolecules. It follows that one of the objects of the present invention is formed by those homopolymers or copolymers comprising (co) monomers and / or by reticulates, at least partly constituted by photochromic compounds (I), ) or (I ") according to the invention.

 In the same vein, the aforementioned compounds (I), (I ') and (I ") can be envisaged as crosslinking agents provided with reactive functions capable of allowing bridging between polymer chains of photochromic nature or No. The reticles, which can thus be obtained, are also another object of the present invention.

In general, in the preceding formulas, according to the invention, the term "alkyl" is preferably used to denote a hydrocarbon group.
linear or branched having from 1 to 12 carbon atoms - by "alkoxyl", a group -O-alkyl,
having, preferably, from 1 to 10 carbon atoms, - "aryl", an aromatic hydrocarbon group
comprising at least 6 carbon atoms, - with "heteroaryl", an aromatic hydrocarbon group
comprising at least 5 atoms and of which at least one is a
heteroatom, - "aralkyl", a group comprising at least one
alkyl and at least one aryl, as defined above, - by "heteroatom", the different atoms of C and H and
preferably belonging to the following group: N, O, and
S.

 The photochromic components used particularly preferably in the context of the invention are therefore, as is apparent from the foregoing, indolinospironaphtoxazines or indolinospirobenzoxazines.

où R1 =

n = 0,1 ou 2 et
R2, R3 = alkyle en C1-C5,
R4 = H, OMe,
R6 = H, OMe ou amino.Among the most advantageous indolinospiroxazines, mention may be made of those of formula

where R1 =

n = 0,1 or 2 and
R2, R3 = C1-C5 alkyl,
R4 = H, OMe,
R6 = H, OMe or amino.

R8 = H, Me, OMe or CF3
It is the merit of the Applicant to have disclosed these compounds, because they have particularly advantageous photochromic properties. More specifically, they are endowed with a strong colorability, in particular in the field of blue. They thus lend themselves well to a combination - in all compatibility and complementarity - with photochromes absorbing in the yellow, orange, red and violet, so as to obtain a broad coverage of the spectrum visible in absorbance and thus shades of brown or gray coloring. dark.

 Their sensitivity, as well as the height and area of their X peaks, in the visible, reach satisfactory values.

 These compounds are, moreover, perfectly stable and compatible with support matrices made of organic polymer or mineral material, both in the form included in the matrix and in the form of a coating.

 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 a light W (365 nm) or a solar-type light source. Finally, they quickly recover their initial color when irradiation ceases.

The compounds of the invention may be obtained by condensation of an indoline derivative substituted with an asymmetric aliphatic monocyclic R1 group and an aromatic nitrosoalcohol derivative such as those described, for example, in US Pat. Nos. 3,578,602 and 4,634,767. , US 4,913,544 and EP-A-600,669. This reaction can be carried out in solvents such as ethanol, toluene or dichloroethane.

The indoline derivatives are obtained by methods adapted from the literature.

Step 1 is carried out according to a procedure described in Katritzky et al., Tetrahedron, 1991, 47, 2683. The nitrosation of the amine (step 2) is carried out by reaction with sodium nitrite - hydrochloric acid and the reduction of the nitroso derivative (step 3) is carried out by reaction with LiAlH 4 in THF (Fridman et al., Russian
Chemical Reviews 1971, 40 (1), 34). The last synthesis stage (4) is carried out by reaction of the hydrazine with the appropriate ketone in an acid medium, for example hydrochloric acid / ethanol or acetic acid (for a general review on this reaction, it is possible to consult
Robinson "Fischer indole synthesis" Wiley-Interscience, 1982).

 As regards the applications of the compounds according to the present invention, it should be noted that they can be used as photochromic material dispersed in the surface part or in the mass of a polymer or mineral matrix. They can also be used in solution.

 A photochromic solution can be obtained by solubilizing the compound in an organic solvent, such as toluene, dichloromethane, tetrahydrofuran or ethanol. The solutions obtained are generally colorless and transparent. Exposed to sunlight, they develop a strong coloration and return to the colorless state when they are placed in an area of least exposure to solar radiation or, in other words, when they are no longer subjected to the W. In general, a very low concentration of product (of the order of 0.01 to 5 W) is sufficient to obtain an intense coloration.

