WO2000005325A1 - Photochromic compounds, process for their preparation and their use in polymeric materials - Google Patents

Photochromic compounds, process for their preparation and their use in polymeric materials Download PDF

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WO2000005325A1
WO2000005325A1 PCT/EP1999/004873 EP9904873W WO0005325A1 WO 2000005325 A1 WO2000005325 A1 WO 2000005325A1 EP 9904873 W EP9904873 W EP 9904873W WO 0005325 A1 WO0005325 A1 WO 0005325A1
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group
groups
branched
linear
general formula
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PCT/EP1999/004873
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French (fr)
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Vincenzo Malatesta
Christiane Salemi-Delvaux
Marie-Hélène DENIEL
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Great Lakes Chemical (Europe) Gmbh
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Publication of WO2000005325A1 publication Critical patent/WO2000005325A1/en

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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/72Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/73Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
    • G03C1/733Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds with macromolecular compounds as photosensitive substances, e.g. photochromic
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02Silicon compounds
    • C07F7/21Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10The polymethine chain containing an even number of >CH- groups
    • C09B23/105The polymethine chain containing an even number of >CH- groups two >CH- groups
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00Other synthetic dyes of known constitution
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00Dyes not provided for by a single group of this subclass
    • C09B69/008Dyes containing a substituent, which contains a silicium atom
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02Organic tenebrescent materials
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/685Compositions containing spiro-condensed pyran compounds or derivatives thereof, as photosensitive substances

Definitions

  • the present invention relates to photochromatic com- pounds.
  • the present invention relates to silylated photochromatic compounds, a process for their preparation and their use in polymeric materials.
  • a furtner object of the present invention relates to polymeric compositions containing said photochromatic compounds ana the 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.
  • photochromatic char- acte ⁇ stics which belong to various groups of both organic and inorganic compounds such as, for example, those described m the texts "Photochromism”, by G.H. Brown (Ed.), Vol. Ill of the Weissberger series “Techniques of Organic Chemistry", Wiley Interscience, New York (1971) and m “Photochromism: Molecules and Systems", by H. Durr and H. Bouas- Laurent (Ed.), Vol. 40 of the series “Studies m Organic Chemistry” Elsevier (1990) .
  • organic photochromatic compounds those belonging to the groups of spiro-indolmo-oxazmes, 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, m the production of photochromatic lenses for eye-glasses, special inks, toys, and in many other applications.
  • the Applicant has now found silylated photochromatic compounds which have good photochromatic characteristics, good fatigue resistance and good colourability characte ⁇ s- tics.
  • the present invention therefore relates to photochro- matic compounds having general formula (i;
  • X represents an oxygen atom; a sulfur atom; a selenium atom; an NH group; or an NR a 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 C ⁇ -C 6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; R'x represents 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 fluo-
  • R' represents a linear or branched Ci-Cio alkyl group; a linear or branched C 2 -C ⁇ 0 acyl group; a linear or branched C 2 -C ⁇ o heteroalkyl group in which the heteroa- tom is selected from nitrogen, oxygen, sulfur and sele- nium;
  • R' ' represents a hydrogen atom; a halogen atom selected from fluorine, chlorine and bromine; a linear or branched Ci-C ⁇ alkyl group; a linear or branched C ⁇ -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 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-C ⁇ 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 -C6 alkenyl group; an aryl group selected from phenyl, biphenyl and naphthyl, said aryl group optionally substituted with linear or branched C ⁇ -C 6 alkoxyl groups, carboxyl groups, amine groups, N,N-dialkyl (C ⁇ -C 6 ) amine groups; a C00R' a ester group wherein R
  • R 3 , R 4 , R 5 andR 6 represent a hydrogen atom; a halogen atom selected from fluorine, chlorine, bromine and iodine; a linear or branched Ci- C 6 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 C ⁇ -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
  • 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 repre- sented by general formula (VIII); isoquinolinic repre- ' sented 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); dibenzofuran represented by general formula (XIV) :
  • Y represents CH or a nitrogen atom.
  • Preferred photochromatic compounds having general formula (I) for the purposes of the present invention are those wherein:
  • X represents an oxygen atom
  • R' ⁇ represents a methyl
  • R' 2 represents an OH group; or a photochromatic com- pound 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 linear or branched C 2 -C 4 heteroalkyl group in which the heteroa- torn is selected from nitrogen, oxygen, sulfur and selenium;
  • R' ' represents a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, or a phenyl group
  • Y represents N or CH
  • P' represents one of the groups having general formula (III), (IV) or (V) wherein:
  • R and R 7 represent one of the following groups: methyl, ethyl, isopropyl, 2- allyl, 2-methallyl, 2-hydroxyethyl, 2-carbo- xymethyl, phenyl, 4-N,N-dimethylaminoaniline, 4- methoxybenzene, 4-cyanobenzene;
  • Ri and R 2 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 , R 5 and R 6 represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or one of the following groups: methyl, isopropyl, hydroxyl, methoxyl, N,N-di- methylamine, piperidine, morpholine, carboxyl, carboxymethyl, N,N-dimethylcarboxy-amide, cyano, ' nitro, methylketone, phenylketone, phenyl; P represents one of the groups having general formula from (VI) to (XIV), wherein: (a) two consecutive substituents between R 8 and R i3 , R ⁇ 4 and R 2 ⁇ , R 22 and R 28 , R 30 and R 35 , R 3 ⁇ and R 4i , R 42 and R 47 , R 4 s and R 57 , R58 and R 6 , R ⁇ s and R 75 , independently represent the condensation points with the oxa
  • a further object of the present invention relates to a process for the preparation of 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)
  • substituents R' ⁇ and X have the same meanings described above, in the presence of an inert organic solvent such as, for example, acetone, ethyl alcohol, isopropanol, toluene, dioxane, or a mixture of these solvents, at a temperature ranging from 50°C to 100°C, preferably from 60°C to 80°C, for a time ranging from 1 hour to 10 hours, preferably from 2 hours to 5 hours.
