Naphthopyrans having a perfluoroalkyl substituent in position 5, preparation and compositions and matrices containing them
First Claim
Patent Images
1. A compound having the following formula (I):
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in which;
X is a linear or branched perfluoroalkyl comprising 1 to 6 carbon atoms;
R1 and R2, which are identical or different, independently represent;
hydrogen, a linear or branched alkyl group comprising 1 to 12 carbon atoms, a cycloalkyl group comprising 3 to 12 carbon atoms, an aryl group comprising in its basic structure 6 to 24 carbon atoms or a heteroaryl group comprising in its basic structure 4 to 24 carbon atoms and at least one heteroatom selected from sulfur, oxygen and nitrogen, said aryl or heteroaryl group'"'"'s basic structure being optionally substituted with at least one substituent selected from the group consisting of;
a halogen, a hydroxy group, a linear or branched alkyl group comprising 1 to 12 carbon atoms, a linear or branched alkoxy group comprising 1 to 12 carbon atoms, a haloalkyl or haloalkoxy group corresponding respectively to the (C1-C12) alkyl or alkoxy groups above which are substituted with at least one halogen atom, a phenoxy or naphthoxy group optionally substituted with at least one linear or branched alkyl or alkoxy group comprising 1 to 12 carbon atoms, a linear or branched alkenyl group comprising 2 to 12 carbon atoms, an —
NH2 group, an —
NHR group, R representing a linear or branched alkyl group comprising 1 to 6 carbon atoms, or a phenyl group optionally substituted with at least one linear or branched alkyl group comprising 1 to 6 carbon atoms, agroup wherein R′ and
R″
, which are identical or different, independently represent a linear or branched alkyl group comprising 1 to 6 carbon atoms or a phenyl group optionally substituted with at least one linear or branched alkyl group comprising 1 to 6 carbon atoms or wherein R′ and
R″
represent together with the nitrogen atom to which they are bound a 5- to 7-membered ring which optionally comprises at least one other heteroatom selected from oxygen, sulfur, and nitrogen, said nitrogen being optionally substituted with an R′
″
group, which is a linear or branched alkyl group comprising 1 to 6 carbon atoms, and a methacryloyl group or an acryloyl group, or an aralkyl or heteroaralkyl group, the alkyl part of which is linear or branched and comprises 1 to 4 carbon atoms and the aryl part or heteroaryl part of which has the same definition as that given above for the aryl and or heteroaryl group;
or
said two substituents R1 and R2 together form an adamantyl, norbornyl, fluorenylidene, di(C1-C6)alkylanthracenylidene, or spiro(C5-C6)cycloalkylanthracenylidene group, said group being optionally substituted with at least one substituent selected from the group consisting of;
a halogen, a hydroxy group, a linear or branched alkyl group comprising 1 to 12 carbon atoms, a linear or branched alkoxy group comprising 1 to 12 carbon atoms, a haloalkyl or haloalkoxy group corresponding to the (C1-C12) alkyl or alkoxy groups above, respectively, which are substituted with at least one halogen atom, a linear or branched alkenyl group comprising 2 to 12 carbon atoms, an —
NH2 group, an —
NHR group, wherein R represents a linear or branched alkyl group comprising 1 to 6 carbon atoms, agroup, wherein R′ and
R″
, which are identical or different, represent, independently, a linear or branched alkyl group comprising 1 to 6 carbon atoms or R′ and
R″
, together with the nitrogen atom to which they are bound, represent a 5- to 7-membered ring which optionally comprises at least one other heteroatom selected from oxygen, sulphur, and nitrogen, said nitrogen being optionally substituted with an R′
″
group, which is a linear or branched alkyl group comprising 1 to 6 carbon atoms, and a methacryloyl group or an acryloyl group;
R3, which are identical or different, represent, independently;