 The most interesting applications are those in which the photochromic is dispersed uniformly within or on the surface of a polymer, copolymer or mixture of polymers. The implementation methods that can be envisaged are very varied. Among those known to those skilled in the art, there may be mentioned, for example, the diffusion in the (co) polymer, from a suspension or solution of photochromic, in a silicone oil, in an aliphatic hydrocarbon or aromatic, in a glycol, or from another polymer matrix. The diffusion is commonly carried out at a temperature of 50 to 2000C for a period of 15 minutes to a few hours, depending on the nature of the polymer matrix.

 Another implementation technique consists in mixing the photochromic in a formulation of polymerizable materials, depositing this mixture on a surface or in a mold and then performing the polymerization.

These and other processing techniques 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.

 According to a variant of the invention, it is also possible to graft the photochromic onto (co) polymers. Thus, another subject of the invention is formed by the (co) polymers grafted with at least one of the photochromics described above.

By way of examples of preferred polymeric materials for optical applications of the photochromic compounds according to the invention, mention may be made of the following products: polyacrylate or alkyl polymethacrylate, cycloalkyl,
aryl or arylalkyl (mono, di, tri or tetra)
optionally halogenated or having at least one
ether and / or ester and / or carbonate group and / or
carbamate and / or thiocarbamate and / or urea and / or amide, - polystyrene, polycarbonate (eg polycarbonate
bisphenol-A, allyl polycarbonate diethylene glycol),
polyepoxy, polyurethane, polythiourethane, polysiloxane,
polyacrylonitrile, polyamide, aliphatic polyester or
aromatic, vinyl polymers, cellulose acetate,
cellulose triacetate, cellulose acetate propionate
or polyvinylbutyral, - copolymers of two or more types of monomer or
polymer mixtures referred to above, preferably
polycarbonate-polyurethane, poly (meth) acrylate
polyurethane, polystyrene-poly (meth) acrylate or
polystyrene-polyacrylonitrile, advantageously a mixture
polyester and polycarbonate or poly (meth) acrylate.

 The amount of photochromic used depends on the degree of darkening desired. Usually, an amount of from 0.001 to 20 W by weight is used.

 The photochromic compounds according to the invention may be used alone or as a mixture with other products to form a composition which may be in solid or liquid form, for example in solution or in dispersion, as already indicated above. These compositions, which constitute another subject of the invention, may therefore comprise the compounds (I), (I ') and (I ") of the invention and other complementary photochromic compounds which make it possible to obtain dark colorations. for example gray or brown, desired by the public in applications such as ophthalmic or solar eyewear.These complementary photochromic compounds have an X, and a surface of absorbance in the visible such that, after association with the compounds of the invention an absorbance spectrum covering all the visible and conferring the desired hue is obtained on the mixture of activated photochromes.

The photochromic (s) likely to be associated with the compounds of the invention are those known to those skilled in the art and described in the literature, for example chromenes (US Pat. No. 3,567,605, US Pat. No. 5,238,981). 94 22 850,
EP 0 562 915) spiropyrans or naphthospyropyrans (US 5,238,981) and spiroxazines (JC CRANO et al., "Applied
Photochromic Polymer Systems, "Ed. Blackie & Son Ltd, 1992, Chapter 2).

These compositions according to the invention may also comprise
non-photochromic dyes for adjusting the hue,
and / or one or more stabilizers, for example an antioxidant,
- and / or one or more anti-W,
and / or one or more antiradicals,
and / or one or more photochemical excited state quenchers.

 These additives can make it possible to improve the durability of said compositions.

 According to another of its aspects relating to the application of photochromic compounds (I), (I ') and (I "), the present invention also relates to ophthalmic articles, such as ophthalmic or solar eyewear, comprising at least one compound according to the invention and / or at least one (co) polymer formed, at least in part, of recurring units of the type (I), (I ') or (I ") and / or at least one composition comprising the compounds (I), (I ') or (ifs) according to the invention, as defined above, and / or at least one matrix, as defined above, of organic polymer material or mineral material or still mineral-organic hybrid material incorporating at least one compound of the invention.

 In practice, the articles more particularly targeted by the present invention are ophthalmic lenses or photochromic lenses, glazing (windows for buildings, for locomotion machines, motor vehicles), optical devices, decorative items, sun protection articles, storage of information, etc ...

 The present invention will be better understood in the light of the following examples, of synthesis and photochromic validation of the compounds (I), (I ') and (I ") it relates.