  • an inert organic solvent such as, for example, acetone, ethyl alcohol, isopropanol, toluene, dioxane, or a mixture of these solvents
  • the reaction product thus obtained is generally purified on a silica column, with subsequent crystallization from a solvent such as, for example, ace- • tone, toluene, pentane, heptane, diethyl ether, or by repeated precipitations with methanol and dried with toluene.
  • a solvent such as, for example, ace- • tone, toluene, pentane, heptane, diethyl ether, or by repeated precipitations with methanol and dried with toluene.
  • 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 , ⁇ -unsaturated aldehydes hav- ing 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
  • the condensation reaction is carried out in the presence of an inert organic solvent such as, for example, ethyl alcohol, isopropanol, toluene, or a mixture of these sol- vents, and in the presence of an amine such as, for example, triethylamine, morphoiine, piperidine, or of an acid such as, for example, paratoluenesulfonic acid, sulfuric acid, acid alumina, or of a metal complex such as, for example, titanium (IV) tetraethoxide, 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.
  • an inert organic solvent such as, for example, ethyl alcohol, isopropanol, toluene, or a mixture of these sol- vents
  • an amine such as, for example, triethylamine, morphoi
  • the reaction product thus obtained is generally purified by elution on a silica column with subsequent crystallization from a solvent such as, for example, acetone, toluene, heptane, pentane, diethyl ether.
  • a solvent such as, for example, acetone, toluene, heptane, pentane, diethyl ether.
  • 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, chlorides, 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/ethylenediamine acetylide complex as described, for example, in U.S. patents 5,585,042 and 5,238,981.
  • the compounds deriving from ⁇ , ⁇ -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 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, ⁇ -naphthol or phenol.
  • isoindoline compounds having general formula (XVI), or indoline compounds having general formula (XVII), are the following:
  • nitroso compounds having general formula (XX) are the following:
  • the photochromatic compounds having general formula (I) of the present invention are brightly yellow or dark yellow- coloured, oily or crystalline products.
  • 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.
  • 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.
  • a solvent 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 carrier 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.
  • 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.
  • 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 im- pregnation 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 the method described, for example, in U.S. patent 5,130,353.
  • a transparent substrate such as, for example, polycarbonate, polymethyl methacrylate or polydiethyleneglycol bis (allyl carbonate
  • 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 techniques described above, into various organic polymers such as, for example, high density polyethylene (HDPE), low density poly- ethylene (LDPE) , ethylene-vinylacetate copolymer, polyether amides, polypropylene, polymethyl methacrylate, polyvinyl alcohol, polyvinyl butyral, cellulose acetate butyrate, ep- oxy, polysiloxane or urethane resins, polycarbonate, polydi- ethylene glycol bis (allyl carbonate), polyamides, polyes- ters, polystyrene, polyvinylchloride, polyethylacrylate, siliconic polymers.
  • HDPE high density polyethylene
  • LDPE low density poly- ethylene
  • ethylene-vinylacetate copolymer polyether amides
  • polypropylene polymethyl methacrylate
  • a further object of the present invention therefore relates to polymeric compositions comprising the above polymeric materials and the above photochromatic compounds hav- ing general formula (I) and the photochromatic articles ob- tained 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 compositions, 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. 3C, pages 5789-5792.
  • the above coating compositions can be applied to the substrate (metal, plastic, wood, etc.) using the conventional 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 .
  • 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, have a brightly yellow or dark yellow colouring, 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.
  • 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 pH 14 is reached: a yellow-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 31.5 g.
  • a quantity equal to 31.5 g of the above product is placed in a 100 ml inox steel autoclave together with 20 ml of toluene and 23.8 g of methyliodide.
  • the autoclave is heated to 85°C and is maintained at this temperature, under a nitrogen atmosphere, for 6 hours.
  • 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.
  • 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 neutral col- umn of active aluminum oxide 90 (activity degree I), eluting with a mixture of heptane/ethyl acetate in a ratio of 1/1.
  • the aqueous phase is further washed with toluene, treated with aqueous sodium hydroxide (solution at 30%) until reaching pH 14 and with toluene.
  • the organic phases obtained are concentrated and dried.
  • the above mixture is heated to 90 °C and maintained at this temperature, under stirring, under a nitrogen atmosphere, for 6 hours.
  • the raw reaction product obtained is dried and repeatedly extracted with boiling heptane to which 1 g of activated carbon has been added.
  • the heptane extracts are concentrated and boiled with an additional 0.6 g of activated carbon.
  • reaction raw product obtained is filtered and subsequently purified by passage on a silica column eluting with a mixture of toluene/hexane in a ratio of 1/1.
