US 5,658,501 AGranted

Substituted naphthopyrans

AssigneeTransitions Optical, Inc.

InventorsAnil Kumar, David B. Knowles, Barry Van Gemert

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Abstract

Described are novel reversible photochromic 2H-naphtho[1,2-b] pyran compounds, examples of which are compounds having certain substituents at the number 5 carbon atom of the naphtho-portion of the naphthopyran and at the 2-position of the pyran ring. Certain substituents may also be present at the number 6, 7, 8, 9 or 10 carbon atoms of the naphtho portion of the naphthopyran. Also described are organic host materials that contain or that are coated with such compounds. Articles such as ophthalmic lenses or other plastic transparencies that incorporate the novel naphthopyran compounds or combinations thereof with complementary photochromic compounds, e.g., spiro(indoline) type compounds, are also described.

Claims20

Dependent claims

A naphthopyran compound represented by the following graphic formula:

##STR12## wherein, (a) R.sub.1 is selected from the group consisting of, --SR.sub.7, --OR.sub.4, --CH(COOR.sub.7).sub.2, --CH.sub.2 COOR.sub.7, --N(R.sub.5)R.sub.6, --N(R.sub.7)C(O)R.sub.7, --C(R.sub.7).sub.2 OH, --CN, --CF.sub.3, halogen, C.sub.1 -C.sub.6 alkyl, C.sub.3 -C.sub.7 cycloalkyl, the mono-, di- and tri- substituted ary1 groups phenyl and naphthyl, unsubstituted and mono-substituted phenyl(C.sub.1 -C.sub.3)alkyl, unsubstituted and mono-substituted naphthyl(C.sub.1 -C.sub.3)alkyl, (C.sub.1 -C.sub.6)alkoxy(C.sub.2 -C.sub.4)alkyl, the unsubstituted, mono- and di-substituted heterocyclic aromatic groups pyridyl, pyrrolyl, indolyl, furanyl, benzofuranyl, thienyl and benzothienyl;
wherein R.sub.7 is C.sub.1 -C.sub.6 alkyl, or the mono-, di- or tri-substituted aryl groups phenyl and naphthyl, R.sub.4 is hydrogen, C.sub.1 -C.sub.6 alky, the mono- or di-substituted aryl groups phenyl and naphthyl, unsubstituted or mono-substituted phenyl(C.sub.1 -C.sub.3)alkyl, unsubstituted or mono-substituted naphthyl(C.sub.1 -C.sub.3)alkyl, (C.sub.1 -C.sub.6)alkoxy(C.sub.2 -C.sub.4)alkyl, C.sub.3 -C.sub.7 cycloalkyl, mono(C.sub.1 -C.sub.4)alkyl substituted C3-C.sub.7 cycloalkyl, C.sub.1 -C.sub.6 haloalkyl, allyl, the group, --CH(R.sub.14)X, wherein X is --CN, --CF.sub.3, halogen, or --C(O)W, W being --OR.sub.12, wherein R.sub.12 is hydrogen, allyl, C.sub.1 -C.sub.6 alkyl, unsubstituted or mono-substituted phenyl, unsubstituted or mono-substituted phenyl (C.sub.1 -C.sub.3)alkyl, (C.sub.1 -C.sub.6)alkoxy(C.sub.2 -C.sub.4)alkyl, or C.sub.1 -C.sub.6 haloalkyl, and R.sub.14 is hydrogen or C.sub.1 -C.sub.6 alkyl;
or R.sub.4 is the group;
--C(O)Y, wherein Y is hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, unsubstituted, mono- or disubstituted phenyl, unsubstituted, mono- or di-substituted phenoxy, R.sub.5 and R.sub.6 are each selected from the group consisting of hydrogen, C.sub.1 -C.sub.6 alkyl, C5-C.sub.7 cycloalkyl, phenyl, mono- or di-substituted phenyl, or R.sub.5 and R.sub.6 together with the nitrogen atom form an unsubstituted, mono-substituted, or di-substituted heterocyclic ring selected from the group consisting of 1-indolinyl, morpholino, piperidino, 1-pyrrolidyl, 1-imidazolidyl, 2-imidazolin-1-yl, pyrazolidyl, pyrazolinyl and 1-piperazinyl, each of the said phenyl, phenoxy and heterocyclic substituents being selected from the group consisting of hydroxy, amino, C.sub.1 -C.sub.6 monoalkylamino, C.sub.1 -C.sub.6 dialkylamino, piperidino, morpholino, pyrryl, indolinyl, pyrrolidyl, trimethylsilyloxy, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.1 -C.sub.6 alkoxy, mono(C.sub.1 -C.sub.6)alkoxy(C.sub.1 -C.sub.4)alkyl, acryloxy, methacryloxy and halogen, each of said halogen or (halo) groups being fluoro or chloro;