EXAMPLES
SYNTHESIS AND PROPERTIES OF PHOTOCHROMIC COMPOUNDS (1) TO (4)
ACCORDING TO THE INVENTION (EXAMPLES 1 TO 4)
The formulas of the compounds (1) to (4) are given below
(see Table 1)
EXAMPLE 1 SYNTHESIS OF THE COMPOUND (1)

STEP 1
SYNTHESIS OF 2-METHYLCYCLOHEXYLPHENYLAMINE
In a 100 ml flask, the mixture is refluxed for 30 hours according to 9.3 g of aniline, 11.2 g of 2-methylcyclohexanone and 12 g of benzotriazole. Subsequently, 200 ml of methanol and 5 g of Na BH4 were added portionwise and the mixture was refluxed for 30 minutes. The solution was allowed to cool and 100 ml of water was added and extracted with 2 x 100 ml of diisopropyl ether. The organic phase is recovered, dried over magnesium sulfate and then reduced to dryness. This gives 7 g of the desired amine.

2ND STEP
SYNTHESIS OF 1- (2-METHYLCYCLOHEXYL) -1-PHENYLHYDRAZINE
The amine of the preceding step (7 g) is suspended in 100 ml of hydrochloric acid (1 N), and the mixture is then kept at 0 ° C. with stirring. Then, in small portions, an aqueous solution of NaNO 2 (2 g in 20 ml of water) is added. The temperature is then allowed to rise to ambient temperature and the nitroso derivative is extracted with 2 × 100 ml of diisopropyl ether. After evaporation of the organic solvent, 8 g of product are recovered. This product is then slowly added in tetrahydrofuran (80 ml) containing 3 g of LiAlH 4 and then the mixture is refluxed for 1 hour. Subsequently, the mixture is cooled to 0 ° C., then the excess of hydride is neutralized with an aqueous solution of sodium hydroxide. Next, 30 g of Na 2 SO 4 are added, and then the organic phase is recovered by filtration and reduced to dry. 7 g of the desired hydrazine are obtained.

STEP 3
SYNTHESIS OF THE 2-METHYLENE INDOLINE DERIVATIVE.

 In a 100 ml flask, 7 g of the hydrazine of the preceding step and 3 g of 3-methylbutanone-2 are reacted in 30 ml of ethanol containing 1 drop of acetic acid at 500 ° C. 5 ml of concentrated hydrochloric acid are then added and the mixture is refluxed for 10 minutes. The medium is then neutralized with sodium hydroxide and the indole derivative extracted with 100 ml of diisopropyl ether.

After evaporation of the solvent, 3 g of the desired product are obtained.

STEP 4
SYNTHESIS OF SPIROXAZINE (1)
The product of the preceding step (3 g) and 1.8 g of 1-nitroso-2-naphthol are solubilized in 30 ml of ethanol, and then the mixture is heated at 700 ° C. for 30 minutes. The solvent is then evaporated under vacuum and the product is then isolated by chromatography on a silica column with toluene as eluent. The product obtained (1 g) is crystallized from heptane. 450 mg of slightly green product is 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 1200 ° C. for 24 hours: 12 g of 3,4-dimethylaniline, 11 g of 2-methylcyclohexanone and 12 g of benzotriazole. 2-methylcyclohexyl-2,4-dimethylphenyl amine is isolated after reduction, as in step 1 of Example 1. 18 g of an oily product are isolated.

Steps 2, 3 and 4
These steps were performed as before. The spiroxazine (2) is synthesized from 3.5 g of the indoline derivative and 2.2 g of 1-nitroso-2-naphthol in ethanol at 600 ° C. for 2 hours. 1.5 g of product are isolated after chromatography. Its structure is confirmed by spectroscopy
NMR. The latter shows the existence of several isomers, because of the positioning of the two methyls on the phenyl of the indole (the derivative 4,5 and the derivative 5,6-dimethyl) and the positioning of the nitrogen on the cycle (cis and trans relative to the 2-methyl group).

EXAMPLE 3: SYNTHESIS OF THE COMPOUND (3)
Step 1
In a 250 ml flask, equipped with a separator "Dean
Stark®, the following mixture is refluxed: 12-dimethylaniline, 20 g of menthone, 14 g of benzotriazole and 200 ml of toluene After recovery of the theoretical amount of water (16 hours), the mixture is reduced to dryness and then solubilized in 200 ml of methanol and the product is reduced with NaBH 4 as before, 25 g of an oily product are isolated.

Steps 2, 3 and 4
These steps were performed as before. The spiroxazine (3) is synthesized from 5 g of the indoline derivative and 3.5 g of 1-nitroso-2-naphthol in 60 ml of ethanol at 500 ° C. for 1 hour. After chromatography, 2 g of product are isolated. Its structure is confirmed by NMR spectroscopy.