a halogen, a hydroxy, a linear or branched alkyl group comprising 1 to 12 carbon atoms, a cycloalkyl group comprising 3 to 12 carbon atoms, a linear or branched alkoxy group comprising 1 to 12 carbon atoms, a haloalkyl, halocycloalkyl, or haloalkoxy group corresponding respectively to the alkyl, cycloalkyl, and alkoxy groups above, which are substituted with at least one halogen atom, an aryl or heteroaryl group having the same definition as that given above for R1, R2, an aralkyl or heteroaralkyl group, the alkyl part of which is linear or branched and comprises 1 to 4 carbon atoms and the aryl and heteroaryl part of which has the same definitions as those given above for R1, R2, a phenoxy or naphthoxy group optionally substituted with at least one linear or branched alkyl or alkoxy group comprising 1 to 12 carbon atoms, an amine or amide group;
—
NH2, —
NHR, —
CONH2, —
CONHR,
wherein R represents a linear or branched alkyl group comprising 1 to 6 carbon atoms and wherein R′ and
R″
, which are identical or different, represent, independently, a linear or branched alkyl group comprising 1 to 6 carbon atoms or R′ and
R″
, together with the nitrogen atom to which they are bound, represent a 5- to 7-membered ring which optionally comprises at least one other heteroatom selected from oxygen, sulphur, and nitrogen, said nitrogen being optionally substituted with an R′
″
group, which is a linear or branched alkyl group comprising 1 to 6 carbon atoms, an —
OCOR6 or —
COOR6 group, R6 representing a linear or branched alkyl group comprising 1 to 6 carbon atoms, a cycloalkyl group comprising 3 to 6 carbon atoms, or a phenyl group, optionally substituted with at least one substituent selected from the group consisting of;
a halogen, a hydroxy group, a linear or branched alkyl group comprising 1 to 12 carbon atoms, a linear or branched alkoxy group comprising 1 to 12 carbon atoms, a haloalkyl or haloalkoxy group corresponding to the (C1-C12) alkyl or alkoxy groups above, respectively, which are substituted with at least one halogen atom, a linear or branched alkenyl group comprising 2 to 12 carbon atoms, an —
NH2 group, an —
NHR group, wherein R represents a linear or branched alkyl group comprising 1 to 6 carbon atoms, agroup, wherein R′ and
R″
, which are identical or different, represent, independently, a linear or branched alkyl group comprising 1 to 6 carbon atoms or R′ and
R″
, together with the nitrogen atom to which they are bound, represent a 5- to 7-membered ring which optionally comprises at least one other heteroatom selected from oxygen, sulphur, and nitrogen, said nitrogen being optionally substituted with an R′
″
group, which is a linear or branched alkyl group comprising 1 to 6 carbon atoms, and a methacryloyl group or an acryloyl group;
or
at least two of the adjacent R3 groups together form an aromatic or non-aromatic cyclic group having one or two annelated rings, optionally comprising at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen, this or these annelated rings being independently 5- to 7-membered aromatic or non-aromatic rings and being optionally substituted with at least one substituent selected from those having the definition given above for the aryl or heteroaryl groups representing R1 or R2;
m is an integer of 0 to 4; and
R4 represents a hydrogen, a hydroxy, a linear or branched alkyl comprising 1 to 12 carbon atoms, a linear or branched alkoxy comprising 1 to 12 carbon atoms, an aryl or heteroaryl as defined above for R1 or R2, or an ester of formula OCOR6, where R6 is as defined above.
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Abstract
The present invention relates to novel compounds of the naphthopyran type which have a perfluoroalkyl group (X) in position 5. These compounds are of formula (I) given below:
These compounds (I) possess interesting photochromic properties. The invention also relates to their preparation, their applications as photochromes as well as the compositions and matrices containing them.