  • An almost pure photochromatic product (yellow-white solid) is obtained, which is further purified by crystallization from toluene.
  • 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 7C°C for 15 minutes: the reaction raw product is filtered, concentrated and cooled.
  • the precipitated raw product is filtered obtaining 6.3 g of a solid white product corresponding to the Compound having formula (XVIIa) -3 which is identified by gas-mass
  • the reaction raw product obtained is purified by passage on a silica column, eluating with ethyl acetate and then with acetone.
  • reaction raw product obtained is purified by repeated precipitations with methanol and dried with toluene.
  • EXAMPLE 10 Evaluation of the photochromatic activity.
  • the photochromatic activity is evaluated in ethanol, at 10°C, of Compounds (Ia)-(Ic) obtained as described in Examples 7-9.
  • Solutions are prepared at a concentration equal to 10 ⁇ 4 M of the various Compounds (Ia)-(Ic) in ethanol and subse- quently 2 ml of each solution i? 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 photodiode detector (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 wave-lengths. The following parameters are determined using the measurements obtained as described above and with a calculation effected with the GRAFit program of Erithaeus Software Ltd.
  • t ⁇ /2 (s) time in which the absorbance of the merocya- nine open form is equal to half of the initial absorbance value
  • k ⁇ (s _1 ) constant of the oxazine ring closing thermal reaction rate
  • ⁇ PMC (nm) 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.

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Abstract

Photochromatic compounds having general formula (I). The above photochromatic compounds can be used in polymeric materials, obtaining photochromatic articles.

Description

PHOTOCHROMIC 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 silylated photochromatic compounds, a process for their preparation and their use in polymeric materials.
A furtner object of the present invention relates to polymeric compositions containing said photochromatic compounds ana the 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 char- acteπstics, which belong to various groups of both organic and inorganic compounds such as, for example, those described m the texts "Photochromism", by G.H. Brown (Ed.), Vol. Ill of the Weissberger series "Techniques of Organic Chemistry", Wiley Interscience, New York (1971) and m "Photochromism: Molecules and Systems", by H. Durr and H. Bouas- Laurent (Ed.), Vol. 40 of the series "Studies m Organic Chemistry" Elsevier (1990) .
Among organic photochromatic compounds, those belonging to the groups of spiro-indolmo-oxazmes, 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, m the production of photochromatic lenses for eye-glasses, special inks, toys, and in many other applications.
As an example, tne 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 silylated photochromatic compounds which have good photochromatic characteristics, good fatigue resistance and good colourability characteπs- tics. The present invention therefore relates to photochro- matic compounds having general formula (i;
Figure imgf000005_0001
wherein:
X represents an oxygen atom; a sulfur atom; a selenium atom; an NH group; or an NRa group wherein Ra 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 Cι-C6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; R'x represents 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 fluo- rine, chlorine and bromine, hydroxyl groups, linear or ' branched Cι-C6 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 C2-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-C6 amine groups; 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 bro- mine, hydroxyl groups, linear or branched Ci-Cio alkyl groups, linear cr branched Cι-Cδ alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; R'2 represents an OH group; or a photochromatic com- pound having general formula (II).
Figure imgf000006_0001
R' represents a linear or branched Ci-Cio alkyl group; a linear or branched C2-Cι0 acyl group; a linear or branched C2-Cιo heteroalkyl group in which the heteroa- tom is selected from nitrogen, oxygen, sulfur and sele- nium;
R' ' represents a hydrogen atom; a halogen atom selected from fluorine, chlorine and bromine; a linear or branched Ci-Cβ alkyl group; a linear or branched Cι-C6 alkoxyl group; a phenyl group; a phenoxyl group; P' represents one of the following groups having general formula (III), (IV) or (V):
Figure imgf000007_0001
R7 /R7
( V ) ;
R and R, 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; an allyl or methallyl group; a linear or branched C2-C6 alkenyl group; an aryl group selected from phenyl, biphenyl and naphthyl, said aryl group optionally substituted with linear or branched Cι-C6 alkoxyl groups, carboxyl groups, amine groups, N,N-dialkyl (Cι-C6) amine groups; a C00R'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; Ri and R2, 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 fluo- rine, chlorine and bromine, or with C(X')3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Cι-C6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; a vinyl group; an allyl or methallyl group; an acrylic or methacrylic group; a heteroallyl group; a linear or branched C2-Cι0 alkenyl group; a C00R'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 C-i-Cio alkyl groups, linear or branched Cι-C6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; a linear or branched Cι-C6 alkoxyl group; an N-alkyl (Cι-C6) amine group; an N,N-dialkyl (Cι-C6) amine group; or Ri and R2, considered jointly with the carbon atom to which they are bound, represent a C4-C10 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 (Cι-C6) amine groups, N,N-dialkyl (Ci-Cβ) amine groups; an N,N-dialkyl (Ci-Cβ) amide group; an aryl group selected from phenyl and biphenyl; a cyano group;