EXAMPLE 4: SYNTHESIS OF THE COMPOUND (4)
This spiroxazine (4) is synthesized from 6 g of the indoline derivative of Example 3 and 4 g of 1-nitroso-7-hydroxy-2-naphthol in ethanol at 600 ° C. for 1 hour. The intermediate product 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) INTO
Polyacrylate.

General procedure: 10 mg of each of the compounds (1) to (4) are solubilized in bisphenol dimethylmethacrylate
A tetraethoxylated compound sold under the name DIACRYL 121 by the company AKZO) also containing 40 mg of 2'2'-azobis (2-methylbutyronitrile). The solution is then degassed, inerted with argon, and then poured into a glass lens mold 8 cm in diameter and 2 mm thick. The mold is then placed in an oven at 700 ° C for 12 hours.

After demolding, a transparent and rigid lens is obtained. Under solar irradiation, the glass quickly develops an intense blue color and becomes colorless in the dark. The photochromic characteristics are given in Table 1 below. By way of comparison, the characteristics of the compounds C1, C2, C3, C4 and C5 of the prior art are also given in Table 1 below.

TABLE 1
LEGENDS - Xmax measured in the D121 under 2 mm thick under
exposure of a 60,000 Lux xenon lamp at 220C, - TO = initial transmission (not activated state) measured at Xtnax, - TD15 = transmission after 15 min exposure measured at Amaxf - DOI = Induced Optic Density [Log (T0 / TD15)], - Rs = recovery of the initial transmission after 5 min of discoloration.

TABLE 1

<tb><SEP> Cc .'- <SEP> struchne <SEP> Rate <SEP> DOI <SEP> lxx
<tb><SEP> mn <SEP> rm <SEP> 46 <SEP> Z <SEP>%
<tb> 0.1 <SEP> 614 <SEP> 89 <SEP> 23 <SEP> 0.59 <SEP> 72
<tb><SEP> y <SEP> 41 <SEP> 624 <SEP> 89 <SEP> 4,8 <SEP> 127 <SEP> 60
<tb><SEP> h <SEP> 0.1 <SEP> 624 <SEP> 84 <SEP><SEQ> 1.82 <SEP> 45
<tb><SEP> Ex. <SEP> 4 <SEP><SEP> 4 <SEP> | <SEP> 13S <SEP>! <SEP> 40
<tb><SEP> (To
<tb><SEP> C <SEP> tw <SEP> 41 <SEP> 604 <SEP> 90 <SEP> 39 <SEP> 0.36 <SEP> 83
<tb><SEP> Q <SEP> 93 <SEP> 0.1 <SEP> 610 <SEP> 86 <SEP> 22 <SEP> 0 $ 9 <SEP> 74
<tb><SEP> C3 <SEP> 0 &<SEP> 41 <SEP> 616 <SEP> 86 <SEP> 18 <SEP> 0.69 <SEP> 68
<tb><SEP> C4 <SEP> 0.1 <SEP> 624 <SEP> 91 <SEP> 17 <SEP> 0.73 <SEP> 70
<tb><SEP> a <SEP> My <SEP> 0.1 <SEP> 620 <SEP> 81 <SEP> 19 <SEP> 03 <SEP> 63
<Tb>
A comparison of the properties of Example 1 and Comparative Examples C1 and C2, on the one hand, and Examples 2 and 3 and Comparative Examples C3-C5, on the other hand, show that the compounds of the prior art of similar structure but not possessing an asymmetric aliphatic monocyclic group according to the invention do not possess the advantageous combination of the desired properties.

In particular, it is found that the compounds of the invention have a better compromise initial weak staining and strong induced optical density.

Claims (14)

 1 - Photochromic compounds of general formula (I) below

 in which - R1 is an asymmetric aliphatic monocyclic group  directly linked to the nitrogen atom, having from 5 to 7  chain members, which may comprise at least one heteroatom and which corresponds to the formula

