Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
  • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D311/78—Ring systems having three or more relevant rings
  • C07D311/92—Naphthopyrans; Hydrogenated naphthopyrans
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
  • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D311/78—Ring systems having three or more relevant rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
  • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D311/94—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
  • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
  • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B57/00—Other synthetic dyes of known constitution
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B57/00—Other synthetic dyes of known constitution
  • C09B57/02—Coumarine dyes
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/22—Absorbing filters
  • G02B5/23—Photochromic filters
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/146—Laser beam

Definitions

• the present invention relates to novel annelated naphthopyran-type compounds which have, in particular, photochromic properties.
• the invention also relates to photochromic compositions and photochromic ophthalmic articles (lenses for example) which contain said naphthopyrans.
• the invention also covers the preparation of these novel naphthopyrans.
• the photochromic compounds are capable of changing colour under the influence of a poly- or monochromatic light (UV for example) and of returning to their initial colour when the luminous irradiation ceases, or under the influence of temperature and/or a poly- or monochromatic light different from the first.
• a poly- or monochromatic light UV for example
• the photochromic compounds find applications in various fields, e.g. for the manufacture of ophthalmic lenses, contact lenses, solar protection glasses, filters, camera optics or photographic apparatus optics or other optical devices and observation devices, glazing, decorative objects, bill elements or even for information storage by optical inscription (coding).
• a photochromic lens which comprises one or more photochromic compounds must have : - a high transmission in the absence of ultraviolets,
• tint acceptable to the consumer grey or brown preferably
• a maintenance of the chosen tint during the coloration and the discoloration of the lens - a maintenance of the performances, the properties, within a temperature range of O-40°C
• benzopyrans or naphthopyrans may be cited which are described in patents or patent applications : US-A-3,567,605, US-A-3,627,690, US-A-4,826,977, US-A-5,200,116, US-A-5,238,981, US-A-5,411,679, US-A-5,429,744, US-A-5 ,451,344, US-A- 5,458,814, US-A-5,651,923, US-A-5,645,767, US-A-5,698,141, WO-A-95 05382, FR- A-2,718,447, WO-A-96 14596, and WO-A-97 21698 which are of the reduced formula below :
• the photochromic compounds according to US-A-5,645,767 are obtained from substituted or non-substituted benzophenones, which are allowed to react with a succinic acid ester, such as the dimethyl ester, in the presence of toluene and potassium tert-butoxide.
• a half-ester is thus produced which is successively converted into acetoxynaphthalene and then into carboxynaphthol which is cyclised to obtain a naphthol fused with a benzo furanone residue.
• the reaction of this latter compound with a propargylic alcohol in the presence of DBSA leads to a naphthopyran fused with an indenone ring.
• the indene homologue of this naphthopyran can be obtained by starting from a precursor having a reduced ketone function.
• This carbon of the indene can be substituted in various ways.
• the naphthopyrans fused with benzo or naphthofuran residues according to US-A-5,657,923 they are prepared by reaction of a naphthol fused with an indenone ring or a naphthofuran ring, on the one hand, and with a propargylic alcohol on the other.
• the naphthol fused with an indenone ring is obtained for example as described in US-A-5,645,767 ; while the naphthol fused with a naphthofuran ring originates from a reaction between a naphthoquinone and a 1 ,3-dihydroxynaphthalene, with or without subsequent methylation of at least one hydroxy.