R3, R4, R5 andR6, the same or different, represent a hydrogen atom; a halogen atom selected from fluorine, chlorine, bromine and iodine; a linear or branched Ci- C6 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 Cι-C6 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-C6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; a hydroxyl group; a linear or branched Cι-C6 alkoxyl group; an amine group; an N-alkyl (Ci-Cβ) amine group; an N,N- ' dialkyl (Cι-Ce) amine group; a piperidine, piperazine or morpholine group; a Cι-C6 carboxyalkyl group; a C2-C6 carboxyalkenyl group; a carboxyamide group; an N-alkyl (Ci-Ce) carboxyamide group; an N,N-dialkyl (Cι-C6) carboxyamide group; a cyano group; a nitro group; a sul- fonic group; an aryl group selected from phenyl, biphenyl and naphthyl, said aryl group optionally substituted with N,N-dialkyl (Ci-Ce) amine groups, linear or branched Cι-C6 alkoxyl groups, hydroxyl groups, linear or branched Cι~C6 alkyl groups; an acyl group of the alkyl ketone, aryl ketone or benzyl ketone type; a vinyl group; an allyl or methallyl group; an acrylic or methacrylic group; a heteroallyl group; a linear or branched C2-C6 alkenyl group, said alkenyl group optionally substituted with one or two N,N-dialkyl- (Ci- Cβ) -4-aniline groups; an N-2, 3-dihydroindoline group; a linear or branched Cι-C6 thioether group; two consecutive substituents between R3 and R6 can rep- resent 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 repre- sented by general formula (VIII); isoquinolinic repre-' sented 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); dibenzofuran represented by general formula (XIV) :
Figure imgf000012_0001
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000014_0002
wherein: - at least two consecutive substituents between R8 and Ri3, Ri4 and R2ι, R22 and R28, R3o and R35, R36 and R41, R42 and R47, R48 and R57, Rss and R67, Rββ and R75, represent the condensation points with the oxazine or pyran ring, the other substituents having the meaning described for substituents R3, R4, R5 and Re;
Y represents CH or a nitrogen atom.
Preferred photochromatic compounds having general formula (I) for the purposes of the present invention, are those wherein:
X represents an oxygen atom;
R'ι represents a methyl;
R'2 represents an OH group; or a photochromatic com- pound having general formula (II);
R' represents a linear or branched C1-C4 alkyl group; a linear or branched C2-C4 acyl group; a linear or branched C2-C4 heteroalkyl group in which the heteroa- torn is selected from nitrogen, oxygen, sulfur and selenium;
R' ' represents a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, or a phenyl group; Y represents N or CH; P' represents one of the groups having general formula (III), (IV) or (V) wherein:
R and R7, the same or different, represent one of the following groups: methyl, ethyl, isopropyl, 2- allyl, 2-methallyl, 2-hydroxyethyl, 2-carbo- xymethyl, phenyl, 4-N,N-dimethylaminoaniline, 4- methoxybenzene, 4-cyanobenzene;
Ri and R2, 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;
R3, R4, R5 and R6, the same or different, represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or one of the following groups: methyl, isopropyl, hydroxyl, methoxyl, N,N-di- methylamine, piperidine, morpholine, carboxyl, carboxymethyl, N,N-dimethylcarboxy-amide, cyano, ' nitro, methylketone, phenylketone, phenyl; P represents one of the groups having general formula from (VI) to (XIV), wherein: (a) two consecutive substituents between R8 and Ri3, Rι4 and R2ι, R22 and R28, R30 and R35, R3β and R4i, R42 and R47, R4s and R57, R58 and R6 , Rεs and R75, independently 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, hydroxyl, methoxyl, 2-hydrcxyethyl, 2-allyl, piperidine, morpholine, N,N-dimethylamine, carboxyl, carboxymethyl, N,N-dimethylcarboxyamide, cyano, nitro, methylketone, ethylketone, phenylketone, methylthiol;
(b) two consecutive substituents between R8 and R13, Ri4 and R2ι, R22 and R28, R30 and R35, R30 and R4i, R42 and R47, R48 and R57, R58 and R67, Res and R75, different from those indicated under point (a) , represent the condensation points with the benzenic or qui- nonic ring.
Specific examples of preferred compounds according to the present invention are: Compound having formula (la):
Figure imgf000017_0001
Compound having formula (lb):
Figure imgf000017_0002
Compound having formula (Ic)
Figure imgf000018_0001
A further object of the present invention relates to a process for the preparation of 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)
Figure imgf000019_0001
wherein the substituents R', R'', P, P' and Y have the same meanings described above, with silylated tetramers having general formula (XV) :
Figure imgf000019_0002
wherein the substituents R'ι and X have the same meanings described above, in the presence of an inert organic solvent such as, for example, acetone, ethyl alcohol, isopropanol, toluene, dioxane, or a mixture of these solvents, at a temperature ranging from 50°C to 100°C, preferably from 60°C to 80°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 column, with subsequent crystallization from a solvent such as, for example, ace- tone, toluene, pentane, heptane, diethyl ether, or by repeated precipitations with methanol and dried with toluene. 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 , β-unsaturated aldehydes hav- ing 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
Figure imgf000020_0001
- 11 Scheme 2
Figure imgf000021_0001
Scheme 3
Figure imgf000021_0002
(XXI)
(XVIII) (XVIIIa)
Scheme 4
Figure imgf000021_0003
(XIX) (XXI) (XVIIIa)
wherein the substituents R, from Rx to R7, 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, or a mixture of these sol- vents, and in the presence of an amine such as, for example, triethylamine, morphoiine, piperidine, or of an acid such as, for example, paratoluenesulfonic acid, sulfuric acid, acid alumina, or of a metal complex such as, for example, titanium (IV) tetraethoxide, 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 generally purified by elution on a silica column with subsequent crystallization from a solvent such as, for example, acetone, toluene, heptane, pentane, diethyl ether.
