PHOTOCHROMATIC COMPOUNDS, PROCESS FOR THEIR PREPARATION AND THEIR USE IN POLYMERIC MATERIALS

Abstract: Photochromatic compounds having general formula (I): the photochromatic compounds can be used in polymeric materials to obtain photochromatic articles.

Description: PHOTOCHROMATIC COMPOUNDS, PROCESS FOR THEIR PREPARATION AND THEIR USE IN POLYMERIC MATERIALS. The present invention relates to photochromatic com- pounds. More specifically, the present invention relates to photochromatic compounds bound to a triazine nucleus, a process for their preparation and their use in polymeric materials . A further object of the present invention relates to polymeric compositions containing said photochromatic compounds and to photochromatic articles obtained from their processing. Photochromatic compounds are substances which have the characteristic of reversibly changing colour and/or degree of light transmission when exposed to solar or artificial light in the band ranging from UV to visible, or to some types of electromagnetic radiation, returning to their original state of colour and transmission when the initial light source is removed. There are numerous substances with photochromatic characteristics, which belong to various groups of both organic and inorganic compounds such as, for example, those described in the texts "Photochromism", by G.H. Brown (Ed.), Vol. Ill of the Weissberger series "Techniques of Organic Chemistry", Wiley Interscience, New York (1971) and in "Photochromism: Molecules and Systems", by H. Dϋrr and H. Bouas- Laurent (Ed.), Vol. 40 of the series "Studies in Organic Chemistry", Elsevier (1990) . Among organic photochromatic compounds, those belonging to the groups of spiro-indolino-oxazines, spiro-pyrans and chromenes, are particularly known and used. The above compounds are capable of giving photochromatic characteristics to polymerized organic materials used, for example, in the production of photochromatic lenses for eye-glasses, special inks, toys, and in many other applications. As an example, the following patents can be mentioned: USA 3,562,172, USA 3,578,602, USA 4,215,010, USA 4,342,668, USA 5,055,576, USA 5,110,922, USA 5,186,867, EP 146,135, EP 134,633, EP 141,407, EP 245,020, IT 1,233,348 and IT 1,238,694. The Applicant has now found photochromatic compounds bound to a triazine nucleus which have good photochromatic characteristics, good fatigue resistance and good coloura- bility characteristics . The present invention therefore relates to photochromatic compounds having general formula (I) : wherein : R'ι represents a hydrogen atom; an OH group; or a pho- tochromatic compound having general formula (II) . - R' represents a linear or branched Cι-Cχo alkyl group; a linear or branched C 2 -Cιo acyl group; a hydroxyl group; a linear or branched Ci-Cε alkoxyl group; an amine group, said amine group optionally substituted with a linear or branched Cι~C 6 alkyl group; an N-alkyl (Cι-C 6 ) amine group; an N,N-dialkyl (Ci-Cβ) amine group; a pi- peridine, piperazine or morpholine group; a carboxylic acid group; a chloro carbonyl (CO-Cl) group; an amide group; a COOR' a ester group wherein R' a represents a linear or branched Ci-Cio alkyl group; a linear or branched C 2 -Cιo heteroalkyl group in which the heteroa- torn is selected from nitrogen, oxygen, sulfur and selenium; a vinyl group; a (meth) allyl group; a (meth) acrylic group; a C 3 -Cg 1-alkenyloxyl group; R' ' represents a hydrogen atom; a halogen atom selected from fluorine, chlorine and bromine; a linear or branched Cι~C 6 alkyl group; a linear or branched Cι~C 6 alkoxyl group; a phenyl group; a phenoxyl group; P' represents one of the following groups having general formula (III), (IV) or (V): R and R 7 , the same or different, represent a linear or branched Ci-Cio alkyl group, said alkyl group optionally substituted with 1-10 halogen atoms selected from fluorine, chlorine and bromine, or with C(X') 3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Cι-C 6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2,2, 6, 6-tetramethylpiperidine group; a vinyl group; an allyl or methallyl group; a linear or branched C 2 -C 6 alkenyl group; an aryl group selected from phenyl, biphenyl and naphthyl, said aryl group optionally sub- stituted with linear or branched Cι-C 6 alkoxyl groups, carboxyl groups, amine groups, N,N-dialkyl (Cι-C 6 ) amine groups; a 4-N,N-dialkyl (Ci-Cε) aminoaniline group; an OH group; an NH 2 or NHR a group wherein R a represents a linear or branched Ci-Cio alkyl group; a ben- zyl group, said benzyl group optionally substituted with 1-5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X')3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Ci-Cio alkyl groups, linear or branched Ci-C 6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; a carboxylic acid group; a chloro carbonyl group; an amide group; a COOR' a ester group wherein R' a represents a linear or branched Ci-Cio alkyl group; a benzyl group, said benzyl group optionally substituted with 1-5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X') 3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Ci-Cio alkyl groups, linear or branched Ci-Cβ alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; Ri and R 2 , the same or different, represent a linear or branched Ci-Cio alkyl group, said alkyl group optionally substituted with 1-10 halogen atoms selected from fluorine, chlorine and bromine, or with C(X') 3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Ci-Cβ alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; a vinyl group; a (meth)allyl group; a (meth) acrylic group; a C 3 -C 8 1- alkenyloxyl group; a linear or branched C 2 -Cχo alkenyl group; a COOR' a ester group wherein R' a represents a linear or branched Ci-Cio alkyl group; a benzyl group, said benzyl group optionally substituted with 1-5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X')3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Ci-Cio alkyl groups, linear or branched Ci-Cε alkoxyl groups, carboxyl groups, cyano groups, or with a 2,2, 6, 6-tetramethylpiperidine group; a linear or branched C_.