 where 1 = 1 to 12, and R9 is H or alkyl, alkoxy, dialkylamino, alkyl ester or CN with the proviso that at least one of R9 is not H.  less an aromatic or heteroaromatic cycle.  R8 can possibly be taken together to form at  definition as that given above for R4 to R7, - A represents a (hetero) aromatic ring which may be substituted by one or more R8 radicals, which may be identical or different, and which satisfy the same definition as that given above for R4 to R7, n is an integer and when n 2 2, two of the radicals  radicals, identical or different, and responding to the same  being possibly substituted by one or more  at least one heterocyclic ring, this (these) last (s)  optionally, at least one heteroatom, so as to form  5 to 7 members, said (or said) ring (s) comprising,  5- or 6-membered aromatic or aliphatic having  possibly together form at least one cycle  group comprising CF3, CN, NO2 and SCN, - at least two of the radicals R4, RS, R6, R7 being  or an electron-withdrawing group chosen in the  optionally, one or more heteroatoms,  * or an aminocyclic radical containing,  aralkyl, mono or disubstituted according to its nature,  tertiary, said amine being alkyl, aryl or  in (I), to a primary, secondary or  an amino radical giving birth, once bound  (poly) carbamate, a (poly) urea or a (poly) ester,  a (poly) ether, a (poly) amide, a (poly) carbonate, a  cycloalkyl and / or aryl,  OR, SR, -OCOR, -COOR, with R = H, alkyl and / or  a halogen,  group being optionally halogenated,  aryl, heteroaryl, aryloxyl or aralkyl, said  an alkyl, cycloalkyl, alkenyl or alkynyl group,  hydrogen  represent  heterocyclic ring of 5 to 10 atoms, - R4, R5, R6, R7 are the same or different and  together to form a carbocyclic group or  cycloalkyl, R2 and R3 may possibly be taken  carbon, alkenyl, alkynyl, aryl, alkylaryl,  alkyl group, linear or branched, from 1 to 12 atoms - R2, R3 are identical or different and represent a

 2. Photochromic compounds according to claim 1, characterized in that the group R1 is chosen from the following  where A, and R1 to R7 are as defined in the preceding claims, and D is an aromatic or aliphatic ring of 5 to 7 members, optionally comprising a heteroatom, which may or may not be substituted by one or more radicals, which are identical or different , and meeting the same definition as that given for R4 to R7.

 3. Photochromic compounds according to claim 1 or 2, characterized in that they correspond to the general formula  wherein R1 to R4 and R6 to R8 are as defined in claim 1, and n and m are 0 to 4.

 4. Photochromic compounds according to any one of claims 1 to 3, characterized in that they have the following general formula (I ")  5. Photochromic compounds according to claims 1 to 4, characterized in that the groups R1 to R9 of formulas (I), (I ') and (I ") according to the invention comprise and / or form at least one reactive group. polymerization and / or crosslinking, selected from alkenyl, methacryloyl, acryloyl, acryloxyalkyl, methacryloxyalkyl and epoxy.

 6. Photochromic compounds according to any one of claims 1 to 5, characterized in that they have the following formula where R1 = R6 = H, OMe or amino. R4 = H, OMe, R2, R3 = C1-C4 alkyl  n = 0,1 or 2 and

 R8 = H, Me, OMe or CF3.  7. (Co) polymer and / or crosslink obtained by polymerization and / or crosslinking of at least one monomer consisting of at least one photochromic compound according to claim 5.  8. (Co) polymer, characterized in that it is grafted with at least one of the photochromic compounds according to any one of claims 1 to 6.  and optionally at least one other photochromic compound and / or at least one dye and / or at least one stabilizer.  at least one compound according to any one of claims 1 to 6 and / or at least one (co) polymer according to claim 7 or 8,  9. Photochromic composition, characterized in that it comprises  and / or at least one composition according to claim 9.  and / or at least one (co) polymer according to claim 7 or 8,  at least one compound according to any one of claims 1 to 6,  10. Matrix (co) polymer, characterized in that it comprises  11. Matrix according to claim 10, characterized in that the (co) polymer is selected from the following list - polyacrylate or polymethacrylate alkyl, cycloalkyl, aryl or arylalkyl (mono, di, tri or tetra) optionally halogenated or having at least one ether and / or ester and / or carbonate and / or carbamate and / or thiocarbamate and / or urea and / or amide, - polystyrene, polycarbonate, polyepoxy, polyurethane, polythiourethane, polysiloxane, polyacrylonitrile, polyamide , aliphatic or aromatic polyester, polyvinyl acetate, cellulose acetate, cellulose triacetate, cellulose acetate propionate or polyvinylbutyral, - copolymers of two or more types of the monomers or polymer mixtures referred to above.  and / or at least one composition according to claim 9.  and / or at least one (co) polymer according to claim 7 or 8,  at least one compound according to any one of claims 1 to 6,  12. Ophthalmic or solar article comprising  13. Article according to claim 12, characterized in that it consists of a lens.  and / or at least one matrix according to claim 10 or 11.  and / or at least one composition according to claim 9,  and / or at least one (co) polymer according to claim 7 or 8,  at least one compound according to any one of claims 1 to 6,  14. Glazing and / or optical device comprising