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, chlorides, 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/ethylenediamine acetylide 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 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:
Figure imgf000024_0001
Figure imgf000024_0002
Figure imgf000024_0003
CH-
Specific examples of nitroso compounds having general formula (XX) are the following:
NO
Figure imgf000025_0001
NO
Figure imgf000025_0002
Figure imgf000025_0003
The photochromatic compounds having general formula (I) of the present invention are brightly yellow or dark yellow- coloured, oily or crystalline products.
Their solutions in common organic solvents such as, for example, benzene, toluene, methanol, ethanol, when exposed to light sources, are brightly yellow or dark yellow- coloured. These solutions, if exposed to a light source, either visible or ultraviolet, become blue or green. The colouring quickly decays 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 carrier 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 im- pregnation 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 the 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 techniques described above, into various organic polymers such as, for example, high density polyethylene (HDPE), low density poly- ethylene (LDPE) , ethylene-vinylacetate copolymer, polyether amides, polypropylene, polymethyl methacrylate, polyvinyl alcohol, polyvinyl butyral, cellulose acetate butyrate, ep- oxy, polysiloxane or urethane resins, polycarbonate, polydi- ethylene glycol bis (allyl carbonate), polyamides, polyes- ters, polystyrene, polyvinylchloride, polyethylacrylate, siliconic polymers.
A further object of the present invention therefore relates to polymeric compositions comprising the above polymeric materials and the above photochromatic compounds hav- ing general formula (I) and the photochromatic articles ob- tained 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 compositions, 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. 3C, pages 5789-5792. The above coating compositions can be applied to the substrate (metal, plastic, wood, etc.) using the conventional 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, have a brightly yellow or dark yellow colouring, 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 itself. EXAMPLE 1 Preparation of 1 , l,4,7-tetramethyl-N-allyl~3-methylene- isoindoline iodide having formula (XV ')~A:
Figure imgf000030_0001
CH2 (XVI')-A CH
CH2
40 g of acetonylacetone, 16 g of allylylamine hydrochloride, 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 pH 14 is reached: a yellow-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 31.5 g. This product is identified as 1, 1, 4,7-tetramethyl-isoindoline, by gas-mass (molecular weight = 227) . A quantity equal to 31.5 g of the above product is placed in a 100 ml inox steel autoclave together with 20 ml of toluene and 23.8 g of methyliodide. The autoclave is heated to 85°C and 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.
43.6 g of product are obtained, corresponding to 1,1,4, 7-tetramethyl-N-allyl-3-methylene-isoindoline iodide having formula (XVI') -A. The free base, corresponding to Compound (XVI'), is identified by gas-mass (molecular weight = 241) and the salt by NMR. EXAMPLE 2 Preparation of the compound having formula (XVTa) -1 :
Figure imgf000031_0001
4 g of 1, i, 4, 7-tetramethyl-N-aliyl-3-methylene-isoindoline iodide obtained as described in Example 1, 2.9 g of the sodium salt of l-nitroso-2-hydroxydibenzofuran and 60 ml of acetone are charged into a 250 ml flask, equipped with a re- flux 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 neutral col- umn of active aluminum oxide 90 (activity degree I), eluting with a mixture of heptane/ethyl acetate in a ratio of 1/1.
An almost pure photochromatic product (yellow solid) is obtained which is further purified by crystallization from pentane. After crystallization, 2 g of a solid, white product are obtained, corresponding to the compound having formula (XVIa)-l which is identified by gas-mass (molecular weight = 422) . EXAMPLE 3 Preparation of l,l-dimethyl-N-methyl-allyl-2-methylene- indoline iodide having formula (XVII') -A:
Figure imgf000033_0001
7,2 g of 2, 3, 3-trimethylindoline, 8.1 g of potassium iodide, 5.4 g of allylamine hydrochloride, 20 ml of water and 12 ml of acetonitrile are charged into a 100 ml closed test-tube.
The above mixture is heated to 90 °C for 8 hours. At the end, the raw product obtained is washed with water, with toluene and with hydrochloric acid until pH 7.
The aqueous phase is further washed with toluene, treated with aqueous sodium hydroxide (solution at 30%) until reaching pH 14 and with toluene. The organic phases obtained are concentrated and dried.
A pinkish-brown oil is obtained: the yield is 8.3 g. This product is identified as 1, l-dimethyl-N-methylallyl-2- methylene-indoline iodide by gas-mass (molecular weight = 213) . EXAMPLE 4 Preparation of the compound having formula (XVIIa) -1 : (XVIIa)-l
Figure imgf000034_0001
1.7 g of 1, l-dimethyl-N-methyl-allyl-2-methylene- indoline iodide obtained as described in Example 3, 1.73 g of the sodium salt of l-nitroso-2-naphthol and 8 ml of toluene, are charged into a 250 ml flask equipped with a reflux cooler and mechanical stirrer.