(b) R.sub.2 is the group, --OR.sub.4, R.sub.4 being the same as defined in (a);
(c) each R.sub.3 is selected from the group consisting of C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, halogen, unsubstituted and mono-substituted phenyl, unsubstituted and mono-substituted phenoxy, said phenyl and phenoxy substituents being selected from the group consisting of C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy and halogen, each of said halogen groups being fluoro or chloro, and n is selected from the integers 0, 1, 2, and 3;
(d) B and B' are each selected from the group consisting of:
(i) the unsubstituted, mono-, di- and tri-substituted aryl groups phenyl and naphthyl,
(ii) the unsubstituted, mono- and di-substituted heterocyclic aromatic groups pyridyl, furanyl, benzofuranyl, thienyl, benzothienyl, dibenzothienyl, dibenzofuranyl, and carbazolyl, said phenyl, naphthyl and heterocyclic substituents being selected from the group consisting of hydroxy, amino, C.sub.1 -C.sub.6 monoalkylamino, C.sub.1 -C.sub.6 dialkylamino, piperidino, morpholino, 1-indolinyl, pyrrolidyl, 1-imidazolidyl, 2-imidazolin-1-yl, 2-pyrazolidyl, pyrazolinyl, 1-piperazinyl, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.1 -C.sub.6 alkoxy, mono(C.sub.1 -C.sub.6)alkoxy(C.sub.1 -C.sub.4)alkyl, acryloxy, methacryloxy and halogen, each of said halogen or (halo) groups being fluoro or chloro;
(iii) the groups represented by the following graphic formulae:
##STR13## wherein D is carbon or oxygen and E is oxygen or substituted nitrogen, provided that when E is substituted nitrogen, D is carbon, said nitrogen substituent being selected from the group consisting of hydrogen, C.sub.1 -C.sub.6 alkyl and C.sub.2 -C.sub.6 acyl, each R.sub.8 is C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, hydroxy or halogen, said halogen being chloro or fluoro;
R.sub.9 and R.sub.10 are each hydrogen or C.sub.1 -C.sub.6 alkyl;
and m is the integer 0, 1, or 2;
(iv) C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.1 -C.sub.6 alkoxy(C.sub.1 -C.sub.4) alkyl, C.sub.3 -C.sub.6 cycloalkyl, mono (C.sub.1 -C.sub.6) alkoxy (C.sub.3 -C.sub.6) cycloalkyl, mono (C.sub.1 -C.sub.6) alkyl (C.sub.3 -C.sub.6) cycloalkyl and halo(C.sub.3 -C.sub.6)cycloalkyl, said halo groups being fluoro or chloro;
and
(v) the group represented by the following graphic formula:
##STR14## wherein U is hydrogen or C.sub.1 -C.sub.4 alkyl, and V is selected from the group consisting of the unsubstituted, mono- and di-substituted members of the group consisting of naphthyl, phenyl, furanyl and thienyl, wherein the substituents for each member of said group are C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, fluoro, or chloro;
or
(vi) B and B' taken together form an unsubstituted, mono- or di-substituted fluoren-9-ylidene or a member selected from the group consisting of saturated C.sub.3 -C.sub.12 spiro-monocyclic hydrocarbon rings, saturated C.sub.7 -C.sub.12 spiro-bicyclic hydrocarbon rings, and saturated C.sub.7 -C.sub.12 spiro-tricyclic hydrocarbon rings, said fluoren-9-ylidene substituents being selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, fluoro and chloro.

