Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
  • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
  • C07D498/10—Spiro-condensed systems

Definitions

• the subject of the invention is new photochromic compounds of the spiro [indoline- [2,3 '] - benzoxazine] type comprising at least one electron-attractor group linked in position 5' and / or 6 'to the benzoxazine part by a radical.
• di valent de junction comprising one ethylenic double bond or several conjugated ethylenic double bonds, and their use in the field of ophthalmic optics, in particular in and / or on ophthalmic lenses.
• positions 5 ', 6' to which reference is made above are defined by numbering according to the rules of international nomenclature the positions of the atoms on the basic structural element spiro [indoline- [2,3'J-benzoxazine] . By convention, this same indexing will be kept for the positions of the different atoms of the basic structural element of the compounds of the invention whatever the substituents and nuclei condensed on this basic structural element.
• Photochromism has been known for many years.
• a compound is said to be photochromic when this compound, irradiated by a beam of ultraviolet light, changes color and returns to its original color as soon as the irradiation ceases.
• any compound with photochromic property is not necessarily usable in the field of ophthalmic optics.
• 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;
• the photochromic compound suitable, alone or in combination with other photochromic compounds, for use in ophthalmic glasses or lenses;
• 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 compounds photochromic state of the art is their lifespan. 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.
• Document JP-A-03 251 587 describes photochromic compounds with a spiro [indoline- [2,3 '] - benzoxazine] structure substituted at 6'.
• the document WO-96/04590 describes photochromic compounds of spiro [indoline- [2,3 '] - benzoxazine] structure having a cyano or phenylsulfonyl group in the 6' position.
• the compounds of document WO-96/04590 have a high colorability, in their open form, in the visible range. Their colors are blue-green. They have, in their colored form, wavelengths at the absorption maximum of up to 659 nm.
• the photochromic compounds of this document exhibit a displacement of their absorption bands in the region of UV / visible radiation.
• the present invention relates to new photochromic compounds having improved characteristics compared to the compounds of the above prior art, and in particular for some of them, wavelength values at the maximum of absorption (form open) higher than for the compounds of document WO 96/04590.
• the photochromic compounds of the invention also exhibit, in their closed form, a displacement of their absorption bands towards UV / visible.
• the present invention also relates to such photochromic compounds whose photochromism manifests itself over a wide temperature range preferably ranging from 0 ° C to 40 ° C and more particularly at least up to 35 ° C, with excellent kinetics of coloring-discoloration at 35 ° C.
• the present invention also relates to optical and ophthalmic articles, such as glasses or lenses, incorporating these new photochromic compounds or coated with coating compositions comprising these new photochromic compounds.
• compositions intended to be used for coating optical or ophthalmic articles, in particular ophthalmic lenses, or their incorporation in these articles are also compositions intended to be used for coating optical or ophthalmic articles, in particular ophthalmic lenses, or their incorporation in these articles.
• Other objects of the invention will appear on reading the description and the examples which follow.
• the photochromic compounds in accordance with the invention are compounds comprising a spiro [indoline- [2,3 '] - benzoxazine] structure, characterized in that they comprise at least one, preferably two, electron-attracting groups linked in position 5 'or 6' with the spiro [indoline- [2,3 '] benzoxazine] structure by a divalent junction radical comprising an ethylenic double bond or several conjugated ethylenic double bonds, preferably 1 to 4 ethylenic double bonds and better one or two ethylenic double bonds.
• An electron-attractor group is a group attracting electronic density.
• the group in question can be of the inducer-attractor or mesomer-attractor type.
• bathochromic displacement will be all the more important as the attracting effect exerted via the divalent junction radical, on the benzoxazine fragment, will be high.
• any electron-attractor group attached to the end of the radical joining chain will cause the desired bathochromic effect.
• electron-attracting groups will be chosen having a value of ⁇ para greater than or equal to 0.2, and better still, greater than or equal to 0.3, by reference to the Hammett scale.
