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WO1999057219A1 - Composes photochromes, procedes de leur preparation et de leur utilisation dans des substances polymeres - Google Patents

Composes photochromes, procedes de leur preparation et de leur utilisation dans des substances polymeres Download PDF

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Publication number
WO1999057219A1
WO1999057219A1 PCT/EP1999/002952 EP9902952W WO9957219A1 WO 1999057219 A1 WO1999057219 A1 WO 1999057219A1 EP 9902952 W EP9902952 W EP 9902952W WO 9957219 A1 WO9957219 A1 WO 9957219A1
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Prior art keywords
group
groups
branched
linear
bromine
Prior art date
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Ceased
Application number
PCT/EP1999/002952
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English (en)
Inventor
Vincenzo Malatesta
Christiane Salemi-Delvaux
Marie-Hélène DENIEL
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Lanxess Switzerland GmbH
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Great Lakes Chemical Europe GmbH
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Filing date
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Application filed by Great Lakes Chemical Europe GmbH filed Critical Great Lakes Chemical Europe GmbH
Priority to EP99924854A priority Critical patent/EP1084208A1/fr
Priority to AU41368/99A priority patent/AU4136899A/en
Publication of WO1999057219A1 publication Critical patent/WO1999057219A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D498/20—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent 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
    • C09K9/02—Organic tenebrescent materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/685—Compositions containing spiro-condensed pyran compounds or derivatives thereof, as photosensitive substances

