US 6,608,215 B2 · Oxygen-containing heterocyclic fused naphthopyrans

Abstract

Novel naphthopyrans having an oxygen-containing heterocyclic group F annelated on the f, i, j, or k side of the naphthopyran ring. These naphthopyrans may have the formula (I) presented below: These compounds (I) have interesting photochromic properties. Various organic host materials that contain such compounds are described. Articles such as ophthalmic lenses or other plastic transparencies that incorporate the novel naphthopyran compounds or combinations are enabled.

Claims44

Dependent claims

A photochromic article comprising a layer of polymeric binder containing a naphthopyran having a central nucleus of the formula:

wherein F is an oxygen-containing 5- to 7-member heterocyclic ring group, its 2,3 or 3,2 positions fused to the f, i, j, or k side of the ring, and
R1 and R2 are the atoms or groups providing photochromic properties to the naphthopyran.

A photochromic article comprising a layer of polymeric binder containing a naphthopyran having a central nucleus of the formula:

wherein F is an oxygen-containing 5- to 7-member heterocyclic ring group, its 2,3 or 3,2 positions fused to the f, i, j, or k side of the ring, and
R1 and R2 are the atoms or groups necessary to provide photochromic properties to the naphthopyran and R5 and R6 are selected from the group consisting of:
a hydrogen,
a halogen,
a linear or branched alkyl group of 1 to 12 carbon atoms,
a cycloalkyl group of 3 to 12 carbon atoms,
a linear or branched alkoxy group of 1 to 12 carbon atoms;,
a haloalkyl, halocycloalkyl, or haloalkoxy group,
a linear or branched alkenyl or alkynyl group of 1-12 carbon atoms,
a linear or branched alkenyloxy or alkynyloxy group of 1-12 carbon atoms,
an aryl or heteroaryl group,
an aralkyl or heteroaralkyl group, the alkyl group, which is linear or branched, of 1 to 4 carbon atoms;
an amine or amide group:
—NH2, —NHR11, —CONH2, —CONHR11,
R11 representing a linear or branched alkyl group of 1 to 6 carbon atoms, R12 and R13 which are the same or different, independently representing a linear or branched alkyl group of 1 to 6 carbon atoms, or representing together with the nitrogen atom to which they are bound a 5- to 7-membered ring which comprise at least one other heteroatom selected from oxygen, sulfur and nitrogen;
a —C(R16)2X group, wherein X is selected from the group consisting of
—CN, halogen, hydroxy, alkoxy, benzoyloxy, C1-C6 acyloxy, amino, C1-C6 mono-alklamino, C1-C6 dialkyl amino, morpholino, piperidino, 1-indolinyl, pyrrolidyl, or trimethylsilyloxy, R16 is hydrogen, C1-C6 alkyl, phenyl or naphthyl with C1-C6 alkyl or C1-C6 alkoxy substituents,
an —OCOR17 or —COOR17 group, R17 representing a straight or branched alkyl group comprising 1 to 6 carbon atoms, or a cycloalkyl group comprising 3 to 6 carbon atoms, or a phenyl group,
a methacryloyl group or an acryloyl group, an epoxy group,
a polyether, polyamide, polycarbonate, polycarbamate, polyurea or polyester residue;
an aralkyl or heteroaralkyl group, the alkyl group, which is linear or branched, comprising 1 to 4 carbon atoms,
R5 and R6 together form a 5- to 7-member aromatic or non-aromatic ring, the ring may comprising at least one heteroatom selected from oxygen, sulfur, and nitrogen.