• a C j to C 16 alkyl group optionally substituted by one or more hydroxy, halogen, aryl, alkoxy, acyloxy, acryloxy, methacryloxy or vinyl substituents, (ii) a vinyl, allyl, phenyl, arylalkyl, phenyl group mono or disubstituted by alkyl or alkoxy substituents C j -C 6 alkyl or one or more atom (s) halogen,
• R 4 and R 5 are, independently of one another, a C ⁇ -C 8 alkyl group, phenyl, phenyl mono- or disubstituted by C j -C alkyl and or C j -C 5 alkoxy groups, or are combined to form a ring chain of 6 to 8 carbon atoms; d) R 6 represents
• R 8 represent, independently of one another, a hydrogen atom, an alkyl, cycloalkyl, phenyl, substituted phenyl group or R 7 and R 8 combine to form a cycloalkyl, optionally substituted and containing one or more heteroatoms ,
• R 9 represents a hydrogen atom, a C ⁇ -C 6 alkyl, aryl or heteroaryl group,
• R 9 represents a hydrogen atom, a C ⁇ -C 6 alkyl, aryl or heteroaryl group,
• a halogen atom represents a monohaloalkyl group C, - C 4 or a polyhalkyle group C j -C 4 alkyl;
• 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 .
• alkyl groups mention may be made of methyl, ethyl, n-propyl, isopropyl and n-butyl groups.
• X is a radical c '
• n is an integer from 0 to 3, preferably equal to 0 or 1
• at least one of the groups R a or R b is an electron-attractor group and the another is a hydrogen atom ! or an alkyl, aryl, alkylaryl or arylalkyl radical.
• R a and R b are both electron-attracting groups, and in particular, R a and R b are both cyano groups.
• R a or R b is an electron-withdrawing group 15
• the other is a hydrogen atom or an alkyl radical, preferably a C j -C 5 such as methyl , ethyl, propyl and n-butyl.
• electron-attracting groups suitable for the present invention, mention may be made of the groups: 20 ⁇ N0 2 , quaternary ammonium, -CN, -SO3R 15 , -S0 2 R 15 ,
• OR 15 is chosen from the list of substituents that R 3 can represent under (i), (iii) and (iv),
• R 16 is chosen from the list of substituents that R 6 can represent under (i), (ii), (iii) and (iv), m ', m "and m" can take independently of each other, integer values from 1 to 5 (inclusive), and t is an integer from 1 to 6 inclusive.
• R 3 , R 4 and R 5 preferably represent hydrogen or a C 1 -C 5 alkyl radical and more particularly a methyl radical.
• R 1 or R 2 which is not a radical of formula (II) is preferably a hydrogen atom or a C j -C 5 alkyl radical, and in particular methyl.
• the preferred aromatic hydrocarbon rings represented by Cy are 5 or 6-membered rings, in particular 6-membered rings, optionally substituted by one or more alkyl groups, preferably C ⁇ -C 5 .
• the aromatic heterocycle Cy is more particularly represented by formula (III):
• Z 1, Z 2 and Z 3 denote independently of each other, CR 18 wherein R 18 is hydrogen, alkyl C j -C 6 alkyl or a phenyl group, the carbon atom being connected 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; p, q and r being integers equal to 0 or 1;
• R 17 denotes hydrogen, a C ⁇ -C 6 alkyl group, a phenyl group, or R 17 and Z 2 or R 17 and Z 3 may jointly form a 5 or 6-membered ring, aromatic or not, preferably benzene, or a naphthalene ring, optionally substituted by one or more groups (R 19 ) s , R 19 having the meaning of any of the groups R, R 5 , as defined above and s having an integer value from 1 to 4 when we have a benzene cycle or from 1 to 6 when we have a naphthalene cycle; Z 1 , Z 2 , Z 3 and CR 17 being chosen so as to ensure the aromaticity of the condensed heterocycle.
• the particularly preferred heterocyclic rings are chosen from the groups of formula (III) in which p is equal at zero, Z 2 denotes O, S or N and Z 3 denotes CR 17 where Z 2 denotes CR 18 and Z 3 denotes O, S or N, R 17 and R 18 having the meanings indicated above, Z 2 denoting by preferably O or S.