16 more elements

Dependencies are inferred from the claim text.

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Abstract

A naphthopyran compound represented by the following graphic formula:

##STR12## wherein, (a) R.sub.1 is selected from the group consisting of, --SR.sub.7, --OR.sub.4, --CH(COOR.sub.7).sub.2, --CH.sub.2 COOR.sub.7, --N(R.sub.5)R.sub.6, --N(R.sub.7)C(O)R.sub.7, --C(R.sub.7).sub.2 OH, --CN, --CF.sub.3, halogen, C.sub.1 -C.sub.6 alkyl, C.sub.3 -C.sub.7 cycloalkyl, the mono-, di- and tri- substituted ary1 groups phenyl and naphthyl, unsubstituted and mono-substituted phenyl(C.sub.1 -C.sub.3)alkyl, unsubstituted and mono-substituted naphthyl(C.sub.1 -C.sub.3)alkyl, (C.sub.1 -C.sub.6)alkoxy(C.sub.2 -C.sub.4)alkyl, the unsubstituted, mono- and di-substituted heterocyclic aromatic groups pyridyl, pyrrolyl, indolyl, furanyl, benzofuranyl, thienyl and benzothienyl;
wherein R.sub.7 is C.sub.1 -C.sub.6 alkyl, or the mono-, di- or tri-substituted aryl groups phenyl and naphthyl, R.sub.4 is hydrogen, C.sub.1 -C.sub.6 alky, the mono- or di-substituted aryl groups phenyl and naphthyl, unsubstituted or mono-substituted phenyl(C.sub.1 -C.sub.3)alkyl, unsubstituted or mono-substituted naphthyl(C.sub.1 -C.sub.3)alkyl, (C.sub.1 -C.sub.6)alkoxy(C.sub.2 -C.sub.4)alkyl, C.sub.3 -C.sub.7 cycloalkyl, mono(C.sub.1 -C.sub.4)alkyl substituted C3-C.sub.7 cycloalkyl, C.sub.1 -C.sub.6 haloalkyl, allyl, the group, --CH(R.sub.14)X, wherein X is --CN, --CF.sub.3, halogen, or --C(O)W, W being --OR.sub.12, wherein R.sub.12 is hydrogen, allyl, C.sub.1 -C.sub.6 alkyl, unsubstituted or mono-substituted phenyl, unsubstituted or mono-substituted phenyl (C.sub.1 -C.sub.3)alkyl, (C.sub.1 -C.sub.6)alkoxy(C.sub.2 -C.sub.4)alkyl, or C.sub.1 -C.sub.6 haloalkyl, and R.sub.14 is hydrogen or C.sub.1 -C.sub.6 alkyl;
or R.sub.4 is the group;
--C(O)Y, wherein Y is hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, unsubstituted, mono- or disubstituted phenyl, unsubstituted, mono- or di-substituted phenoxy, R.sub.5 and R.sub.6 are each selected from the group consisting of hydrogen, C.sub.1 -C.sub.6 alkyl, C5-C.sub.7 cycloalkyl, phenyl, mono- or di-substituted phenyl, or R.sub.5 and R.sub.6 together with the nitrogen atom form an unsubstituted, mono-substituted, or di-substituted heterocyclic ring selected from the group consisting of 1-indolinyl, morpholino, piperidino, 1-pyrrolidyl, 1-imidazolidyl, 2-imidazolin-1-yl, pyrazolidyl, pyrazolinyl and 1-piperazinyl, each of the said phenyl, phenoxy and heterocyclic substituents being selected from the group consisting of hydroxy, amino, C.sub.1 -C.sub.6 monoalkylamino, C.sub.1 -C.sub.6 dialkylamino, piperidino, morpholino, pyrryl, indolinyl, pyrrolidyl, trimethylsilyloxy, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.1 -C.sub.6 alkoxy, mono(C.sub.1 -C.sub.6)alkoxy(C.sub.1 -C.sub.4)alkyl, acryloxy, methacryloxy and halogen, each of said halogen or (halo) groups being fluoro or chloro;
(b) R.sub.2 is the group, --OR.sub.4, R.sub.4 being the same as defined in (a);