The above mixture is heated to 90 °C and maintained at this temperature, under stirring, under a nitrogen atmosphere, for 6 hours. The raw reaction product obtained, is dried and repeatedly extracted with boiling heptane to which 1 g of activated carbon has been added. The heptane extracts are concentrated and boiled with an additional 0.6 g of activated carbon.
The reaction raw product obtained is filtered and subsequently purified by passage on a silica column eluting with a mixture of toluene/hexane in a ratio of 1/1. An almost pure photochromatic product (yellow-white solid) is obtained, which is further purified by crystallization from toluene.
After crystallization, 1.2 g of a solid white product are obtained, corresponding to the compound having formula (XVIIa)-l which is identified by gas-mass (molecular weight = 368) . EXAMPLE 5 Preparation of the compound having formula (XVIIa) -2
(XVIIa)-2
Figure imgf000035_0001
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 atmos- ' phere, until dissolution. 10.7 g of sulfuric acid diluted in 30 ml of water are subsequently added dropwise and the reaction temperature is maintained at 0°C to 5°C. After 30 min- utes 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.
18.6 g of 2, 7-dihydroxy-l-nitroso-naphthalene are mixed with 17 g of 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 7C°C for 15 minutes: the reaction raw product is filtered, concentrated and cooled.
The precipitated raw product is filtered obtaining 7.0 g of a solid white product corresponding to the Compound having formula (XVIIa) -2 which is identified by gas-mass (molecular weight = 344. EXAMPLE 6 Preparation of the compound having formula (XVIIa) -3 :
Figure imgf000037_0001
6.9 g of Compound (XVIIa) -2 obtained in Example 5, 25 ml of toluene, 25 ml of acetonitrile and 4 ml of triethylamine are charged into a 250 ml flask, equipped with a reflux cooler and mechanical stirrer, obtaining a solution which is not completely homogeneous. This solution is maintained under a stream of nitrogen to prevent the product from oxidation. The above mixture is heated to 20 °C and a solution of 1.8 g of acryloyl chloride in 10 ml of toluene are added dropwise, obtaining a crystalline precipitate. After 10 minutes 50 ml of water and 5.0 g of sodium carbonate are added; the mixture is stirred and the two phases are separated. The organic phase is concentrated under vacuum obtaining a dark oil which is cooled.
The precipitated raw product is filtered obtaining 6.3 g of a solid white product corresponding to the Compound having formula (XVIIa) -3 which is identified by gas-mass
(molecular weight = 398) .
EXAMPLE 7
Preparation of the compound having formula (la) :
Figure imgf000038_0001
0.15 g of 2, 4, 6, 8-tetramethylcyclotetrasiloxane of Al-
drich (95%), a catalytic quantity of the complex platinu -
divinyltetramethyl-disiloxane and 10 ml of anhydrous toluene
are charged into a 100 ml flask, equipped with a reflux
cooler and mechanical stirrer. The mixture is maintained at
60°C, under stirring and in a nitrogen atmosphere, for 5
minutes. 1.0 g of the Compound (XVI-a)-l, obtained as described in Example 2, dissolved in 20 ml of anhydrous toluene is then added: this mixture is maintained at 80°C for 3 hours. At the end the solvent is eliminated by evaporation under vacuum.
The reaction raw product obtained is purified by passage on a silica column, eluating with ethyl acetate and then with acetone.
0.28 g of a product (dark yellow oil) are obtained, corresponding to the Compound having formula (la), which is identified by liquid chromatography coupled with a mass spectrometer (molecular weight = 1116.5) . EXAMPLE 8 Preparation of the compound having formula (lb) :
Figure imgf000040_0001
0.10 g of 2, 4, 6, 8-tetramethylcyclotetrasiloxane of Al- drich (95%), a catalytic quantity of the complex platinum- divinyltetramethyl-disiloxane and 5.0 ml of anhydrous toluene are charged into a 100 ml flask, equipped with a reflux cooler and mechanical stirrer. The mixture is maintained at 80°C, under stirring and in a nitrogen atmosphere, for 5 minutes.
0.8 g of the Compound (XVII-a)-l, obtained as described in Example 4, dissolved in 20 ml of anhydrous toluene are then added: this mixture is maintained at 80°C for 4 hours. At the end the solvent is eliminated by evaporation under vacuum.
- 31 The reaction raw product obtained is purified by repeated precipitations with methanol and dried with toluene.
0.25 g of a product (dark yellow oil) are obtained, corresponding to the Compound having formula (lb), which is identified by liquid chromatography coupled with a mass spectrometer (molecular weight = 1360.5). EXAMPLE 9 Preparation of the compound having formula (Ic) :
Figure imgf000041_0001
0.26 g of 2, 4, 6, 8-tetramethylcyclotetrasiloxane of Al- drich (95%), a catalytic quantity of the complex platinum- divinyltetramethyl-disiloxane and 20 ml of anhydrous toluene are charged into a 250 ml flask, equipped with a reflux cooler and mechanical stirrer. The mixture is maintained at 70°C, under stirring and in a nitrogen atmosphere, for 10 minutes .
1.8 g of the Compound (XVII-a)-3, obtained as described in Example 6, dissolved in 40 ml of anhydrous toluene are then added: this mixture is maintained at 70 °C for 8 hours.
At the end the solvent is eliminated by evaporation under vacuum.