19 more elements

A photochromic article comprising a polymeric binder and a naphthopyran of the formula (I):

in which:
F is an oxygen-containing 5- to 7-member heterocyclic ring with or without substitutions, its 2,3 or 3,2 positions fused to the f, i, j, or k side of the ring,
R1 and R2 independently represent:
a hydrogen,
a linear or branched alkyl group which comprises 1 to 12 carbon atoms,
a cycloalkyl group which comprises 3 to 12 carbon atoms,
an aryl or heteroaryl group which comprises in its basic structure (that is, in its ring atoms, the rings comprising 5, 6 or 7 atoms) 6 to 24 carbon atoms or 4 to 24 carbon atoms respectively and at least one heteroatom selected from sulfur, oxygen and nitrogen;
the basic structure being optionally substituted with at least one substituent selected from:
a halogen atom,
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 —NHR11 group, R11 representing a linear or branched alkyl group comprising 1 to 6 carbon atoms,
a
group, in which R12 and R13, which are the same or different, independently representing a linear or branched alkyl group comprising 1 to 6 carbon atoms, or representing, together with the nitrogen atom to which they are bound, a 5- to 7-membered ring which can comprise at least one other heteroatom selected from oxygen, sulfur and nitrogen, said nitrogen being optionally substituted with an R14 group, which is a linear or branched alkyl group comprising 1 to 6 carbon atoms,
a methacryloyl group or an acryloyl group,
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
the two substituents R1 and R2 together forming ring group selected from the group consisting of adamantyl, norbornyl, fluorenylidene, 5,5- or 10,10-di(C1-C6)alkylanthracenylidene, 5 (or 10)-(C1-C6)alkyl-5 (or 10)-OH (or OR15)anthracenylidene or spiro(C5-C6)cycloalkylanthracenylidene ring group;
said ring group being optionally substituted with at least one of the substituents listed above in the definitions for R1, R2;
said ring group being optionally substituted with two adjacent groups that form a 5- to 6-member aromatic or non-aromatic ring which can comprise at least one heteroatom selected from oxygen, sulfur, and nitrogen;
R5 and R6 are the same or different and they represent, independently:
a hydrogen,
a halogen, and notably fluorine, chlorine or bromine,
a linear or branched alkyl group which comprises 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 to the alkyl, cycloalkyl, alkoxy groups above respectively, which are substituted with at least one halogen atom, selected from the group consisting of fluorine, chlorine and bromine,
a linear or branched alkenyl or alkynyl group comprising 1-12 carbon atoms,
a linear or branched alkenyloxy or alkynyloxy group comprising 1-12 carbon atoms,
an aryl or heteroaryl group having the same definition as that given above for aryl or heteroaryl groups within the definitions of R1, R2,
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 above for R1, R2,
an amine or amide group:
—NH2, —NHR11, —CONH2, —CNHR11,
R11, R12, and R13 having their respective definitions given above for the amine substituents of the values R1, R2,
a —C(R16)2X group, wherein X is —CN, halogen, hydroxy, alkoxy, benzoyloxy, C1-C6 acyloxy, amino, C1-C6 mono-alklamino, C1-C6 dialkyl amino, morpholino, piperidino, 1-indolinyl, pyrrolidyl, or trimethylsilyloxy, R16 is hydrogen, C1-C6 alkyl, phenyl or naphthyl with C1-C6 alkyl or C1-C6 alkoxy substituents,
an —OCOR17 or —COOR17 group, R17 representing a straight or branched alkyl group comprising 1 to 6 carbon atoms, or a cycloalkyl group comprising 3 to 6 carbon atoms, or a phenyl group, optionally substituted with at least one of the substituents listed above within the values in the definitions of R1, R2,
a methacryloyl group or an acryloyl group, or an epoxy group having the formula,
in which k=1, 2 or 3,
R5 and R6 together form a 5- to 7-member aromatic or non-aromatic ring which can comprise at least one heteroatom selected from oxygen, sulfur, and nitrogen, and/or at least one substituent selected from the group consisting of a C1 to C6 alkyl group which is linear or
branched, a C1 to C6 alkoxy group which is linear or branched, and an amine group of formula —NH2, NHR11, or
as defined in R1 and R2 for amine groups,
a polyether, polyamide, polycarbonate, polycarbamate, polyurea or polyester residue;
each R7 group can be same or different, independently representing
a hydrogen, a halogen selected from the group consisting of fluorine, chlorine or bromine,
a linear or branched alkyl group which comprises 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 to the alkyl, cycloalkyl, alkoxy groups described above respectively, which are substituted with at least one halogen atom selected from the group consisting of fluorine, chlorine and bromine,
a linear or branched alkenyl or alkynyl group comprising 1-12 carbon atoms,
a linear or branched alkenyloxy or alkynyloxy group comprising 1-12 carbon atoms,
an aryl or heteroaryl group having the same definition as that given supra for R1, R2,
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 above for R1, R2,
an amine or amide group, such as —NH2, —NHR11, —CONH2, —CONHR11,
R9, R10, and R12 having their respective definitions given above for the amine substituents and for the definitions of R1, R2,
a —C(R16)2X group, wherein X is —CN, halogen, hydroxy, alkoxy, benzoyloxy, C1-C6 acyloxy, amino, C1-C6 mono-alklamino, C1-C6 dialkyl amino, morpholino, piperidino, 1-indolinyl, pyrrolidyl, or trimethylsilyloxy, R16 is hydrogen, C1-C6 alkyl, phenyl or naphthyl with C1-C6 alkyl or C1-C6 alkoxy substituents,
an —OCOR17 or —COOR17 group, R17 representing a straight or branched alkyl group comprising 1 to 6 carbon atoms, or a cycloalkyl group comprising 3 to 6 carbon atoms, or a phenyl group, optionally substituted with at least one of the substituents listed above for the values of R1, R2:aryl or heteroaryl,
a methacryloyl group or an acryloyl group, an epoxy group having the formula,
in which k 1, 2 or 3,
a polyether, polyamide, polycarbonate, polycarbamate, polyurea or polyester residue,
m is an integer from 0 to 2;
F may be substituted with one or more groups R8 group, which may be the same or different, and independently represent
a hydrogen,
a halogen, and notably fluorine, chlorine or bromine,
a linear or branched alkyl group which comprises 1 to 12 carbon atoms,
a cycloalkyl group comprising 3 to 12 carbon atoms, and
two of the R8 groups, which are adjacent or bonded to the same carbon atom in the group F, form a 5- to 6-membered non-aromatic ring which can comprise at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen.