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Citations
27 Claims
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1. A compound having the following formula (I):
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in which; X is a linear or branched perfluoroalkyl comprising 1 to 6 carbon atoms;
R1 and R2, which are identical or different, independently represent;
hydrogen, a linear or branched alkyl group comprising 1 to 12 carbon atoms, a cycloalkyl group comprising 3 to 12 carbon atoms, an aryl group comprising in its basic structure 6 to 24 carbon atoms or a heteroaryl group comprising in its basic structure 4 to 24 carbon atoms and at least one heteroatom selected from sulfur, oxygen and nitrogen, said aryl or heteroaryl group'"'"'s basic structure being optionally substituted with at least one substituent selected from the group consisting of;
a halogen, a hydroxy group, a linear or branched alkyl group comprising 1 to 12 carbon atoms, a linear or branched alkoxy group comprising 1 to 12 carbon atoms, a haloalkyl or haloalkoxy group corresponding respectively to the (C1-C12) alkyl or alkoxy groups above which are substituted with at least one halogen atom, a phenoxy or naphthoxy group optionally substituted with at least one linear or branched alkyl or alkoxy group comprising 1 to 12 carbon atoms, a linear or branched alkenyl group comprising 2 to 12 carbon atoms, an —
NH2 group,an —
NHR group, R representing a linear or branched alkyl group comprising 1 to 6 carbon atoms, or a phenyl group optionally substituted with at least one linear or branched alkyl group comprising 1 to 6 carbon atoms,a group wherein R′ and
R″
, which are identical or different, independently represent a linear or branched alkyl group comprising 1 to 6 carbon atoms or a phenyl group optionally substituted with at least one linear or branched alkyl group comprising 1 to 6 carbon atoms or wherein R′ and
R″
represent together with the nitrogen atom to which they are bound a 5- to 7-membered ring which optionally comprises at least one other heteroatom selected from oxygen, sulfur, and nitrogen, said nitrogen being optionally substituted with an R′
″
group, which is a linear or branched alkyl group comprising 1 to 6 carbon atoms, anda methacryloyl group or an acryloyl group, or an aralkyl or heteroaralkyl group, the alkyl part of which is linear or branched and comprises 1 to 4 carbon atoms and the aryl part or heteroaryl part of which has the same definition as that given above for the aryl and or heteroaryl group;
or
said two substituents R1 and R2 together form an adamantyl, norbornyl, fluorenylidene, di(C1-C6)alkylanthracenylidene, or spiro(C5-C6)cycloalkylanthracenylidene group, said group being optionally substituted with at least one substituent selected from the group consisting of;
a halogen, a hydroxy group, a linear or branched alkyl group comprising 1 to 12 carbon atoms, a linear or branched alkoxy group comprising 1 to 12 carbon atoms, a haloalkyl or haloalkoxy group corresponding to the (C1-C12) alkyl or alkoxy groups above, respectively, which are substituted with at least one halogen atom, a linear or branched alkenyl group comprising 2 to 12 carbon atoms, an —
NH2 group,an —
NHR group, wherein R represents a linear or branched alkyl group comprising 1 to 6 carbon atoms,a group, wherein R′ and
R″
, which are identical or different, represent, independently, a linear or branched alkyl group comprising 1 to 6 carbon atoms or R′ and
R″
, together with the nitrogen atom to which they are bound, represent a 5- to 7-membered ring which optionally comprises at least one other heteroatom selected from oxygen, sulphur, and nitrogen, said nitrogen being optionally substituted with an R′
″
group, which is a linear or branched alkyl group comprising 1 to 6 carbon atoms, anda methacryloyl group or an acryloyl group;
R3, which are identical or different, represent, independently;