Definitions

  • the present invention relates to photochromatic compounds . 5 More specifically, the present invention relates to photochromatic compounds belonging to the group of spiro-isoindolino-oxazines, a process for their preparation and their use in polymeric materials.
  • a further object of the present invention relates 10 to polymeric compositions containing said photochromatic compounds and the photochromatic articles obtained from their processing.
  • Photochromatic compounds are substances which have the characteristic of reversibly changing colour and/or 15 degree of luminous 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 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. Duerr and H. Bouas-Laurent (Ed.), Vol. 40 of the series “Studies in Organic Chemistry” Elsevier (1990) .
  • 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 lenses for eye-glasses, special inks, toys, and in many other applications.
  • lino-oxazines have, with respect to other known compounds such as, for example, compounds belonging to the group of spiro-pyrans, the advantage of having a much higher fatigue resistance when subjected to light and dark cycles and also have good colourability characteristics .
  • the Applicant has now found photochromatic compounds belonging to the group of spiro-isoindolino- oxazines which have excellent photochromatic character- istics and excellent fatigue resistance.
  • these photochromatic compounds unlike the known spiro- indolino-oxazines and spiro-isoindolino-oxazines, have a dark green colouring.
  • the present invention therefore relates to photo- chromatic compounds belonging to the group of spiro- isoindolino-oxazines having general formula (I) :
  • R represents a linear or branched C ⁇ C.
  • 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 1 -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 select- ed from phenyl , diphenyl and naphthyl , said aryl group optionally substituted with linear or branched C 1 -C 6 alkoxyl groups, carboxyl groups, amine groups, N,N-dialkyl (C,-C 6 ) amine groups; a COOR' ester group wherein R' represents a linear or branched C,,
  • -4- 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 1 -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 10 alkenyl group; a COOR' ester group wherein R' represents a linear or branched C.,-C 10 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,,-C 10 alkyl groups, linear or
  • R 3 , R 4 , R 5 , R 6 R 8 , R 9 , R 10 , R , R 12 and R 13 represent a hydrogen atom; a halogen atom selected from fluorine, chlorine, bromine and iodine; a linear or branched C 1 -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 1 -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
  • (C,-C 6 ) amine groups linear or branched C 1 -C 6 alkoxyl groups, hydroxyl groups, linear or branched C 1 -C 6 alkyl groups; an acyl group of the alkyl ketone, aryl ketone or benzyl ketone type; a linear or branched C 2 -C 6 alkenyl group, said alkenyl group optionally subsituted with one or two N,N-dialkyl- (C 1 -C 6 ) -4 -aniline groups; an N-2 , 3- dihydroindoline group; a linear or branched C 1 -C 6 thioether group; two consecutive substituents between R 3 and R 6 , between R 8 and R ?
  • R 7 represents a hydrogen atom; a halogen atom selected from fluorine, chlorine and bromine; a linear or branched C 1 -C 6 alkyl group; a linear or branched C 1 -C 6 alkoxyl group; a phenyl group; a phenoxyl group ;
  • Z represents CH or a nitrogen atom
  • - Y represents an oxygen atom; a nitrogen atom; a sulfur atom; or a selenium atom.
  • Preferred compounds having general formula (I) for the purposes of the present invention are those wherein: - R represents one of the following groups: methyl, ethyl, isopropyl, 2-allyl, 2-hydroxyethyl , 2-car- boxymethyl, phenyl, 4-N,N-dimethylaminoaniline, 4- methoxybenzene, 4-cyanobenzene; R 1 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 , R 5 , R 6 , R 8 , R 9 , R 10 R ⁇ , R 12 and R 13 represent a hydrogen atom, a fluo- rine atom, a chlorine atom, a bromine atom, or one of the following groups: methyl, isopropyl, hydroxyl, methoxyl, N,N-dimethylamine, piperidine, mor- pholine, carboxyl, carboxymethyl , N, N-dimethyl - carboxyamide, cyano, nitro, methylketone, phenyl - ketone, phenyl;
  • R 7 represents a hydrogen atom, a chlorine atom, a bromine atom, a methyl group or a phenyl group; Z represents N; Y represents 0.
  • Specific examples of preferred compounds of the present invention are:
  • 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 isoindoline compounds having general formula (II) :
  • R a to R 13 and Y have the same meanings described above and R' ' represents a sodium, potassium, lithium, rubidium or cesium atom.
  • ⁇ 12- zation from a solvent such as, for example, acetone, toluene, pentane, heptane, diethyl ether.
  • the isoindoline compounds having general formula (II) 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.
  • isoindoline compounds having general formula (II) are usually conserved in the form of salts (isoindoline compounds having general formula (II') indicated in Scheme 1) such as, for example, iodides, bromides, chlorides, as the free base is very oxidable in air.
  • nitroso compounds having general formula (III) 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.
  • isoindoline compounds having general formula (II) which can be used in the above process, are the following:
  • the salts of the above isoindoline compounds having general formula (Ila) - (lid) are preferably used; even more preferably the iodine salts (iodides) of the above compounds .'
  • a specific example of a nitroso compound having general formula (III) which can be used in the above process, is the following: sodium salt of l-nitroso-2-hydroxybenzofuran having formula (Ilia) :
  • photochromatic compounds having general formula (I) of the present invention are colourless or
  • 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 hereun- der.