65 more elements

Dependencies are inferred from the claim text.

Abstract

Claims44

Dependent claims

A photochromic article comprising a layer of polymeric binder containing a naphthopyran having a central nucleus of the formula:

wherein F is an oxygen-containing 5- to 7-member heterocyclic ring group, its 2,3 or 3,2 positions fused to the f, i, j, or k side of the ring, and
R1 and R2 are the atoms or groups providing photochromic properties to the naphthopyran.

A photochromic article comprising a layer of polymeric binder containing a naphthopyran having a central nucleus of the formula:

wherein F is an oxygen-containing 5- to 7-member heterocyclic ring group, its 2,3 or 3,2 positions fused to the f, i, j, or k side of the ring, and
R1 and R2 are the atoms or groups necessary to provide photochromic properties to the naphthopyran and R5 and R6 are selected from the group consisting of:
a hydrogen,
a halogen,
a linear or branched alkyl group of 1 to 12 carbon atoms,
a cycloalkyl group of 3 to 12 carbon atoms,
a linear or branched alkoxy group of 1 to 12 carbon atoms;,
a haloalkyl, halocycloalkyl, or haloalkoxy group,
a linear or branched alkenyl or alkynyl group of 1-12 carbon atoms,
a linear or branched alkenyloxy or alkynyloxy group of 1-12 carbon atoms,
an aryl or heteroaryl group,
an aralkyl or heteroaralkyl group, the alkyl group, which is linear or branched, of 1 to 4 carbon atoms;
an amine or amide group:
—NH2, —NHR11, —CONH2, —CONHR11,
R11 representing a linear or branched alkyl group of 1 to 6 carbon atoms, R12 and R13 which are the same or different, independently representing a linear or branched alkyl group of 1 to 6 carbon atoms, or representing together with the nitrogen atom to which they are bound a 5- to 7-membered ring which comprise at least one other heteroatom selected from oxygen, sulfur and nitrogen;
a —C(R16)2X group, wherein X is selected from the group consisting of
—CN, halogen, hydroxy, alkoxy, benzoyloxy, C1-C6 acyloxy, amino, C1-C6 mono-alklamino, C1-C6 dialkyl amino, morpholino, piperidino, 1-indolinyl, pyrrolidyl, or trimethylsilyloxy, R16 is hydrogen, C1-C6 alkyl, phenyl or naphthyl with C1-C6 alkyl or C1-C6 alkoxy substituents,
an —OCOR17 or —COOR17 group, R17 representing a straight or branched alkyl group comprising 1 to 6 carbon atoms, or a cycloalkyl group comprising 3 to 6 carbon atoms, or a phenyl group,
a methacryloyl group or an acryloyl group, an epoxy group,
a polyether, polyamide, polycarbonate, polycarbamate, polyurea or polyester residue;
an aralkyl or heteroaralkyl group, the alkyl group, which is linear or branched, comprising 1 to 4 carbon atoms,
R5 and R6 together form a 5- to 7-member aromatic or non-aromatic ring, the ring may comprising at least one heteroatom selected from oxygen, sulfur, and nitrogen.