-C 6 alkoxyl group; an N-alkyl (Cχ-C 6 ) amine group; an N,N-dialkyl (Cι-C 6 ) amine group; or Ri and R 2 , considered jointly with the carbon atom to which they are bound, represent a C 4 -Cι 0 cycloalkyl group, said cy- cloalkyl group optionally substituted with halogen atoms selected from fluorine, chlorine and bromine, or with hydroxyl groups, linear or branched Cτ-C 6 alkoxyl groups, carboxyl groups, cyano groups, amine groups, N- alkyl (Ci-Cε) amine groups, N,N-dialkyl (Cι-C 6 ) amine groups; an N,N-dialkyl (Cτ-C 6 ) amide group; an aryl group selected from phenyl and biphenyl; a cyano group; R 3 , R 4 , R5 and Re, the same or different, represent a hydrogen atom; a halogen atom selected from fluorine, chlorine, bromine and iodine; a linear or branched Ci-Cβ alkyl group, said alkyl group optionally substituted with 1-6 halogen atoms selected from fluorine, chlorine and bromine, or with C(X') 3 groups wherein X' is selected from fluorine, chlorine and bromine, hy- droxyl groups, linear or branched Cι-C 6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2,2,6,6- tetramethylpiperidine group; a benzyl group, said benzyl group optionally substituted with 1-5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X') 3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Ci-Cio alkyl groups, linear or branched Cι~C 6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; a hydroxyl group; a linear or branched Cι-C 6 alkoxyl group; an amine group; an N-alkyl (Ci-Ce) amine group; an N,N- dialkyl (Ci-Cβ) amine group; a piperidine, piperazine or morpholine group; a carboxylic acid group; a chloro carbonyl (CO-Cl) group; an amide group; a COOR' a ester group wherein R' a represents a linear or branched Cχ-Cιo alkyl group; a benzyl group, said benzyl group optionally substituted with 1-5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X' 3 ) groups wherein X 1 is selected from fluorine, chlorine and bro- mine, hydroxyl groups, linear or branched Cι-Cι 0 alkyl groups, linear or branched Cι-C 6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2,2,6,6- tetramethylpiperidine group; a Cι-C 6 carboxyalkyl group; a C 2 -C 6 carboxyalkenyl group; a carboxyamide group; an N-alkyl (Ci-Ce) carboxyamide group; an N,N- dialkyl (Ci-Cβ) carboxyamide group; a cyano group; a nitro group; a sulfonic group; an aryl group selected from phenyl, biphenyl and naphthyl, said aryl group optionally substituted with N,N-dialkyl (Ci-Cε) amine groups, linear or branched Ci-Cβ alkoxyl groups, hy- droxyl groups, linear or branched Cι-C 6 alkyl groups; an acyl group of the alkyl ketone, aryl ketone or benzyl ketone type; a vinyl group; a (meth) allyl group; a (meth) acrylic group; a C 3 -C 8 1-alkenyloxyl group; a linear or branched C 2 -C 6 alkenyl group, said alkenyl group optionally substituted with one or two N,N-di- alkyl- (Cι-C 6 ) -4-aniline groups; an N-2, 3-dihydroindo- line group; a linear or branched Cι-C 6 thioether group; two consecutive substituents between R 3 and R 6 can represent the condensation points with other aromatic, heterocyclic or quinonic rings; P represents a monocyclic or polycyclic aromatic nucleus, belonging to one of the following types: ben- zenic represented by general formula (VI) ; naphthalenic represented by general formula (VII) ; quinolinic represented by general formula (VIII) ; isoquinolinic represented by general formula (IX) ; cumarinic represented by general formula (X) ; quinazolinic represented by general formula (XI) ; phenanthrenic represented by general formula (XII) ; anthracenic represented by general formula (XIII); or a group with general formula (XIV): wherein: at least two consecutive substituents between R 8 and R i3 , R i4 and R 21 , R 22 and R 28 , R 30 and R 35 , R 36 and R 41 , R 42 and R 47 , Rs and R 57 , R 58 and R 67 , Res and R 75 , represent the condensation points with the oxazine or pyran ring, the other substituents having the meaning described for substituents R 3 , R 4 , R 5 and R 6 ; Xi represents an oxygen atom; a sulfur atom; a selenium atom; an NH group; an NR a group wherein R a represents a linear or branched Ci-Cio alkyl group; Y represents CH or a nitrogen atom. Preferred photochromatic compounds having general for- mula (I) for the purposes of the present invention, are those wherein: R'ι represents an OH group; or a photochromatic compound having general formula (II) ; R' represents a linear or branched Cχ-C 4 alkyl group; a linear or branched C 2 -C 4 acyl group; a hydroxyl group; a linear or branched Cι-C 6 alkoxyl group; an amine group; an N-alkyl (Cι-C 6 ) amine group; an N,N-dialkyl (Ci-Cδ) amine group; a piperidine, piperazine or mor- pholine group; a carboxylic acid group; a chloro car- bonyl (CO-Cl) group; a (meth)allyl group; a (meth) - acrylic group; a C 3 -C 8 1-alkenyloxyl group; R' ' represents a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, or a phenyl group; Y represents a nitrogen atom; or CH; - P 1 represents one of the groups having general formula (III), (IV) or (V) wherein: - - R and R 7 , the same or different, represent one of the following groups: methyl, ethyl, isopropyl, 2- allyl, 2-methallyl, 2-hydroxyethyl, 2- carboxymethyl, phenyl, 4-N,N-dimethylaminoaniline, 4-methoxybenzene, 4-cyano-benzene; a linear or branched Cι-C 6 alkoxyl group; a linear or branched C 2 -C 6 amine group; an N,N-dialkyl (Cτ-C 6 ) amine group; - Ri and R 2 , the same or different, represent a methyl or phenyl group; or considered jointly with the carbon atom to which they are bound, represent a cyclohexyl group; R 3 , R, R5 and R 6 , the same or different, rep- resent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or one of the following groups: methyl, isopropyl, hydroxyl, methoxyl, N,N-dimethylamine, piperi- dine, morpholine, carboxyl, carboxymethyl, N,N-dimethylcarboxyamide, cyano, nitro, meth- ylketone, phenylketone, phenyl; a linear or branched Ci-C δ alkoxyl group; an amine group; an N-alkyl (Cι-C 6 ) amine group; an N,N- dialkyl (Cι-C 6 ) amine group; a piperidine, piperazine or morpholine group; a carboxylic acid group; an amide group; a chloro carbonyl (CO-Cl) group; a COOR' a ester group wherein R' a represents