(c) each R.sub.3 is selected from the group consisting of C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, halogen, unsubstituted and mono-substituted phenyl, unsubstituted and mono-substituted phenoxy, said phenyl and phenoxy substituents being selected from the group consisting of C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy and halogen, each of said halogen groups being fluoro or chloro, and n is selected from the integers 0, 1, 2, and 3;
(d) B and B' are each selected from the group consisting of:
(i) the unsubstituted, mono-, di- and tri-substituted aryl groups phenyl and naphthyl,
(ii) the unsubstituted, mono- and di-substituted heterocyclic aromatic groups pyridyl, furanyl, benzofuranyl, thienyl, benzothienyl, dibenzothienyl, dibenzofuranyl, and carbazolyl, said phenyl, naphthyl and heterocyclic substituents being selected from the group consisting of hydroxy, amino, C.sub.1 -C.sub.6 monoalkylamino, C.sub.1 -C.sub.6 dialkylamino, piperidino, morpholino, 1-indolinyl, pyrrolidyl, 1-imidazolidyl, 2-imidazolin-1-yl, 2-pyrazolidyl, pyrazolinyl, 1-piperazinyl, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.1 -C.sub.6 alkoxy, mono(C.sub.1 -C.sub.6)alkoxy(C.sub.1 -C.sub.4)alkyl, acryloxy, methacryloxy and halogen, each of said halogen or (halo) groups being fluoro or chloro;
(iii) the groups represented by the following graphic formulae:
##STR13## wherein D is carbon or oxygen and E is oxygen or substituted nitrogen, provided that when E is substituted nitrogen, D is carbon, said nitrogen substituent being selected from the group consisting of hydrogen, C.sub.1 -C.sub.6 alkyl and C.sub.2 -C.sub.6 acyl, each R.sub.8 is C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, hydroxy or halogen, said halogen being chloro or fluoro;
R.sub.9 and R.sub.10 are each hydrogen or C.sub.1 -C.sub.6 alkyl;
and m is the integer 0, 1, or 2;
(iv) C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.1 -C.sub.6 alkoxy(C.sub.1 -C.sub.4) alkyl, C.sub.3 -C.sub.6 cycloalkyl, mono (C.sub.1 -C.sub.6) alkoxy (C.sub.3 -C.sub.6) cycloalkyl, mono (C.sub.1 -C.sub.6) alkyl (C.sub.3 -C.sub.6) cycloalkyl and halo(C.sub.3 -C.sub.6)cycloalkyl, said halo groups being fluoro or chloro;
and
(v) the group represented by the following graphic formula:
##STR14## wherein U is hydrogen or C.sub.1 -C.sub.4 alkyl, and V is selected from the group consisting of the unsubstituted, mono- and di-substituted members of the group consisting of naphthyl, phenyl, furanyl and thienyl, wherein the substituents for each member of said group are C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, fluoro, or chloro;
or
(vi) B and B' taken together form an unsubstituted, mono- or di-substituted fluoren-9-ylidene or a member selected from the group consisting of saturated C.sub.3 -C.sub.12 spiro-monocyclic hydrocarbon rings, saturated C.sub.7 -C.sub.12 spiro-bicyclic hydrocarbon rings, and saturated C.sub.7 -C.sub.12 spiro-tricyclic hydrocarbon rings, said fluoren-9-ylidene substituents being selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, fluoro and chloro.

16 more elements