The reaction raw product obtained is purified by repeated precipitations with methanol and dried with toluene. 0.85 g of a product (dark yellow oil) are obtained, corresponding to the Compound having formula (Ic) , which is identified by liquid chromatography coupled with a mass spectrometer (molecular weight = 1832.5). EXAMPLE 10 Evaluation of the photochromatic activity.
The photochromatic activity is evaluated in ethanol, at 10°C, of Compounds (Ia)-(Ic) obtained as described in Examples 7-9.
Solutions are prepared at a concentration equal to 10~4 M of the various Compounds (Ia)-(Ic) in ethanol and subse- quently 2 ml of each solution i? 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 photodiode detector (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 wave-lengths. The following parameters are determined using the measurements 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 absorbance value; kΔ (s_1) : constant of the oxazine ring closing thermal reaction rate; λPMC (nm) : 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 (XVIIa) -3: Compounds (la) - (Ic) show an increase in the value of the kΔ (s_1) constant.
The data obtained are indicated in Table 1.
TABLE 1
Figure imgf000044_0002
*: the samples analyzed have two values of the kΔ
Figure imgf000044_0001
constant .

Claims

1. Photochromatic compounds having general formula (i;
Figure imgf000045_0001
wherein:
X represents an oxygen atom; a sulfur atom; a selenium atom; an NH group; or an NRa group wherein Ra represents a linear or branched Ci-Cio alkyl group; a benzyl group, said benzyl group option- ally 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 Cχ-Cιo alkyl groups, linear or branched Cι-C6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2,2, 6, 6-tetramethylpiperidine group;
R'╬╣ represents a linear or branched C-i-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 C╬╣-C6 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 C2-C6 alkenyl group; an aryl group selected from phenyl, diphenyl and naphthyl, said aryl group optionally substituted with linear or branched C╬╣~C6 alkoxyl groups, carboxyl groups, amine groups, N,N-dialkyl (Ci-C╬▓) amine groups; 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 C╬╣-C6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2,2,6,6- tetramethylpiperidine group;
R'2 represents an OH group; or a photochromatic compound having general formula (II) :
Figure imgf000047_0001
R' represents a linear or branched Ci-Cio alkyl group; a linear or branched C2-C╬╣o acyl group; a linear or branched C2-C╬╣0 heteroalkyl group in which the heteroatom is selected from nitrogen, oxygen, sulfur and selenium;
R' ' represents a hydrogen atom; a halogen atom selected from fluorine, chlorine and bromine; a linear or branched Ci-C╬╡ alkyl group; a linear or branched C╬╣~C6 alkoxyl group; a phenyl group; a phenoxyl group;
P' represents one of the following groups having general formula (III), (IV) or (V):
Figure imgf000047_0002
Figure imgf000048_0001
R and R7, the same or different, represent a linear or branched Ci-Cio alkyl group, said alkyl group op- tionally 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~C6 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 C2-C╬▓ alkenyl group; an aryl group selected from phenyl, diphenyl and naphthyl, said aryl group optionally substi- tuted with linear or branched C╬╣-C6 alkoxyl groups, carboxyl groups, amine groups, N,N-dialkyl (C╬╣-C6) amine groups; a COOR'a ester group wherein R'a represents a linear or branched Ci-Cio alkyl group; a benzyl group, said benzyl group optionally substi- tuted 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╬╣-C10 alkyl groups, linear or branched Cj-C╬▓ alkoxyl groups, carboxyl groups, cyano groups, or with a 2,2,6, 6-tetramethylpiperidine group; Ri and R2, 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 C╬╣-C6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; a vinyl group; an allyl or methallyl group; an acrylic or methacrylic group; a heteroallyl group; a linear or branched C2-C╬╣0 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 C╬╣-C6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; a linear or branched Ci-C╬▓ alkoxyl group; an N-alkyl (C╬╣-C6) amine group; an N,N-dialkyl (Ci-C╬▓) amine group; or
Ri and R2, considered jointly with the carbon atom to which they are bound, represent a C4-C╬╣0 cycloalkyl group, said cycloalkyl group optionally substituted with halogen atoms selected from fluorine, chlorine and bromine, or with hydroxyl groups, linear or branched Cj-C╬▓ alkoxyl groups, carboxyl groups, cyano groups, amine groups, N-alkyl (C╬╣-C6) amine groups, N,N-dialkyl (C╬╣-C6) amine groups; an N,N-dialkyl (C╬╣-C6) amide group; an aryl group se- lected from phenyl and bip enyl; a cyano group;
R3, R4, R5 and R6, the same or different, represent a hydrogen atom; a halogen atom selected from fluorine, chlorine, bromine and iodine; a linear or branched C╬╣-C6 alkyl group, said alkyl group op- tionally 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-C╬╡ alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperid- ine 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- Ce alkoxyl groups, carboxyl groups, cyano groups, or with a 2,