a linear or branched C1-C 10 alkyl group; esents one of the groups having general formula from (VI) to (XIV), wherein: (a) two consecutive substituents between R 8 and R13, Ru and R 2i , R 22 and R 28 , R 30 and R 35 , R 36 and R 41 , R 42 and R 47 , R 48 and R 57 , R 58 and R 6 , Res and R 75 , in- dependently represent the condensation points with the oxazine or pyran ring; and the other substituents each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or one of the following groups: methyl, isopropyl, 2- (meth) allyl, (meth)acryl, hydroxyl, methoxyl, 2- hydroxyethyl, amine, N-methylamine, N-ethylamine, N,N-dimethylamine, piperidine, morpholine, carboxyl, carboxymethyl, N,N-dimethylcarboxyamide, cyano, nitro, methylketone, ethylketone, phenylke- tone, methylthiol; (b) two consecutive substituents between R 8 and Rι 3 , R 1 and R 2i , R 22 and R 28 , R 30 and R 35 , R 3 6 and R 4i , R 42 and R 47 , R 48 and R 57 , R 58 and R 67 , Res and R 75 , different from those indicated under point (a) , rep- resent the condensation points with a benzene or a quinone ring; Xi represents an oxygen atom; a sulfur atom; a selenium atom; an NH group. Specific examples of preferred compounds according to the present invention are: Compound having formula (la) : Compound having formula (lb) : Compound having formula (Ic) A further object of the present invention relates to a process for the preparation of the photochromatic compounds having general formula (I) . The photochromatic compounds having general formula (I) can be prepared by the condensation of photochromatic compounds having general formula (II) : wherein the substituents R 1 , R 1 ', P, P' and Y have the same meanings described above, with a cyanuryl halide having general formula (XV) : X N-^^N wherein X represents a halogen atom such as fluorine, chlorine, bromine or iodine, in the presence of an inert organic solvent such as, for example, acetone, ethyl alcohol, iso- propanol, toluene, dioxane, or of a mixture of these solvents, at a temperature ranging from 20°C to 100°C, preferably from 20°C to 40°C, for a time ranging from 1 hour to 10 hours, preferably from 2 hours to 5 hours. The reaction product thus obtained is generally purified on a silica col- umn, with subsequent crystallization from a solvent such as, for example, acetone, toluene, pentane, heptane, diethyl ether. The photochromatic compounds having general formula (II) are obtained by the condensation of isoindoline compounds having general formula (XVI), or of indoline compounds having general formula (XVII) , or of compounds deriving from propargyl alcohol having general formula (XVIII) , or of compounds deriving from α, β-unsaturated aldehydes having general formula (XIX) , with nitroso compounds or aldehyde compounds having general formula (XX) , or with hydroxy- aryl compounds having general formula (XXI), to give the respective photochromatic compounds having general formula (XVIa) , (XVIIa) and (XVIIIa) , indicated in Schemes 1-4: Scheme 1 Scheme 2 Scheme 3 (XXI) (XVIII) (XVIIIa) Scheme 4 (XIX) (XXI) (XVIIIa) wherein the substituents R, from R λ to R 7 , R'', Y and P have the same meanings described above and Y' represents an NO or CHO group. The condensation reaction is carried out in the presence of an inert organic solvent such as, for example, ethyl alcohol, isopropanol, toluene, acetonitrile, or of a mixture of these solvents, and in the presence of an amine such as, for example, triethylamine, morpholine, piperidine, or of an acid such as, for example, paratoluenesulfonic acid, sulfu- ric acid, acid alumina, or of a metal complex such as, for example, titanium (IV) tetra-ethoxide, at a temperature ranging from 50°C to 100°C, preferably from 60°C to 75°C, for a time ranging from 1 hour to 10 hours, preferably from 2 hours to 3 hours. The reaction product thus obtained is gen- erally purified by elution on a silica column and subsequent crystallization from a solvent such as, for example, acetone, toluene, hexane, heptane, pentane, diethyl ether, di- chloromethane . The isoindoline compounds having general formula (XVI) can be prepared according to processes known in the art and described, for example, in: "Tetrahedron" (1966), Vol. 22, page 2481; "Journal of Organic Chemistry" (1979), Vol. 44, page 1519; "Angewandte Chemie International (1968), Vol. 7, page 373. The indoline compounds having general formula (XVII) can be prepared by the reaction of 2, 3, 3-trimethylindolenine compounds with an alkyl or (meth)allyl halide as described, for example, in Japanese patent application JP 03/176467. The isoindoline compounds having general formula (XVI) and the indoline compounds having general formula (XVII) , are usually kept in the form of salts such as, for example, iodides, bromides, chlQrides, as the free base is very oxidable in air. The compounds deriving from propargyl alcohol having general formula (XVIII) can be prepared by the reaction of ketone compounds with sodium acetylide in xylene or with a lithium acetylide/ethylenediamine complex as described, for example, in U.S. patents 5,585,042 and 5,238,981. The compounds deriving from α, β-unsaturated aldehydes having general formula (XIX) can be prepared according to the processes known in the art as described, for example, in Japanese patent application JP 48/016481; or in "Organic Synthesis" (1970), Vol. 50, page 66. The nitroso compounds having general formula (XX) can be prepared by the reaction of phenol compounds with nitrous acid or butyl nitrite, as described, for example, in Italian patent IT 1,176,858. The aldehyde compounds having general formula (XX) can be prepared by the reaction of phenol compounds with para- formaldehyde, hexamethylenetetramine, or acetic acid, followed by the addition of an aqueous solution of sulfuric acid at 60%-70%, as described, for example, in German patent DE 2,425,430. The hydroxy-aryl compounds having general formula (XXI) are normally products which are commercially available such as, for example, β-naphthol or phenol. Specific examples of isoindoline compounds having general formula (XVI), or indoline compounds having general formula (XVII), are the following: 1 ) A specific example of a nitroso compound having general formula (XX) is the following: NO A specific example of an aldehyde compound having general formula (XX) is the following: # CHO The compounds having general formula (XV) are generally products which are commercially available. A specific example of a compound having general formula (XV) is the following: Cl The photochromatic compounds having general formula (I) of the present invention are colourless or slightly yellow- coloured, crystalline products. Their solutions in common organic solvents such as, for example, benzene, toluene, methanol, ethanol, when not exposed to light sources, are colourless or slightly yellow- coloured. These solutions, if exposed to a light source, either visible or ultraviolet, become blue or orange-red coloured. The colouring quickly fades when the light source is removed. The photochromatic compounds having general formula (I) can be applied to the surface or incorporated in mass into the desired articles, using techniques already known in the art and described hereunder. Some polymeric photochromatic end-articles can be obtained with moulding techniques such as, for example, injection or compression moulding, starting from polymers in which one or more of the photochromatic compounds having formula (I) are homogeneously dispersed in mass. Alternatively, the photochromatic compounds having general formula (I) can be dissolved in a solvent, together with the polymeric material such as, for example, polymethyl methacrylate, polyvinyl alcohol, polyvinyl butyral, cellulose acetate butyrate or epoxy, polysiloxane, urethane resin. The mixture thus obtained is deposited on a transparent support to form, after evaporation of the solvent, a photochromatic coating. The photochromatic compounds having general formula (I) can also be added to a polymerizable monomer such as, for example, a meth (acrylic) or allyl carbonate monomer, so that, after polymerization carried out in the presence of a suitable initiator such as, for example, azo-bis (isobutyro- nitrile) in the case of the meth (acrylic) monomer or a per- oxyketal in the case of the allyl carbonate monomer, they are uniformly incorporated in the resin formed. Finally, the photochromatic compounds having general formula (I) can be applied to a transparent substrate such as, for example, polycarbonate, polymethyl methacrylate or polydiethyleneglycol bis (allyl carbonate), by surface impregnation obtained by putting the substrate in contact, at a suitable temperature, with a solution or dispersion containing one or more of the photochromatic compounds having general formula (I) , operating according to a method described, for example, in U.S. patent 5,130,353. The photochromatic compounds having general formula (I) of the present invention have the characteristic of being able to be incorporated in mass or using one of the tech- niques described above, into various organic polymers such as, for example, high density polyethylene (HOPE), low density polyethylene (LDPE) , ethylene-vinylacetate copolymer, polyether amides, polypropylene, polymethyl methacrylate, polyvinyl alcohol, polyvinyl butyral, cellulose acetate bu- tyrate, epoxy, polysiloxane or urethane resins, polycarbonate, polydiethylene glycol bis (allyl carbonate), polyamides, polyesters, polystyrene, polyvinylchloride, polyethy- lacrylate, siliconic polymers. A further object of the present invention therefore re- lates to polymeric compositions comprising the above polymeric materials and the above photochromatic compounds having general formula (I) and the photochromatic articles obtained from their processing. The photochromatic compounds having general formula (I) of the present invention, are added to the above polymeric compositions in a quantity ranging from 0.01% to 5% by weight, preferably between 0.1% and 2% by weight, with respect to the weight of said polymeric compositions. The photochromatic compounds having general formula (I) of the present invention can also be added to coating compositions, such as for example, paints, lacquers, paints or lacquers based on hybrid polysiloxanes and/or silica gel, compositions based on plastic materials. A further object of the present invention consequently relates to coating compo- sitions, such as for example, paints, lacquers, paints or lacquers based on hybrid polysiloxanes and/or silica gel, compositions based on plastic materials, comprising said photochromatic compounds . The photochromatic compounds having general formula (I) of the present invention are added to the above coating compositions in a quantity ranging from 0.01% to 5% by weight, preferably between 0.1% and 2% by weight, with respect to the weight of said coating compositions. Paints or lacquers based on hybrid polysiloxanes and/or silica gel are obtained by means of the "sol-gel" process described, for example, by M. Nogami, Y. Abe in: "Journal of Materials Science" (1995), Vol. 30, pages 5789-5792. The above coating compositions can be applied to the substrate (metal, plastic, wood, etc.) using the conven- tional methods such as, for example, brushing, spraying, pouring, dipping or electrophoresis. The photochromatic compounds having general formula (I) of the present invention can optionally be used in the presence of usual additives for organic polymers such as, for example, phenolic antioxidants, sterically hindered amines, benzotriazoles, benzophenones, phosphites or phosphonites. The photochromatic compounds having general formula (I) of the present invention which, as already mentioned above, are colourless or slightly yellow-coloured, can be used as such, mixed with each other, or combined with other suitable organic photochromatic compounds, in order to obtain, after activation, the formation of other colourings such as brown and grey. For this purpose, photochromatic compounds belonging to the group of spiro-indolino-oxazines or spiro-pyrans described in the art such as, for example, in U.S. patent 5,066,818, are particularly useful for the purpose. Some illustrative examples are provided hereunder for a better