19 more elements

A photochromic article comprising a polymeric binder and a naphthopyran of the formula (I):

in which:
F is an oxygen-containing 5- to 7-member heterocyclic ring with or without substitutions, its 2,3 or 3,2 positions fused to the f, i, j, or k side of the ring,
R1 and R2 independently represent:
a hydrogen,
a linear or branched alkyl group which comprises 1 to 12 carbon atoms,
a cycloalkyl group which comprises 3 to 12 carbon atoms,
an aryl or heteroaryl group which comprises in its basic structure (that is, in its ring atoms, the rings comprising 5, 6 or 7 atoms) 6 to 24 carbon atoms or 4 to 24 carbon atoms respectively and at least one heteroatom selected from sulfur, oxygen and nitrogen;
the basic structure being optionally substituted with at least one substituent selected from:
a halogen atom,
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 —NHR11 group, R11 representing a linear or branched alkyl group comprising 1 to 6 carbon atoms,
a
group, in which R12 and R13, which are the same or different, independently representing a linear or branched alkyl group comprising 1 to 6 carbon atoms, or representing, together with the nitrogen atom to which they are bound, a 5- to 7-membered ring which can comprise at least one other heteroatom selected from oxygen, sulfur and nitrogen, said nitrogen being optionally substituted with an R14 group, which is a linear or branched alkyl group comprising 1 to 6 carbon atoms,
a methacryloyl group or an acryloyl group,
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
the two substituents R1 and R2 together forming ring group selected from the group consisting of adamantyl, norbornyl, fluorenylidene, 5,5- or 10,10-di(C1-C6)alkylanthracenylidene, 5 (or 10)-(C1-C6)alkyl-5 (or 10)-OH (or OR15)anthracenylidene or spiro(C5-C6)cycloalkylanthracenylidene ring group;
said ring group being optionally substituted with at least one of the substituents listed above in the definitions for R1, R2;
said ring group being optionally substituted with two adjacent groups that form a 5- to 6-member aromatic or non-aromatic ring which can comprise at least one heteroatom selected from oxygen, sulfur, and nitrogen;
R5 and R6 are the same or different and they represent, independently:
a hydrogen,
a halogen, and notably fluorine, chlorine or bromine,
a linear or branched alkyl group which comprises 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 to the alkyl, cycloalkyl, alkoxy groups above respectively, which are substituted with at least one halogen atom, selected from the group consisting of fluorine, chlorine and bromine,
a linear or branched alkenyl or alkynyl group comprising 1-12 carbon atoms,
a linear or branched alkenyloxy or alkynyloxy group comprising 1-12 carbon atoms,
an aryl or heteroaryl group having the same definition as that given above for aryl or heteroaryl groups within the definitions of R1, R2,
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 above for R1, R2,
an amine or amide group:
—NH2, —NHR11, —CONH2, —CNHR11,
R11, R12, and R13 having their respective definitions given above for the amine substituents of the values R1, R2,
a —C(R16)2X group, wherein X is —CN, halogen, hydroxy, alkoxy, benzoyloxy, C1-C6 acyloxy, amino, C1-C6 mono-alklamino, C1-C6 dialkyl amino, morpholino, piperidino, 1-indolinyl, pyrrolidyl, or trimethylsilyloxy, R16 is hydrogen, C1-C6 alkyl, phenyl or naphthyl with C1-C6 alkyl or C1-C6 alkoxy substituents,