2, 6, 6-tetramethylpiperidine group; a hydroxyl group; a linear or branched Ci-C╬▓ alkoxyl group; an amine group; an N-alkyl (d-C6) amine group; an N,N-dialkyl (Ci-C╬▓) amine group; a piperidine, piperazine or morpholine group; a C╬╣-C6 carboxyalkyl group; a C2-C╬┤ carboxyalkenyl group; a carboxyamide group; an N-alkyl (C╬╣~C6) carboxyamide group; an N,N-dialkyl (Ci-C╬▓) carboxyamide group; a cyano group; a nitro group; a sulfonic group; an aryl group selected from phenyl, biphenyl and naph- thyl, said aryl group optionally substituted with N,N-dialkyl (C╬╣-C6) amine groups, linear or branched C╬╣-C6 alkoxyl groups, hydroxyl groups, linear or branched Ci-C╬▓ alkyl groups; an acyl group of the alkyl ketone, aryl ketone or benzyl ketone type; a vinyl group; an allyl or methallyl group; an acrylic or methacrylic group; a heteroal- lyl group; a linear or branched C2-C6 alkenyl group, said alkenyl group optionally substituted with one or two N,N-dialkyl- (C╬╣-C6) -4-aniline groups; an N-2,
3-dihydroindoline group; a linear or branched Ci-C╬╡ thioether group; two consecutive substituents between R3 and Re 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: benzenic represented by general formula (VI); naph- thalenic 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) dibenzofuran represented by general formula (XIV) :
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
wherein: at least two consecutive substituents between R8 and R╬╣3, R14 and R2╬╣, R22 and R28, R30 and R35, 36 and R41, R42 and R47, R4s and R57, Rss and R67/ Res and R75, represent the condensation points with the oxazine or pyran ring, the other substituents having the meaning described for substituents R3, R4, R5 and
Re; Y represents CH or a nitrogen atom. 2. The photochromatic compounds having general formula (I) according to claim 1, wherein:
X represents an oxygen atom; - R'╬╣ represents a methyl;
R'2 represents an OH group; or a photochromatic compound having general formula (II); R' represents a linear or branched C╬╣~C alkyl group; a linear or branched C2-C4 acyl group; a linear or branched C2-C4 heteroalkyl group in which the heteroatom is selected from nitrogen, oxygen, sulfur and selenium;
R' ' represents a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, or a phenyl group; - Y represents N or CH;
P' represents one of the groups having general formula (III), (IV) or (V) wherein:
R and R7, the same or different, represent one of the following groups: methyl, ethyl, isopropyl, 2-allyl, 2-methallyl, 2-hydro- xyethyl, 2-carboxymethyl, phenyl, 4-N,N- dimethylaminoaniline, 4-methoxybenze-ne,
4-cyanobenzene;
Ri and R2, 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;
R3, R4, R5 and Re, the same or different, represent 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, piperidine, morpholine, carboxyl, carboxymethyl, N,N-dimethylcarboxyamide, cyano, nitro, meth- ylketone, phenylketone, phenyl;
P represents one of the groups having general formula from (VI) to (XIV), wherein:
(a) two consecutive substituents between R8 and R13, R14 and R2i, R22 and R28, R30 and R35, R36 and R4i, R42 and R4 , R48 and R57, 58 and R╬╡ ,
R68 and R75, 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, hydroxyl, methoxyl, 2-hydroxyethyl, 2-allyl, piperidine, morpholine, N,N- dimethylamine, carboxyl, carboxymethyl, N,N- dimethylcarboxyamide, cyano, nitro, methylke- tone, ethylketone, phenylketone, methylthiol; (b) two consecutive substituents between R8 and R13, Ri4 and R21, R22 and R28, R30 and R35, R36 and R41, R42 and R47, R48 and R57, R58 and R6 , R68 and R75, different from those indicated under point (a) , represent the condensation points with the benzenic or quinonic ring. The photochromatic compound having general formula (I) according to claim 1 or 2, consisting of the compound having formula (la) :
Figure imgf000057_0001
The photochromatic compound having general formula (I) according to claim 1 or 2, consisting of the compound having formula (lb) :
Figure imgf000058_0001
5. The photochromatic compound having general formula (I) according to claim 1 or 2, consisting of the compound having formula (Ic) :
Figure imgf000059_0001
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) :
Figure imgf000059_0002
wherein the substituents R', R'1, P, P' and Y have the same meanings described above, with silylated tetramers having general formula (XV) :
Figure imgf000060_0001
wherein the substituents R'i and X have the same meanings described above, in the presence of an inert organic solvent, or a mixture of inert organic solvents, at a temperature ranging from 50┬░C to 100┬░C, for a time ranging from 1 hour to 10 hours.
7. The process according to claim 6, wherein the inert organic solvent is selected from: acetone, ethyl alcohol, isopropanol, toluene, dioxane, or from mixtures of these solvents.
8. The process according to claim 6 or 7, wherein the reaction temperature ranges from 60┬░C to 80┬░C.
9. The process according to claim 6, 7 or 8, wherein the reaction time ranges from 2 hours to 5 hours.
10. Polymeric compositions comprising at least one photo-
- 5! chromatic compound according to any of the claims from 1 to 9, and at least one organic polymer selected from high density polyethylene, low density polyethylene, ethylene-vinylacetate copolymer, polyether amides, polypropylene, polymethyl methacrylate, polyvinyl alcohol, polyvinyl butyral, cellulose acetate butyrate, ep- oxy, polysiloxane or urethane resins, polycarbonate, polydiethylene glycol bis (allyl carbonate), polyamides, polyesters, polystyrene, polyvinyl chloride, polyethyl- acrylate, 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 claims from 1 to 9.
12. The compositions according to claim 10 or 11, comprising 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 com- pound 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.
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