understanding of the present invention and for its embodiment but in no way limit the scope of the invention. EXAMPLE 1 Preparation of l,l,2,4,7-pentamethyl-3-methγlene-isoindol- ine iodide having formula (XVI') -A: 40 g of acetonylacetone, 12 g of methylamine hydro- chloride, 20 ml of water and 12 ml of ethyl alcohol are charged into a 100 ml flask, equipped with a reflux cooler and mechanical stirrer. The above mixture is heated to 80 °C, under a nitrogen atmosphere, for 24 hours. At the end, the mixture is cooled and subsequently extracted with 30 ml of hexane. The aqueous phase obtained is treated with aqueous sodium hydroxide (solution -at 30%) until a pH of 14 is reached: a yel- low-white precipitate is thus formed, which is rapidly filtered and washed with 30 ml of water and 10 ml of hexane. The product is dried under vacuum and conserved in a nitrogen atmosphere: the yield is 23.5 g. This product is identified as 1, 2, 3, 4, 7-pentamethyl-isoindoline by means of gas-mass (molecular weight = 187) . A quantity equal to 23.5 g of the above product is charged into a 100 ml stainless steel autoclave together with 20 ml of toluene and 16 g of methyliodide. The autoclave is heated to 85 °C and the whole mixture is maintained at this temperature, under a nitrogen atmosphere, for 6 hours. At the end, the autoclave is cooled to room temperature and the raw product is filtered obtaining a crystalline precipitate which is washed with 20 ml of ethyl acetate and finally with 20 ml of hexane. 35 g of product are obtained, corresponding to 1, 1, 2, 4, 7-pentamethyl-3-methylene-isoindoline iodide having formula (XVI 1 ) -A. The free base, corresponding to Compound (XVI' ), is identified by means of gas-mass (molecular weight = 201) . EXAMPLE 2 Preparation of the compound having formula (XVIa) -1 (XVIa) -1 16 g of 2, 7-dihydroxynaphthalene, 7.0 g of sodium nitrate, 100 ml of water and 4.0 g of sodium hydroxide are charged into a 250 ml flask, equipped with a reflux cooler and mechanical stirrer. The above mixture is stirred, under a nitrogen atmosphere, until dissolution. 10.7 g of sulfuric acid diluted in 30 ml of water are subsequently added dropwise and the reaction temperature is maintained between 0°C and 5°C. After 30 minutes at this temperature, the reaction raw product is filtered, washed with water and dried in air. 18.6 g of a dark brown powder corresponding to 2, 7-dihydroxy-l-nitroso- naphthalene, are obtained. 4 g of 1, 1,2,4, 7-pentamethyl-3-methylene-isoindoline iodide obtained as described in Example 1, 2.8 g of 2,7- dihydroxy-1-nitroso-naphthalene, 2.5 g of triethylamine and 60 g of toluene are charged into a 250 ml flask, equipped with a reflux cooler and mechanical stirrer. The above mixture is heated to 70 °C and maintained at this temperature, under stirring, under a nitrogen atmosphere, for 1 hour. The reaction raw product obtained is filtered and subsequently purified by passage on a silica gel column, eluating with a mixture of heptane/ethyl acetate in a ratio of 1/1. An almost pure photochromatic product is obtained yellow solid) , which is further purified by crystallization from toluene. After crystallization, 2.5 g of a solid white product are obtained, corresponding to the compound having formula (XVIa)-l which is identified by means of gas-mass (molecular weight 372) . EXAMPLE 3 Preparation of the compound having formula (XVIIa) -1 : 18.6 g of 2, 7-dihydroxy-l-nitroso-naphthalene, obtained as described in Example 2, are mixed with 17 g of 1,3,3- trimethyl-2-methylene-indoline and 30 ml of isopropyl alcohol: the mixture obtained is maintained for 3 hours at reflux temperature. At the end of the reaction, the solvent is eliminated by distillation under vacuum and 40 ml of toluene and 2.0 g of activated carbon are subsequently added. This mixture is heated to 70 °C for 15 minutes: the reaction raw product is filtered, concentrated and cooled. The precipitated raw product is filtered obtaining 7.0 g of . raw product which is further crystallized from toluene obtaining a white solid corresponding to the Compound having formula (XVIIa) -1 which is identified by means of gas-mass (molecular weight = 344) . EXAMPLE 4 Preparation of the compound having formula (XVIIIa) -1 : (XVIIIa) -1 1.66 g of 2, 7-dihydroxynaphthalene diluted in 20 ml of anhydrous toluene are charged into a 250 ml flask, equipped with a reflux cooler and mechanical stirrer. 2.4 g of titanium (IV) tetra-ethoxide in 10 ml of anhy- drous toluene and 2.16 g of β-phenyl-cinnamaldehyde in 20 ml of anhydrous toluene are then added, under an inert atmosphere: at the end of the additions, the mixture obtained is heated to 100 °C for 5 hours. This mixture is subsequently cooled to room temperature and the reaction raw product obtained is poured into an aqueous solution 2M of NH 4 C1 (100 ml) and heated to 80 °C for an hour. At the end, the mixture is cooled again to room temperature and, after filtration of the titanium (IV) tetra- ethoxide, the organic phase is separated, washed with water and dried on magnesium sulfate. The solvent is partially removed at reduced pressure and the resulting solution is cooled to 0°C. The crystallized product obtained is filtered and washed with heptane: a photochromatic product (yellow solid) is obtained. After further crystallization, 2.1 g of a solid white product are obtained, corresponding to the compound having formula (XVIIIa) -1 which is identified by means of gas-mass (molecular weight = 350) . EXAMPLE 5 Preparation of the compound having formula (la) : 2.2 g of triethylamine and 1 g of the compound having formula (XVIa)-l obtained as described in Example 2 dissolved in 45 ml of anhydrous toluene and 45 ml of acetoni- trile, are charged into a 250 ml flask, equipped with a reflux cooler and mechanical stirrer. 