• the present invention thus relates, according to a first of its aspects, to the compounds of formula (I) :
• R. and R ⁇ are identical or different and independently represent :
• an aryl or heteroaryl group which comprises in its basic structure 6 to 24 carbon atoms or 4 to 24 carbon atoms respectively and at least one heteroatom selected from sulphur, oxygen and nitrogen ; said basic structure being optionally substituted with at least one substituent selected from the whole of the substituents given below :
• halogen notably fluorine, chlorine and bromine
• R' and R" which are identical or different, independently representing a linear or branched alkyl group which comprises 1 to 6 carbon atoms, a phenyl group optionally substituted by at least one linear or branched alkyl or alkoxy group which comprises 1 to 6 carbon atoms, or representing together with the
• an aralkyl or heteroaralkyl group the alkyl group, which is linear or branched, comprising 1 to 4 carbon atoms, and the aryl and heteroaryl groups having the definitions given above, or
• said two substituents Ri and R together form an adamantyl, norbornyl, fluorenylidene, di(C ⁇ -C6)alkylanthracenylidene or spiro(C 5 -C 6 )cycloalkylanthracenylidene group ; said group being optionally substituted with at least one of the substituents listed above for Ri, R 2 corresponding to an aryl or heteroaryl group ;
• R 3 which are identical or different, represent, independently :
• halogen notably fluorine, chlorine or bromine
• haloalkyl halocycloalkyl, haloalkoxy group corresponding respectively to the alkyl, cycloalkyl, alkoxy groups above, which are substituted with at least one halogen atom, notably selected
• an aralkyl or heteroaralkyl group the alkyl group, which is linear or branched, comprising 1 to 4 carbon atoms and the aryl and
• heteroaryl groups having the same definitions as those given supra - a phenoxy or naphthoxy group optionally substituted by at least one linear or branched alkyl or alkoxy group which comprises 1 to 6 carbon atoms,
• R, R', R" having their respective definitions given supra for the amine substituents of the values Ri, R : aryl or heteroaryl,
• R 8 representing a straight or 10 branched alkyl group comprising 1 to 6 carbon atoms or a cycloalkyl group comprising 3 to 6 carbon atoms or a phenyl group which is optionally substituted with at least one of the substituents listed above for the values of R 1; R 2 : aryl or heteroaryl ; or 15 at least two adjacent R 3 groups together form at least one aromatic or non-aromatic cyclic group having a single ring or two annelated rings, optionally comprising at least one heteroatom selected from the group comprising : oxygen, sulphur and nitrogen, this or these annelated rings being optionally substituted with at least 20 one substituent selected from those having the definition given above for the aryl or heteroaryl groups which can form Ri and/or R ;
• m is an integer of 0 to 4 ;
• ⁇ R 5 , R ⁇ and R 7 represent, independently :
• halogen notably fluorine, chlorine and bromine
• haloalkyl group corresponding to the linear or branched above alkyl group, which is substituted with at least one halogen atom, notably a fluoroalkyl group,
• 25 independently correspond to an aryl or heteroaryl group, - a -NH 2 , -NHR,
• R, R', R" having their respective definitions given supra for the amine substituents of the values Ri, R 2 : aryl or heteroaryl, - a phenoxy or naphthoxy group optionally substituted by at least one linear or branched alkyl or alkoxy group which comprises 1 to 6 carbon atoms,
• R 9 representing a linear or branched alkyl group comprising 1 to 6 carbon atoms or a cycloalkyl group comprising 3 to 6 carbon atoms or a phenyl or benzyl group which is optionally substituted with at least one of the substituents listed above in the definitions of the radicals Ri, R 2 of formula (I) in the case in which the radicals independently correspond to an aryl or heteroaryl group, - it being possible for two adjacent R 5 groups to together form a
• the compounds of the invention - naphthopyrans of formula (I) - possess a high colourability, even at 40°C, combined with discoloration kinetics which are adapted to the applications sought after.
• the colours, which are easily accessible, vary from orange to blue.
• the compounds considered are of formula (I) in which A corresponds to one of the annelated rings (Ai) or (A 2 ) as defined above.
• the compounds considered correspond to those of formula (I) in which A is one of the annelated rings (A 3 ), (A 4 ) or (A 5 ), as defined above.
• the compounds covered are those which belong to the family in which the compounds are of formula (I) with at least two of adjacent R 3 groups together forming an aromatic or non-aromatic cyclic group having a single ring (a phenyl group, for example) or two annelated rings (a benzofuran group, for example), optionally comprising at least one heteroatom selected from the group comprising : oxygen, sulphur and nitrogen, this or these annelated rings being optionally substituted with at least one substituent selected from those having the definition given above for the aryl or heteroaryl groups which can form Ri and/or R .