a halogen, a hydroxy, a linear or branched alkyl group comprising 1 to 12 carbon atoms, a cycloalkyl group comprising 3 to 12 carbon atoms, a linear or branched alkoxy group comprising 1 to 12 carbon atoms, a haloalkyl, halocycloalkyl, or haloalkoxy group corresponding respectively to the alkyl, cycloalkyl, and alkoxy groups above, which are substituted with at least one halogen atom, an aryl or heteroaryl group having the same definition as that given above for R1, R2, an aralkyl or heteroaralkyl group, the alkyl part of which is linear or branched and comprises 1 to 4 carbon atoms and the aryl and heteroaryl part of which has the same definitions as those given above for R1, R2, a phenoxy or naphthoxy group optionally substituted with at least one linear or branched alkyl or alkoxy group comprising 1 to 12 carbon atoms, an amine or amide group;
—
NH2, —
NHR, —
CONH2, —
CONHR,
wherein R represents a linear or branched alkyl group comprising 1 to 6 carbon atoms and wherein R′ and
R″
, which are identical or different, represent, independently, a linear or branched alkyl group comprising 1 to 6 carbon atoms or R′ and
R″
, together with the nitrogen atom to which they are bound, represent a 5- to 7-membered ring which optionally comprises at least one other heteroatom selected from oxygen, sulphur, and nitrogen, said nitrogen being optionally substituted with an R′
″
group, which is a linear or branched alkyl group comprising 1 to 6 carbon atoms,an —
OCOR6 or —
COOR6 group, R6 representing a linear or branched alkyl group comprising 1 to 6 carbon atoms, a cycloalkyl group comprising 3 to 6 carbon atoms, or a phenyl group, optionally substituted with at least one substituent selected from the group consisting of;
a halogen, a hydroxy group, a linear or branched alkyl group comprising 1 to 12 carbon atoms, a linear or branched alkoxy group comprising 1 to 12 carbon atoms, a haloalkyl or haloalkoxy group corresponding to the (C1-C12) alkyl or alkoxy groups above, respectively, which are substituted with at least one halogen atom, a linear or branched alkenyl group comprising 2 to 12 carbon atoms, an —
NH2 group,an —
NHR group, wherein R represents a linear or branched alkyl group comprising 1 to 6 carbon atoms,a group, wherein R′ and
R″
, which are identical or different, represent, independently, a linear or branched alkyl group comprising 1 to 6 carbon atoms or R′ and
R″
, together with the nitrogen atom to which they are bound, represent a 5- to 7-membered ring which optionally comprises at least one other heteroatom selected from oxygen, sulphur, and nitrogen, said nitrogen being optionally substituted with an R′
″
group, which is a linear or branched alkyl group comprising 1 to 6 carbon atoms, anda methacryloyl group or an acryloyl group;
or
at least two of the adjacent R3 groups together form an aromatic or non-aromatic cyclic group having one or two annelated rings, optionally comprising at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen, this or these annelated rings being independently 5- to 7-membered aromatic or non-aromatic rings and being optionally substituted with at least one substituent selected from those having the definition given above for the aryl or heteroaryl groups representing R1 or R2;
m is an integer of 0 to 4; and
R4 represents a hydrogen, a hydroxy, a linear or branched alkyl comprising 1 to 12 carbon atoms, a linear or branched alkoxy comprising 1 to 12 carbon atoms, an aryl or heteroaryl as defined above for R1 or R2, or an ester of formula OCOR6, where R6 is as defined above. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27)
R1 and R2 are identical or different and independently represent optionally substituted aryl or heteroaryl groups, the basic structure of which is selected from the group consisting of phenyl, naphthyl, biphenyl, pyridyl, finyl, benzofuryl, dibenzofuryl, N-(C1-C6)alkylcarbazole, thienyl, benzothienyl, dibenzothienyl, and julolidinyl groups;
orR1 and R2 together form an adamantyl or norbomyl group.
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4. A compound according to claim 1, wherein at least one of R1 and R2 represents a para-substituted phenyl group.
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5. A compound according to claim 1, wherein at least two adjacent R3 groups together form an aromatic or non-aromatic cyclic group having one or two annelated rings, which rings are 5- to 7-membered, which rings can optionally contain at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen, and which rings are optionally substituted with at least one substituent selected from those having the definition given in claim 1 for the aryl or heteroaryl group representing R1 or R2.