0.2 g of cyanuryl chloride diluted in 10 ml of anhy- drous toluene are subsequently added dropwise, at room temperature and under an inert atmosphere. After 2 hours at room temperature, the reaction raw product is filtered and the solvent is eliminated by evapo- ration under vacuum. A light blue solid is obtained which is purified by repeated washings with 10 ml of diethyl ether and dried by evaporation under vacuum. At the end of the above treatment, 1 g of product (white solid) is obtained, corresponding to the Compound having formula (la) which is identified by liquid chromatog- raphy coupled with a mass spectrometer (molecular weight = 1191) . EXAMPLE 6 Preparation of the compound having formula (lb) 3 g of triethylamine and 1 g of the Compound having formula (XVII-a)-l obtained as described in Example 3, dissolved in 45 ml of anhydrous toluene and 45 ml of acetroni- trile are charged into a 100 ml flask, equipped with a re- flux cooler and mechanical stirrer. 0.24 g of cyanuryl chloride diluted in 20 ml of anhydrous toluene are subsequently added dropwise, at room temperature and under an inert atmosphere. After 1 hour at room temperature, the reaction raw product is filtered and the solvent is eliminated by evaporation under vacuum. A light green solid is obtained, which is purified by repeated washings with 10 ml of diethyl ether and dried by evaporation under vacuum. At the end of the above treatment, 1.32 g of a product (white solid) are obtained, corresponding to the Compound having formula (lb) which is identified by liquid chromatog- raphy coupled with a mass spectrometer (molecular weight = 1107) . EXAMPLE 7 Preparation of the compound having formula (Ic) : 1.9 g of triethylamine and 1 g of the compound having formula (XVIII-a)-l obtained as described in Example 4, dissolved in 30 ml of anhydrous toluene are charged into a 100 ml flask, equipped with a reflux cooler and mechanical stirrer. 0.213 g of cyanuryl chloride diluted in 10 ml of anhydrous toluene are subsequently added dropwise, at room temperature and under an inert atmosphere. After 2 hours at room temperature, the reaction raw product is filtered and the solvent is eliminated by evapo- ration under vacuum. A light orange solid is obtained, which is purified by repeated washings with 10 ml of diethyl ether and dried by evaporation under vacuum. At the end of the above treatment, 0.5 g of a product (beige solid) are obtained, corresponding to the Compound having formula (Ic) which is identified by liquid chromatog- raphy coupled with a mass spectrometer (molecular weight = 1125) . EXAMPLE 8 Evaluation of the photochromatic activity. The photochromatic activity is evaluated in ethanol, at 25°C, of Compounds (Ia)-(Ic) obtained as described in Examples 5-7. Solutions are prepared at a concentration equal to 3.5 * 10 "5 of the various Compounds (Ia)-(Ic) in ethanol and subsequently 2 ml of each solution are placed in a 1 cm quartz cell. The quartz cell containing the solution is introduced into a temperature control system, equipped with a magnetic stirrer (the solution is maintained under stirring during the measurement) . The spectrum of the activated and deactivated forms and the decolouring kinetics are registered with a UV/visible spectrophotometer with a diode battery (HP 8453) equipped with perpendicular optical fibres which give a continuous monochromatic irradiation. The light source is a high pressure Hg lamp and the irradiation wave length is determined by monochromatic filters. This system allows the absorbance to be contemporaneously monitored at all wavelengths . The following parameters are determined using the meas- urements obtained as described above and with a calculation effected with the GRAFit program of Erithaeus Software Ltd. for the mathematical treatment of the graphs: tι / 2 (s) : time in which the absorbance of the merocya- nine open form is equal to half of the initial absorb- ance value; k Λ (s -1 ) : constant of the thermal reaction rate of the oxazine or spirane ring closing; λ PMC (ran) : wave-length of the maximum absorbance of the merocyanine open form; - colourability: difference between the final absorbance and initial absorbance of the merocyanine open form. The data obtained analyzing Compounds (Ia)-(Ic) are compared with the data obtained using Compounds (XVIa)-l, (XVIIa) -1 and (XVIIIa) -1: the data are indicated in Table 1. TABLE 1

Claims: CLAIMS Photochromatic compounds having general formula (I] wherein: R'ι represents a hydrogen atom; an OH group; or a photochromatic compound having general formula (II). - R' represents a linear or branched Ci-Cio alkyl group; a linear or branched C 2 -Cιo acyl group; a hydroxyl group; a linear or branched Cj-C 6 alkoxyl group; an amine group, said amine group optionally substituted with a linear or branched Cι-C 6 alkyl group; an N-alkyl (Cι-C 6 ) amine group; an N,N- dialkyl (Ci-Cε) amine group; a piperidine, piperazine or morpholine group; a carboxylic acid group; a chloro carbonyl (CO-Cl) group; an amide group; a COOR' a ester group wherein R' a represents a linear or branched C_-Cι 0 alkyl group; a linear or branched C 2 -Cιo heteroalkyl group in which the het- eroatom is selected from nitrogen, oxygen, sulfur and selenium; a vinyl group; a (meth) allyl group; a (meth) acrylic group; a C 3 -C 8 1-alke-nyloxyl group; R' ' represents a hydrogen atom; a halogen atom selected from fluorine, chlorine and bromine; a linear or branched Ci-Cε alkyl group; a linear or branched Cι-C 6 alkoxyl group; a phenyl group; a phenoxyl group; P' represents one of the following groups having general formula (III), (IV) or (V): R and R 7 , the same or different, represent a linear or branched Ci-Cio alkyl group, said alkyl group optionally substituted with 1-10 halogen atoms selected from fluorine, chlorine and bromine, or with C(X') 3 groups wherein X 1 is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched -Ce alkoxyl groups, carboxyl groups, cyano groups, or with a 2,2,6,6- tetramethylpiperidine group; a vinyl group; an al- lyl or methallyl group; a linear or branched C 2 -C6 alkenyl group; an aryl group selected from phenyl, biphenyl and naphthyl, said aryl group optionally substituted with linear or branched Ci-Cβ alkoxyl groups, carboxyl groups, amine groups, N,N-dialkyl (Cι-C 6 ) amine groups; a 4-N, N-dialkyl (Ci-Cε) ami- noaniline group; an OH group; an NH 2 or NHR a group wherein R a represents a linear or branched Cχ-Cιo alkyl group; a benzyl group, said