• the family according to this third embodiment comprises, inter alia, the compounds (I) in which two adjacent R 3 form at least one annelated ring, for example a benzo group, and in which carbons 5 and 6 of the phenanthrene skeleton are linked to at least one alicyclic and/or aromatic cycle A corresponding to (Ai), (A 2 ), (A 3 ), (A ) or (A 5 ).
• the compounds according to this third embodiment are, notably, naphthopyrans (I) in which two adjacent R 3 form at least one annelated ring, for example a benzo group, and in which carbons 5 and 6 of the phenanthropyran skeleton are linked to at least one substituted or non-substituted alicyclic or aromatic ring.
• naphthopyrans (I) in which two adjacent R 3 form at least one annelated ring, for example a benzo group, and in which carbons 5 and 6 of the phenanthropyran skeleton are linked to at least one substituted or non-substituted alicyclic or aromatic ring.
• the compounds envisaged are those of formula (I) given above, excluding the compounds in which A corresponds to (Ai) or (A 2 ) with at least one of the R substituents different from hydrogen and in which at least two adjacent R 3 groups do not together form at least one aromatic or non-aromatic cyclic group having a single ring or two annelated rings, optionally comprising at least one heteroatom selected from the group comprising oxygen, sulphur and nitrogen, this or these annelated rings being optionally substituted with at least one substituent selected from those having the definition above for the aryl or heteroaryl groups which can form Ri and/or R .
• the compounds according to the invention are of formula (I) in which :
• R 2 are identical or different and independently represent optionally substituted aryl or heteroaryl groups the basic structure of which is selected from those of phenyl, naphthyl, biphenyl, pyridyl, furyl, benzofuryl, dibenzofuryl,
• the inventors also take the credit in that they have proposed, in this field of photochromes, a novel route of synthesis of the naphthopyrans fused with at least one carbocycle annelated on carbons 5 and 6, in which route a precursor of the naphthol type is obtained from at least one ketone which comprises at least one carbocycle and which is allowed to react with at least one alkyl cyanoacetate, the product obtained being then subjected to a cyclisation.
• the invention also relates, according to a second of its aspects, to a method of preparation, notably of the compounds of formula (I) as defined above.
• This method essentially consists in carrying out the condensation : -»of at least one compound having the formula (II) below : in which R 3 , A and m are as defined supra with reference to the formula (I) ; with at least one derivative of propargylic alcohol, having the formula (III) below :
• the (II)/(III) condensation being advantageously carried out in the presence of a catalyst, this catalyst being preferably selected from the group comprising para-toluenesulphonic acid, dodecylsulphonic acid and bromoacetic acid, or with at least one aldehyde derivative, having the formula (III') below :
• the (II)/(III') condensation being advantageously carried out in the presence of a metal complex, preferably a titanium complex, titanium (IV) ethoxide being particularly preferred.
• a metal complex preferably a titanium complex, titanium (IV) ethoxide being particularly preferred.
• the reaction of condensation between compounds (II) and (III) can be carried out in solvents such as toluene, xylene or tetrahydrofuran, optionally to which appropriate catalysts have been added.
• solvents such as toluene, xylene or tetrahydrofuran
• Said compounds of formula (III) are known to the person skilled in the art and are obtained from the corresponding ketone according to a method described notably in the WO-A-96 14596 patent application.
• the ketone is itself commercial or is prepared according to the known methods such as the Friedel Crafts method (cf WO-A-96 14596 and cited references).
• Aldehydes derived from (III) are obtained by rearrangement in an acid medium (cf. J. Org. Chem., 1977, 42. 3403).
• the object of the invention is
• (co)polymer(s) and/or reticulate(s) obtained by polymerising and/or cross-linking at least one monomer comprising at least one compound (I) as defined above.
• the compounds (I) according to the invention can themselves be (co)monomers and/or can be comprised in (co)polymerisable and/or cross-linkable (co)polymers.
• the (co)polymers and/or reticulates thus obtained can constitute photochromic matrices such as those presented infra.