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6. A method of preparing compounds according to claim 1, said method comprising:
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condensing a compound of formula (II);
in which X, R3, R4, and m are as defined as in claim 1,with a dertivative of a propargylic alcohol of formula (III);
in which R1 and R2 are as defined in claim 1, the (II)/(III) condensation being optionally carried out in the presence of a catalyst selected from the group consisting of para-toluenesulfonic acid, dodecylsulfonic acid, and bromoacetic acid;
orwith an aldehyde derivative, having formula (III′
) below;
in which R1 and R2 are defined as in claim 1, the (II)/(III′
) condensation being optionally carried out in the presence of a metallic complex of titanium.
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7. A (co)polymer and/or reticulate obtained by polymerizing and/or cross-linking and/or grafting at least one monomer comprising at least one compound according to claim 1.
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8. A photochromic compound which is constituted by a compound according to claim 1, or by a mixture of at least two compounds according to claim 1, or by a mixture of at least one compound according to claim 1 and at least one other photochromic compound of a different type and/or at least one non-photochromic coloring agent.
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9. A photochromic composition which comprises:
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at least one compound according to claim 1, and/or at least one linear or crosslinked (co)polymer which contains, in its structure, at least one compound according to claim 1, and optionally, at least one other photochromic compound of a different type and/or at least one non-photochromic coloring agent and/or at least one stabilizing agent.
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10. A (co)polymer matrix, characterized in that it comprises:
at least one compound according to claim 1.
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11. A (co)polymer matrix according to claim 10, wherein the (co)polymer is selected from the group consisting of:
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an alkyl, cycloalkyl, (poly or oligo)ethylene glycol, aryl or arylalkyl mono-, di-, tri-, or tetra-acrylate or mono-, di-, tri- or tetra-methacrylate which is optionally halogenated or which optionally comprises at least one ether and/or ester and/or carbonate and/or carbamate and/or thiocarbamate and/or urea and/or amide group, a polystyrene, polyether, polyester, polycarbonate, polycarbamate, polyepoxide, polyurea, polyurethane, polythiourethane, polysiloxane, polyacrylonitrile, polyamide, aliphatic or aromatic polyester, vinylic polymers, cellulose acetate, cellulose triacetate, cellulose acetate-propionate, or polyvinylbutyral, a (co)polymer obtained from a difunctional monomer of the following formula;
in which;
R10, R′
10, R11 and R′
11 are identical or different and independently are a hydrogen or a methyl group,m1 and n1 independently are integers between 0 and 4 inclusive, X and X′
, which are identical or different, are a halogen, andp1 and q1 independently are integers between 0 and 4 inclusive;
a copolymer of at least two types of copolymerizable monomers selected from the monomers which are precursors of the polymers listed above; and
combinations thereof.
-
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12. A (co)polymer matrix which comprises:
at least one photochromic composition according to claim 9.
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13. A (co)polymer matrix according to claim 12, wherein the (co)polymer is selected from the group consisting of:
-
an alkyl, cycloalkyl, (poly or oligo)ethylene glycol, aryl or arylalkyl mono-, di-, tri-, or tetra-acrylate or mono-, di-, tri- or tetra-methacrylate which is optionally halogenated or which optionally comprises at least one ether and/or ester and/or carbonate and/or carbamate and/or thiocarbamate and/or urea and/or amide group, a polystyrene, polyether, polyester, polycarbonate, polycarbamate, polyepoxide, polyurea, polyurethane, polythiourethane, polysiloxane, polyacrylonitrile, polyamide, aliphatic or aromatic polyester, vinylic polymers, cellulose acetate, cellulose triacetate, cellulose acetate-propionate, or polyvinylbutyral, a (co)polymer obtained from a difunctional monomer of the following formula;
in which;
R10, R′
10, R11 and R′
11 are identical or different and independently are a hydrogen or a methyl group,m1 and n1 independently are integers between 0 and 4 inclusive, X and X′
, which are identical or different, are a halogen, andp1 and q1 independently are integers between 0 and 4 inclusive;
a copolymer of at least two types of copolymerizable monomers selected from the monomers which are precursors of the polymers listed above; and
combinations thereof.