an —OCOR17 or —COOR17 group, R17 representing a straight or branched alkyl group comprising 1 to 6 carbon atoms, or a cycloalkyl group comprising 3 to 6 carbon atoms, or a phenyl group, optionally substituted with at least one of the substituents listed above within the values in the definitions of R1, R2,
a methacryloyl group or an acryloyl group, or an epoxy group having the formula,
in which k=1, 2 or 3,
R5 and R6 together form a 5- to 7-member aromatic or non-aromatic ring which can comprise at least one heteroatom selected from oxygen, sulfur, and nitrogen, and/or at least one substituent selected from the group consisting of a C1 to C6 alkyl group which is linear or
branched, a C1 to C6 alkoxy group which is linear or branched, and an amine group of formula —NH2, NHR11, or
as defined in R1 and R2 for amine groups,
a polyether, polyamide, polycarbonate, polycarbamate, polyurea or polyester residue;
each R7 group can be same or different, independently representing
a hydrogen, a halogen selected from the group consisting of fluorine, chlorine or bromine,
a linear or branched alkyl group which comprises 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 to the alkyl, cycloalkyl, alkoxy groups described above respectively, which are substituted with at least one halogen atom selected from the group consisting of fluorine, chlorine and bromine,
a linear or branched alkenyl or alkynyl group comprising 1-12 carbon atoms,
a linear or branched alkenyloxy or alkynyloxy group comprising 1-12 carbon atoms,
an aryl or heteroaryl group having the same definition as that given supra for R1, R2,
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 above for R1, R2,
an amine or amide group, such as —NH2, —NHR11, —CONH2, —CONHR11,
R9, R10, and R12 having their respective definitions given above for the amine substituents and for the definitions of R1, R2,
a —C(R16)2X group, wherein X is —CN, halogen, hydroxy, alkoxy, benzoyloxy, C1-C6 acyloxy, amino, C1-C6 mono-alklamino, C1-C6 dialkyl amino, morpholino, piperidino, 1-indolinyl, pyrrolidyl, or trimethylsilyloxy, R16 is hydrogen, C1-C6 alkyl, phenyl or naphthyl with C1-C6 alkyl or C1-C6 alkoxy substituents,
an —OCOR17 or —COOR17 group, R17 representing a straight or branched alkyl group comprising 1 to 6 carbon atoms, or a cycloalkyl group comprising 3 to 6 carbon atoms, or a phenyl group, optionally substituted with at least one of the substituents listed above for the values of R1, R2:aryl or heteroaryl,
a methacryloyl group or an acryloyl group, an epoxy group having the formula,
in which k 1, 2 or 3,
a polyether, polyamide, polycarbonate, polycarbamate, polyurea or polyester residue,
m is an integer from 0 to 2;
F may be substituted with one or more groups R8 group, which may be the same or different, and independently represent
a hydrogen,
a halogen, and notably fluorine, chlorine or bromine,
a linear or branched alkyl group which comprises 1 to 12 carbon atoms,
a cycloalkyl group comprising 3 to 12 carbon atoms, and
two of the R8 groups, which are adjacent or bonded to the same carbon atom in the group F, form a 5- to 6-membered non-aromatic ring which can comprise at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen.

65 more elements

Dependencies are inferred from the claim text.

Oxygen-containing heterocyclic fused naphthopyrans

Life of this patent

Abstract

Claims44

Oxygen-containing heterocyclic fused naphthopyrans

Life of this patent

Abstract

Claims44