• aromatic rings which Cy may represent there may be mentioned benzene, hydroxybenzenes, alkoxybenzenes such as methoxybenzene and halobenzenes such as bromobenzene.
• aromatic heterocycles which Cy 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.
• Cy heterocyclic rings are chosen from pyridine, pyrimidine, pyrazine and furan rings, optionally condensed with an aromatic ring to form an optionally substituted benzofuran, thiazole ring.
• the radical R 6 is preferably a hydrogen atom, a C ⁇ -C 5 alkyl radical, for example a methyl, ethyl or propyl radical, a C ⁇ -C 5 alkoxy radical, preferably a methoxy or ethoxy radical.
• Cy is a 6-membered aromatic ring and very particularly a benzene ring.
• R 2 represents the radical of formula (II), that is to say that the radical of formula (II) is preferably in the 5 ′ position.
• Photochromic compounds recommended according to the invention correspond to the formula:
• R 3 , R 4 , R 5 , R 6 and X are defined as above and n is equal to O or 1.
• the photochromic compounds according to the present invention can be synthesized according to synthesis routes known in themselves from the corresponding compounds comprising a
• R 1 , R 3 , R 4 , R 5 , R 6 , R a , R b and n are defined as above.
• the present invention therefore also relates, by way of new products, useful for the synthesis of photochromic compounds according to the invention, the compounds of formula:
• radicals R 19 or R 20 are radical of formula:
• n is an integer from 0 to 3 inclusive
• m an integer from 1 to 4 inclusive, preferably equal to 0 or 1
• the other of the radicals R 19 or R 20 is a group as defined for R 1 or R 2 with the exception of a group of formula (II), and R 3 , R 4 , R 5 and R 6 and Cy are as defined above.
• the preferred compounds of formula (VII) are those substituted in the 5 ′ position and for which R 1 , R 2 , R 3 , R 5 , R 6 and Cy have the preferred meanings indicated above.
• the compounds of formula (VII) can be synthesized in a known manner by condensation of a 3 or 4-hydroxymethyl-1-nitroso-2-naphthol with the corresponding 2-methylene indoline as described in document US-A-5, 166,345 or the corresponding indoleninium in the presence of triethylamine, then by oxidation of the compound obtained for example by the Dess-Martin reagent to obtain the corresponding aldehydes.
• 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.
• 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 usable 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.
• 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.
• the medium can also contain water.
• 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 dimethyl- formamide, polyvinylpyrrolidone in acetonitrile, polystyrene in benzene, ethylcellulose in methylene chloride.
• 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.
• 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.
• 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, propionate cellulose acetate, butyrate acetate cellulose, poly (vinyl acetate), poly (vinyl alcohol), polyurethanes, polycarbonates, polyethyleneterephthalates, polystyrenes, (polystyrene-methyl-methacrylate), copolymers of styrene and acrylonitrile, polyvinylbutyrates. Transparent copolymers or mixtures of transparent polymers are also suitable for producing such materials.
• Polyols (allylcarbonate) are prepared using allyl carbonates of linear or branched aliphatic or aromatic liquid polyols such as aliphatic glycols of bis-allylcarbonate or alkylene bis (allylcarbonate).
• polyols (allylcarbonate) 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 (allylcarbonate), diethylene glycol bis (2-methallylcarbonate), diethylene glycol bis (allylcarbonate), ethylene glycol bis (2-chloro-allylcarbonate), 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 glyco
• the quantity of photochromic compounds to be used in accordance with the invention is not critical and generally depends on the intensity of the color that the composition can impart to the material after exposure to radiation. In general, the more photochromic compounds are added, the greater the coloration under irradiation.
• 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 20% by weight and preferably between 0.05 and 10% 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.
• a temporary transfer support such as a varnish forming a coating on a substrate
• the present invention therefore also includes transfer varnishes including one or more photochromic compounds according to the invention.