benzyl group optionally substituted with 1-5 halogen atoms se- lected from fluorine, chlorine and bromine, or with C(X') 3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Cι-Cι 0 alkyl groups, linear or branched Ci-Cβ alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetrame- thylpiperidine group; a carboxylic acid group; a chloro carbonyl group; an amide group; a COOR' a ester group wherein R' a represents a linear or branched Cχ-Cι 0 alkyl group; a benzyl group, said benzyl group optionally substituted with 1-5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X') 3 groups wherein X 1 is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Ci-Cio alkyl groups, linear or branched Ci-Cε alkoxyl groups, carboxyl groups, cyano groups, or with a 2,2,6,6- tetramethylpiperidine group; Ri and R 2 , the same or different, represent a linear or branched Ci-Cio alkyl group, said alkyl group optionally substituted with 1-10 halogen atoms selected from fluorine, chlorine and bromine, or with C(X') 3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Ci-Cε alkoxyl groups, carboxyl groups, cyano groups, or with a 2,2,6,6- tetramethylpiperidine group; a vinyl group; a (meth) allyl group; a (meth) acrylic group; a C 3 -C 8 1-alkenyloxyl group; a linear or branched C 2 -Cιo alkenyl group; a COOR' a ester group wherein R' a represents a linear or branched Cι-Cχo alkyl group; a benzyl group, said benzyl group optionally substituted with 1-5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X') 3 groups wherein X 1 is selected from fluorine, chlo- rine and bromine, hydroxyl groups, linear or branched Ci-Cio alkyl groups, linear or branched Cχ-C 6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; a linear or branched Ci-Cε alkoxyl group; an N-alkyl (Ci-Cβ) amine group; an N,N-dialkyl (Ci- e) amine group; or Ri and R 2 , considered jointly with the carbon atom to which they are bound, represent a C 4 -Cιo cycloalkyl group, said cycloalkyl group optionally substituted with halogen atoms selected from fluorine, chlorine and bromine, or with hydroxyl groups, linear or branched Ci-Cβ alkoxyl groups, carboxyl groups, cyano groups, amine groups, N-alkyl (Ci-Cε) amine groups, N,N- dialkyl (Ci-Cε) amine groups; an N,N-dialkyl (Cj- Cβ) amide group; an aryl group selected from phenyl and biphenyl; a cyano group; R, R, R5 and Re, the same or different, represent a hydrogen atom; a halogen atom selected from fluorine, chlorine, bromine and iodine; a linear or branched Ci-Cε alkyl group, said alkyl group optionally substituted with 1-6 halogen atoms selected from fluorine, chlorine and bromine, or with C(X') 3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Ci-Cβ alkoxyl groups, carboxyl groups, cyano groups, or with a 2,2,6,6- tetramethylpiperidine group; a benzyl group, said benzyl group optionally substituted with 1-5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X') 3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched C x -Cιo alkyl groups, linear or branched Cι-C 6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2,2,6,6- tetramethylpiperidine group; a hydroxyl group; a linear or branched Cι-C 6 alkoxyl group; an amine group; an N-alkyl (Ci-Ce) amine group; an N,N- dialkyl (Cχ-C 6 ) amine group; a piperidine, piperazine or morpholine group; a carboxylic acid group; a chloro carbonyl (CO-Cl) group; an amide group; a COOR' a ester group wherein R' a represents a linear or branched Cι-Cτ. 0 alkyl group; a benzyl group, said benzyl group optionally substituted with 1-5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X' 3 ) groups wherein X' is se- lected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Cχ-Cιo alkyl groups, linear or branched Ci-Cβ alkoxyl groups, carboxyl groups, cyano groups, or with a 2,2,6,6- tetramethylpiperidine group; a Cι-C 6 carboxyalkyl group; a C 2 -C 6 carboxyalkenyl group; a carboxyamide group; an N-alkyl (Cχ-Ce) carboxyamide group; an N,N-dialkyl (Ci-Cβ) carboxyamide group; a cyano group; a nitro group; a sulfonic group; an aryl group selected from phenyl, biphenyl and naphthyl, said aryl group optionally substituted with N,N- dialkyl (Ci-Cβ) amine groups, linear or branched Ci-Cε alkoxyl groups, hydroxyl groups, linear or branched Cι-C 6 alkyl groups; an acyl group of the alkyl ketone, aryl ketone or benzyl ketone type; a vinyl group; a (meth) allyl group; a (meth) acrylic group; a C 3 -C 8 1-alkenyloxyl group; a linear or branched C 2 -C6 alkenyl group, said alkenyl group optionally substituted with one or two N,N-di- alkyl- (Cι-C 6 ) -4-aniline groups; an N-2,3- dihydroindoline group; a linear or branched ι~ thioether group; two consecutive substituents between R 3 and R can represent the condensation points with other aro- matic, heterocyclic or quinonic rings; P represents a monocyclic or polycyclic aromatic nucleus, belonging to one of the following types benzenic represented by general formula (VI) naphthalenic represented by general formula (VII) quinolinic represented by general formula (VIII) isoquinolinic represented by general formula (IX) cumarinic represented by general formula (X) quinazolinic represented by general formula (XI) phenanthrenic represented by general formula (XII) ; anthracenic represented by general formula (XIII); or a group with general formula (XIV) : wherein: at least two consecutive substituents between R 8 and R 13 , R i4 and R 21 , R 22 and R 28 , R 30 and R 35 , R 36 and Rι, R 42 and R 7 , R 8 and R 57 , R 58 and R 67 , R 68 and R 75 , represent the condensation points with the oxazine or pyran ring, the other substituents having the meaning described for substituents R 3 , R, R 5 and Re; Xi represents an oxygen atom; a sulfur atom; a selenium atom; an NH group; an NR a group wherein R a represents a linear or branched Cι-Cι 0 alkyl group; Y represents CH or a nitrogen atom. The photochromatic compounds having general formula (I) according to claim 1, wherein: R'ι represents an OH group; or a photochromatic compound having general formula (II) ; R' represents a linear or branched C 1 -C 4 alkyl group; a linear or branched C 2 -C 4 acyl group; a hydroxyl group; a linear or branched