• the present invention relates to the use of said compounds of formula (I) of the invention as photochromic agents.
• the object of the invention is, therefore : - firstly, novel photochromic compounds which are constituted by the naphthopyran derivatives such as defined above, taken alone or in a mixture of themselves and/or with at least one other photochromic compound of another type and/or with at least one non-photochromic colouring agent ;
• novel photochromic compositions which comprise at least one naphthopyran derivative (I) as defined above and/or one of its derivatives, and/or at least one linear or cross-linked (co)polymer containing at least one compound (I) according to the invention in its structure.
• Such photochromic compositions can contain at least one other photochromic compound, of another type and/or at least one non-photochromic colouring agent and/or at least one stabilising agent ; these photochromic compounds of another type, non-photochromic colouring agents, and stabilising agents are prior art products known to the person skilled in the art.
• combinations of photochromic compounds of the invention and/or combinations of photochromic compounds of the invention and photochromic compounds of another type according to the prior art are particularly recommended ; such combinations being interesting in that they are suitable for generating grey or brown tints, which are desired by the public in applications such as ophthalmic spectacles or solar spectacles.
• additional photochromic compounds can be those known to the person skilled in the art and described in the literature, e. g.
• compositions according to the invention can also comprise :
• stabilising agents such as an anti-oxidising agent for example
• additives can notably enable improving the durability of said compositions.
• a photochromic solution can be obtained by dissolving at least one of said compounds in an organic solvent such as toluene, dichloromethane, tetrahydrofuran or ethanol.
• the solutions obtained are in general colourless and transparent. When exposed to sunlight, they develop a strong coloration and regain the colourless state when they are placed in an area of less exposure to the sun's rays or, in other words, when they are no longer subjected to UV.
• a very low concentration of product (of the order of 0.01 to 5% by weight) is sufficient to obtain an intense coloration.
• the compounds according to the invention are furthermore compatible with support matrices of organic polymer or of inorganic material, in a form included in said matrices as well as in the form of a coating of said matrices.
• the object of the invention is a matrix which comprises :
• the most interesting applications of the compounds of the invention are in fact those in which the photochrome is dispersed uniformly within or on the surface of a matrix formed by a polymer, and/or copolymer and/or mixture of (co)polymers.
• the compounds (I) included in a polymer matrix are colourless or slightly coloured in the initial state and rapidly develop an intense coloration under a UV light (365 nm) or under a light source of the solar type. Finally, they regain their initial coloration once the irradiation ceases.
• the diffusion in the (co)polymer, from a suspension or solution of the photochrome, in a silicone oil, in an aliphatic or aromatic hydrocarbon, or in a glycol, or from another polymer matrix can be cited for example.
• the diffusion is commonly carried out at a temperature of 50 to 200°C for a period of time of 15 minutes to several hours, according to the nature of the polymer matrix.
• Another implementation technique consists in mixing the photochrome in a formulation of polymerisable matrices, depositing this mixture on a surface or in a mould, and then carrying out the copolymerisation.
• polystyrene polyether
• polyester polycarbonate (e.g. bisphenol-A polycarbonate, diallyl diethylene glycol polycarbonate), polycarbamate, polyepoxy, polyurea, polyurethane, polythiourethane, polysiloxane, polyacrylonitrile, polyamide, aliphatic or aromatic polyester, vinylic polymers, cellulose acetate, cellulose triacetate, cellulose acetate- propionate or polyvinylbutyral,
• ⁇ R ]0 , R' 10 , R u and R' u are identical or different and represent independently a hydrogen or a methyl group ; ⁇ m, and n, are, independently, integers between 0 and 4 (inclusive) ; and are advantageously independently equal to 1 or 2 ; ⁇ X and X', which are identical or different, are a halogen and represent, preferably, a chlorine and/or a bromine ; ⁇ p, and q, are, independently, integers between 0 and 4 (inclusive); - copolymers of at least two types of copolymerisable monomers selected from the precursor monomers of the polymers listed supra, and preferably those belonging to the group comprising : (meth)acrylic monomers, vinylic monomers, allylic monomers, and mixtures thereof.