• photochromic compounds can be used with other photochromic compounds, such as photochromic compounds giving rise to different colorings such as yellow or red, known in the state of the art. This is how chromenes well known in the art can be used.
• This compound is prepared according to the method used for Example 1 from 0.42 g (1 mmol) of Dess-Martin reagent and 0.39 g (1 rrimol) of 5'-hydroxymethyl-5-methoxy -l, 3,3-trimethylspiro [indoline-2,3'-
• the solvent is evaporated.
• the product is purified on a silica column (eluent Pentane / ethyl acetate 80/20).
• This compound is prepared according to the method used for Example 7 starting from 0.36 g (1 mmol) of the compound of Example 1 and from 0.2 g (1 mmol) of 2,3,4, 5,6-pentafluoro phenylacetonitrile.
• This compound is prepared according to the method used for Example 7 from 0.39 g (1 mmol) of the compound of Example 2 and from 0.21 g (1 mmol) of 2,3,4, 5,6-pentafluoro phenylacetonitrile.
• This compound is prepared according to the method used for Example 10 from 0.39 g (1 mmol) of the compound of Example 2 and 0.18 g (1.5 mmol) of ethyl cyanoacetate .
• This compound is prepared according to the method used for Example 10 from 0.36 g (1 mmol) of the compound of Example 1 and 0.13 g (2 mmol) of malononitrile.
• This compound is prepared according to the method used for Example 10 from 0.39 g (1 mmol) of the compound of Example 2 and 0.13 g (2 mmol) of malononitrile.
• This compound is prepared according to the method used for Example 10 from 0.39 g (1 mmol) of the compound of Example 6 and 0.18 g (1.5 mmol) of ethyl cyanoacetate .
• the maximum wavelengths ( ⁇ ma ⁇ ) of the compounds of Examples 1 to 14 were measured at 25 ° C ( ⁇ 1 ° C), in solution in toluene (Carlo Eba, ACS quality, HPLC), at a concentration 2.5 x 10 "5 M, using a spectrophotometer (Beckman DU 7500, UV-visible, diode array detector).
• the solutions are irradiated in a rectangular quartz tank with a side of 1 cm, at by means of an "ozone-free xenon" lamp (ORIEL XE XBO 150 W) supplied by an ORIEL amplifier (68806)
• ORIEL XE XBO 150 W supplied by an ORIEL amplifier (68806)
• A Absorbance in the photo-stationary state
• photochromic concentration 5 ⁇ 10 ⁇ 4 M in toluene
• photochromic compounds of Examples 8, 10, 12 and 14 and of a reference photochromic compound, 6'-cyano-1,3,3-trimethyl-spiro [indoline- [2,3 '] - [3H] -napht- [2, l, b] - [1, 4] - oxazine] described in patent application WO 96/04590.
• the compounds of the invention generally have a value of A (measured at 35 ° C) greater than that of the reference compound of the closest prior art.
• Rigid photochromic discs were produced by polymerization of a composition comprising, in parts by weight, 100 parts of methyl methacrylate (MMA), 2 parts of ethylene glycol dimethacrylate (DMEG), 0.03 parts of azo bis - isobutyronitrile (AIBN) and a photochromic compound according to the invention.
• MMA methyl methacrylate
• DMEG ethylene glycol dimethacrylate
• AIBN azo bis - isobutyronitrile
• compositions are poured into an appropriate mold and then heated for 15 hours at 64 ° C. The temperature is then raised in 10 minutes to 83 ° C and maintained at this value for 8 hours. After cooling to room temperature, rigid photochromic discs are recovered having the following dimensions: diameter: 12 mm; thickness: 0.14 rnm. We determined for each disc at 35 ° C the following photochromic characteristics:
• Tpp - percentage of closed form transmission
• the variation in the percentage of transmission of each disc is measured as a function of time during the two phases by placing it at the wavelength ⁇ ma ⁇ corresponding to the maximum absorption of the photochromic compound of the disc.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Eyeglasses (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

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• 1997
  • 1997-05-06 FR FR9705544A patent/FR2763070B1/fr not_active Expired - Fee Related
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• 1998
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