Ci-Cε alkoxyl group; an amine group; an N-alkyl (Ci-Cβ) amine group; an N,N-dialkyl (Ci-Cε) amine group; a pi- peridine, piperazine or morpholine group; a carboxylic acid group; a chloro carbonyl (CO-Cl) group; a (meth) allyl group; a (meth) acrylic group; a C3-C8 1-alkenyloxyl group; R' ' represents a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, or a phenyl group; Y represents a nitrogen atom; or CH; P' represents one of the groups having general formula (III), (IV) or (V) wherein: R and R 7 , the same or different, represent one of the following groups: methyl, ethyl, isopropyl, 2-allyl, 2-methallyl, 2- hydroxyethyl, 2-carboxymethyl, phenyl, 4- N,N-dimethylaminoaniline, 4-methoxybenzene, 4-cyanobenzene; a linear or branched Ci-Cε alkoxyl group; a linear or branched C 2 -C 6 amine group; an N,N-dialkyl (Ci-Cε) amine group; Ri and R 2 , the same or different, represent a methyl or phenyl group; or considered jointly with the carbon atom to which they are bound, represent a cyclohexyl group; - R 3 , R 4 , R5 and R 6 , the same or different, rep- resent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or one of the following groups: methyl, isopropyl, hydroxyl, methoxyl, N,N-dimethylamine, piperi- dine, morpholine, carboxyl, carboxymethyl, N,N-dimethylcarboxyamide, cyano, nitro, methylketone, phenylketone, phenyl; a linear or branched Cχ-C 6 alkoxyl group; an amine group; an N-alkyl (Ci-Cβ) amine group; an N,N-dialkyl (Ci-Cε) amine group; a piperi- dine, piperazine or morpholine group; a carboxylic acid group; an amide group; a chloro carbonyl (CO-Cl) group; a COOR' a ester group wherein R' a represents a linear or branched C_-Cιo alkyl group; P represents one of the groups having general formula from (VI) to (XIV), wherein: (a) two consecutive substituents between R 8 and Ri 3 , R 14 and R 2i , R 22 and R 28 , R 3 o and R 35 , R 36 and Rι, R 2 and R 4 , R 8 and Rs 7 , R 58 and R 67 , Rεβ and R 5 , independently represent the condensation points with the oxazine or pyran ring; and the other substituents each independently represent a hydrogen atom, a fluo- rine atom, a chlorine atom, a bromine atom, or one of the following groups: methyl, isopropyl, 2- (meth) allyl, (meth)acryl, hydroxyl, methoxyl, 2-hydroxyethyl, amine, N- methylamine, N-ethylamine, N,N-dimethyl- amine, piperidine, morpholine, carboxyl, carboxymethyl, N,N-dimethylcarboxyamide, cyano, nitro, methylketone, ethylketone, phenylketone, methylthiol; (b) two consecutive substituents between R 8 and Ri3, Ri 4 and R 21 , R 22 and R 28 , R 30 and R 35 , R 36 and Rι, R 42 and R 47 , R 48 and R 57 , R 58 and R 6 , Res and R 75 , different from those indicated under point (a) , represent the condensation points with the benzene or quinone ring; - Xi represents an oxygen atom; a sulfur atom; a selenium atom; an NH group. 3. A photochromatic compound having general formula (I) according to claim 1 or 2, consisting of the compound having formula (la) : A photochromatic compound having general formula (I) according to claim 1 or 2, consisting of the compound having formula (lb) : A photochromatic compound having general formula (I) according to claim 1 or 2, consisting of the compound having formula (Ic) : A process for the preparation of the photochromatic compounds having general formula (I) according to any of the previous claims, comprising the condensation of photochromatic compounds having general formula (II) : wherein the substituents R', R 1 ', P, P' and Y have the same meanings described above, with a cyanuryl halide having general formula (XV) : X wherein X represents a halogen atom such as fluorine, chlorine, bromine or iodine, in the presence of an inert organic solvent, at a temperature ranging from 20°C to 100°C, for a time ranging from 1 hour to 10 hours. 7. The process according to claim 6, wherein the inert or- ganic solvent is selected from acetone, ethyl alcohol, isopropanol, toluene, dioxane, or mixtures of these solvents. 8. The process according to claim 6 or 7, wherein the reaction temperature ranges from 20°C to 40 °C. 9. The process according to claim 6, 7 or 8, wherein the reaction time ranges from 2 hours to 5 hours . lϋ. Polymeric compositions comprising at least one photochromatic compound according to any of the previous claims, and at least one organic polymer selected from high density polyethylene (HDPE) , low density polyethylene (LDPE) , ethylene-vinylacetate copolymer, poly- ether amides, polypropylene, polymethyl methacrylate, polyvinyl alcohol, polyvinyl butyral, cellulose acetate butyrate, epoxy, polysiloxane or urethane resins, poly- carbonate, polydiethylene glycol bis (allyl carbonate), polyamides, polyesters, polystyrene, polyvinyl chloride, polyethylacrylate, siliconic polymers. 11. Coating compositions, such as paints, lacquers, paints or lacquers based on hybrid polysiloxanes and/or silica gel, compositions based on plastic materials, comprising one or more of the photochromatic compounds having general formula (I) according to any of the previous claims . 12. The compositions according to claim 10 or 11, compris- ing additives for organic polymers selected from phenol antioxidants, sterically hindered amines, benzotri- azoles, benzophenones, phosphites or phosphonites. 13. Photochromatic articles obtained from the processing of the compositions according to any of claims 10, 11 or 12. 14. Mixtures comprising at least one photochromatic compound having general formula (I) according to any of the claims from 1 to 9 and at least one photochromatic compound belonging to the group of spiro-indolino- oxazines or spiro-pyrans.

Inventors: DENIEL MARIE-HELENE, GIROLDINI WILLIAM, MALATESTA VINCENZO, SALEMI-DELVAUX CHRISTIANE, DENIEL, MARIE-HELENE, GIROLDINI, WILLIAM, MALATESTA, VINCENZO, SALEMI-DELVAUX, CHRISTIANE
Applicants: DENIEL MARIE HELENE, GIROLDINI WILLIAM, GREAT LAKES CHEMICAL EUROP, MALATESTA VINCENZO, SALEMI DELVAUX CHRISTIANE, DENIEL, MARIE-HELENE, GIROLDINI, WILLIAM, GREAT LAKES CHEMICAL (EUROPE) GMBH, MALATESTA, VINCENZO, SALEMI-DELVAUX, CHRISTIANE
Application year: 1999
Main classification: C09K9
IPC codes: C07D405, C07D498, C07D519, C09K9, G03C1