  • Some polymeric photochromatic end-articles can be obtained with moulding techniques such as, for example, injection or compression moulding, starting from polymers in which the photochromatic compound having formula (I) is homogeneously dispersed in mass.
  • the photochromatic compound 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 polymeric material such as, for example, polymethyl methacrylate, polyvinyl alcohol, polyvinyl butyral, cellulose acetate butyrate or epoxy, polysiloxane, urethane resin.
  • (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 (isobutyronitrile) in the case of the meth (acrylic) monomer or a peroxyketal in the case of the allyl carbonate monomer, they are uniformly incor- porated in the resin formed.
  • a suitable initiator such as, for example, azo-bis (isobutyronitrile) in the case of the meth (acrylic) monomer or a peroxyketal in the case of the allyl carbonate monomer, they are uniformly incor- porated in the resin formed.
  • the photochromatic compound having general formula (I) can be applied to a transparent substrate such as, for example, polycarbonate, poly- methyl methacrylate or polydiethylene glycol bis (allyl carbonate) , by surface impregnation obtained by putting the substrate in contact, at a suitable temperature, with a solution or dispersion containing the photochromatic compound 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, poly- methyl methacrylate or polydiethylene glycol 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
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • ethylene-vinylacetate copolymer polyether amides
  • polypropylene polymethylmethacrylate
  • polyvinyl alcohol polyvinyl butyral
  • cellulose acetate butyrate epoxy, polysiloxane or urethane resins
  • polycarbonate polydiethylene glycol bis (allyl carbonate)
  • polyamides polyesters, polystyrene, vinyl polychloride, polyethylacrylate, siliconic polymers.
  • a further object of the present invention there- fore relates 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 polysil- oxanes and/or silica gel, compositions based on plastic materials.
  • 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 photochrom- atic 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 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 normal additives for organic polymers such as, for example, phenolic antioxidants, sterically hindered amines, benzotriazoles, benzophen-
  • photochromatic compounds having general formula (I) of the present invention which, as already mentioned above, have a dark green 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.
  • 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 .
  • the product is dried under vacuum and conserved in a nitrogen atmosphere: the yield is 23.5 g.
  • a quantity equal to 23.5 g of the above product is placed in a 100 ml inox steel autoclave together with 20 ml of toluene and 21.4 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
  • 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 14 is reached: a yellow-white precipitate is thus formed which is rapidly filtered and washed with 30 ml of water and 20 ml of hexane.
  • the product is dried under vacuum and conserved in a nitrogen atmosphere: the yield is 44 g.
  • a quantity equal to 25 g of the above product is placed in a 100 ml inox steel autoclave together with
  • the above mixture is heated to 80 °C, under a nitrogen atmosphere, for 20 hours. At the end, the mixture is cooled and subsequently extracted with 30 ml of toluene.
  • the aqueous phase obtained is treated with aqueous sodium hydroxide (solution at 30%) until a pH 14 is reached: a yellow-white precipitate is thus formed which is rapidly filtered and washed with 30 ml of water and 20 ml of hexane.
  • the product is dried under vacuum and conserved in
  • the yield is 65 g.
  • a quantity equal to 65 g of the above product is placed in a 200 ml inox steel autoclave together with 120 ml of acetonitrile and 43 g of methyliodide. The autoclave is heated to 80°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.
  • aqueous phase obtained is treated with an excess of aqueous sodium carbonate (aqueous solution at 30%) until a pH 14 is reached: a precipitate is thus formed which is rapidly filtered and washed with 30 ml of water and 10 ml of hexane.
  • a quantity equal to 58 g of the above product is placed in a 200 ml inox steel, autoclave together with 40 ml of toluene and 42 g of methyliodide.
  • the autoclave is heated to 85 °C and is maintained at this temperature, under a nitrogen atmosphere, for 13 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
  • the above mixture is heated to 60 °C and maintained at this temperature, under stirring, under a nitrogen atmosphere, for 2 hours.
  • the reaction raw product obtained is filtered and subsequently purified by passage on a neutral column of active aluminum oxide 90 (activity degree I) , eluating with a mixture of hept- ane/dichl ⁇ ro methane in a ratio of 1/1.
  • the above mixture is heated to 60 °C and maintained at this temperature, under stirring, under a nitrogen atmosphere, for 2 hours.
  • the reaction raw product obtained is filtered and subsequently purified by passage on a neutral column of active aluminum oxide 90 (activity degree I) , eluating with a mixture of hept- ane/dichlo ' romethane in a ratio of 1/1.
  • 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 column of active aluminum oxide 90 (activity degree I) , eluating with a mixture of heptane/ethyl ' acetate in a ratio of 1/1.
  • the photochromatic activity is evaluated in ethanol, at 25°C, of Compounds (la) - (Id) obtained as described in Examples 5-8.
  • Solutions are prepared at a concentration equal to about 10 "4 M of the various Compounds (la) - (Id) in ethanol and subsequently 2 ml of each solution are placed in a quartz cell with an optical path of 1 cm.
  • the quartz cell containing the solution is introduced into a temperature control system, equipped with