-
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14. A (co)polymer matrix which comprises:
at least one (co)polymer and/or reticulate according to claim 7.
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15. A (co)polymer matrix according to claim 14, wherein the (co)polymer is selected from the group consisting of:
-
an alkyl, cycloalkyl, (poly or oligo)ethylene glycol, aryl or arylalkyl mono-, di-, tri-, or tetra-acrylate or mono-, di-, tri- or tetra-methacrylate which is optionally halogenated or which optionally comprises at least one ether and/or ester and/or carbonate and/or carbamate and/or thiocarbamate and/or urea and/or amide group;
a polystyrene, polyether, polyester, polycarbonate, polycarbamate, polyepoxide, polyurea, polyurethane, polythiourethane, polysiloxane, polyacrylonitrile, polyamide, aliphatic or aromatic polyester, vinylic polymers, cellulose acetate, cellulose triacetate, cellulose acetate-propionate, or polyvinylbutyral;
a (co)polymer obtained from a difunctional monomer of the following formula;
in which;
R10, R′
10, R11 and R′
11 are identical or different and independently are a hydrogen or a methyl group,m1 and n1 independently are integers between 0 and 4 inclusive, X and X′
, which are identical or different, are a halogen, andp1 and q1 independently are integers between 0 and 4 inclusive;
a copolymer of at least two types of copolymerizable monomers selected from the monomers which are precursors of the polymers listed above; and
combinations thereof.
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16. An ophthalmic or solar article comprising:
at least one compound according to claim 1.
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17. An article according to claim 16, wherein said article is selected from the group consisting of a lens, a glazing, and an optical device.
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18. An ophthalmic or solar article comprising:
at least one at least one photochromic composition according to claim 9.
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19. An article according to claim 18, wherein said article is selected from the group consisting of a lens, a glazing, and an optical device.
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20. An ophthalmic or solar article comprising:
at least one (co)polymer and/or reticulate according to claim 7.
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21. An article according to claim 20, wherein said article is selected from the group consisting of a lens, a glazing, and an optical device.
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22. An ophthalmic or solar article comprising:
at least one matrix according to claim 10.
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23. An article according to claim 22, wherein said article is selected from the group consisting of a lens, a glazing, and an optical device.
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24. An ophthalmic or solar article comprising:
at least one matrix according to claim 12.
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25. An article according to claim 24, wherein said article is selected from the group consisting of a lens, a glazing, and an optical device.
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26. An ophthalmic or solar article comprising:
at least one matrix according to claim 14.
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27. An article according to claim 26, wherein said article is selected from the group consisting of a lens, a glazing, and an optical device.
Specification
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Current AssigneeCorning Incorporated
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Original AssigneeCorning SA (Corning Incorporated)
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InventorsChan, You-Ping, Breyne, Olivier, Jean, Patrick
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Primary Examiner(s)TUCKER, PHILIP C
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Application NumberUS09/706,121Time in Patent Office578 DaysField of Search252/586, 351/163, 549/389, 549/382, 549/383, 549/384, 549/24, 549/25US Class Current252/586CPC Class CodesC07C 2603/26 Phenanthrenes; Hydrogenated...C07C 37/00 Preparation of compounds ha...C07C 37/07 with simultaneous reduction...C07C 39/38 with at least one hydroxy g...C07D 311/92 Naphthopyrans; Hydrogenated...C09K 9/02 Organic tenebrescent materialsG02B 5/23 Photochromic filters