• the photochromes of the invention are used with resins which have a nanobiphasic structure and which are obtained by copolymerising at least two different, specific difunctional monomers.
• resins have been described in the French application FR-A-2 762 845.
• the amount of photochrome used in the (co)polymer matrix depends upon the degree of darkening desired. Usually, between 0.001 and 20% by weight of it is used.
• ophthalmic articles such as ophthalmic or solar spectacle articles, comprising :
• the articles which are more particularly covered by the present invention are ophthalmic lenses or photochromic solar lenses, glazing (windows for buildings, for locomotion engines, automobile vehicles), optical devices, decorative articles, solar protection articles, information storage, ...
• the present invention is illustrated by the Examples which follow of synthesis and of photochromic validation, of compounds of the invention (naphthopyrans). Said compounds of the invention are compared to prior art compounds, Ci and C 2 .
• Step 2
• the following mixture 2.0 g of the product of the preceding step, 3 g of potassium hydroxide in 30 ml of n-butanol, is heated at about 200-220°C in a 125 ml reactor for 6 hours. After cooling, the mixture is transferred into a flask and then reduced to dryness. The paste is then dissolved in 100 ml of water and then neutralised by the slow and progressive addition of concentrated hydrochloric acid (4 ml). The precipitate is recovered by filtration, washed with 4x20 ml of water and then dried under vacuum at 40°C for one night. Yield 90 %.
• Step 3
• the l-(p-methoxyphenyl)-6-methoxy-3,4-dihydronaphthalene derivative (synthesised according to the method adapted from Org. Synth. Coll. Vol III, p 729) is converted into an epoxy derivative by rearrangement, in basic medium, of the corresponding bromohydrin (according to J. Org. Chem. 1986, 3407).
• the ketone is then obtained by rearrangement in an acidic medium of the epoxy derivative.
• the naphthol derivative of type II is then synthesised in the same way as before.
• Step 2
• Compound (3) is obtained by reaction of the derivative of the preceding step with the l,l-bis(p-methoxyphenyl)-propyn-l-ol as in Example 1.
• the product (3) is obtained after purification. Its structure is confirmed by NMR spectroscopy.
• Compound (4) is obtained by reaction of the derivative intermediate of type II of the preceding Example with the 1-paradimethylaminophenyl-l-p-methoxy-phenyl-propyn- l-ol as in Example 1.
• the product (4) is obtained after purification. Its structure is confirmed by NMR spectroscopy.
• the 2-(l-naphthyl)cyclohexanone derivative is prepared by reaction of the magnesium derivative of 1 -bromonaphthalene with epoxycyclohexane (according to Takahashi et al, Tetrahedron Asym. 1995, 6, 617) followed by an oxidation with pyridinium chlorochromate (according to Corey et al. Tetrahedron Lett. 1975, 2647).
• Step 2
• the intermediate naphthol compound was obtained according to the same method as that indicated in Example 3, from the benzo tetralone (obtained according to A. Eirin et al, Arch. Pharm. 1987, 320, 1110) instead of tetralone.
• Compound (11) is then obtained by coupling with l-(para-dimethylaminophenyl)-l-phenyl-propyn-l-ol as described in Example 1 , followed by a purification by chromatography. Its structure is confirmed by NMR spectroscopy.
• Compound 12 was obtained by reaction of the intermediate naphthol of Example 1 with 1-thienyl-l-phenyl-propyn-l-ol as described in the last step of Example 1, followed by a purification by chromatography. Its structure is confirmed by NMR.
• Comparative compound Cl is synthesised from 1 -naphthol and l,l-bis(p-methoxyphenyl)-propyn-l-ol. It is of formula (Cl).
• Compound C2 is of formula :
• Compound C2 is commercially available.
• Compound C3 is described in the US patent US-A-5, 783,116.

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• Optics & Photonics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
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• 1999
  • 1999-01-06 FR FR9900162A patent/FR2783249B1/fr not_active Expired - Fee Related
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