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Indole Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des composés photochromes appartenant au groupe des spiro-iso-indolino-oxazines correspondant à la formule générale (I). Ces composés photochromes peuvent être utilisés dans des substances polymères.
PCT/EP1999/002952 1998-05-07 1999-05-03 Composes photochromes, procedes de leur preparation et de leur utilisation dans des substances polymeres Ceased WO1999057219A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP99924854A EP1084208A1 (fr) 1998-05-07 1999-05-03 Composes photochromes, procedes de leur preparation et de leur utilisation dans des substances polymeres
AU41368/99A AU4136899A (en) 1998-05-07 1999-05-03 Photochromic compounds, process for their preparation and their use in polymericmaterials

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI98A000991 1998-05-07
IT98MI000991A ITMI980991A1 (it) 1998-05-07 1998-05-07 Composti fotocromatici procedimento per la loro preparazione e loro utilizzo in materiali polimerici

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WO1999057219A1 true WO1999057219A1 (fr) 1999-11-11

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004052966A1 (fr) * 2002-12-09 2004-06-24 Hetero Drugs Limited Nouveau polymorphe de sulfate d'hydrogene de clopidogrel
WO2004065464A1 (fr) * 2003-01-24 2004-08-05 Sunbow Co., Ltd. Procede d'elaboration de resine de polypropylene renfermant des composes photochromiques, et fil de polypropylene elabore a partir de cette resine
CN103285922A (zh) * 2013-06-18 2013-09-11 中北大学 环氧聚合物微球固载四甲基哌啶氮氧自由基催化剂及其制备方法和应用方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0524692A1 (fr) * 1991-07-24 1993-01-27 GREAT LAKES CHEMICAL ITALIA S.r.l. Composés photochromiques et thermochromatiques et leur application en matériaux polymères
US5186867A (en) * 1989-12-12 1993-02-16 Enichem Synthesis, S.P.A. Spiro-indoline oxazine compounds with photochromatic and photosensitizing characteristics and the process for their preparation
US5374723A (en) * 1988-02-08 1994-12-20 Toray Industries, Inc. Spiro-oxazine compound
WO1999001457A1 (fr) * 1997-07-03 1999-01-14 Great Lakes Chemical (Europe) Gmbh Composes photochromiques, leur procede de preparation et leur utilisation dans des materiaux polymeres

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5374723A (en) * 1988-02-08 1994-12-20 Toray Industries, Inc. Spiro-oxazine compound
US5186867A (en) * 1989-12-12 1993-02-16 Enichem Synthesis, S.P.A. Spiro-indoline oxazine compounds with photochromatic and photosensitizing characteristics and the process for their preparation
EP0524692A1 (fr) * 1991-07-24 1993-01-27 GREAT LAKES CHEMICAL ITALIA S.r.l. Composés photochromiques et thermochromatiques et leur application en matériaux polymères
WO1999001457A1 (fr) * 1997-07-03 1999-01-14 Great Lakes Chemical (Europe) Gmbh Composes photochromiques, leur procede de preparation et leur utilisation dans des materiaux polymeres

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004052966A1 (fr) * 2002-12-09 2004-06-24 Hetero Drugs Limited Nouveau polymorphe de sulfate d'hydrogene de clopidogrel
WO2004065464A1 (fr) * 2003-01-24 2004-08-05 Sunbow Co., Ltd. Procede d'elaboration de resine de polypropylene renfermant des composes photochromiques, et fil de polypropylene elabore a partir de cette resine
CN103285922A (zh) * 2013-06-18 2013-09-11 中北大学 环氧聚合物微球固载四甲基哌啶氮氧自由基催化剂及其制备方法和应用方法

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EP1084208A1 (fr) 2001-03-21
AU4136899A (en) 1999-11-23
ITMI980991A1 (it) 1999-11-07

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