Indeno-fused photochromic naphthopyrans

Described are novel reversible photochromic indenonaphthopyran compounds, examples of which are 2H-naphtho[1,2-b]pyrans characterized by having a substituted or unsubstituted indeno group fused at the 2,3 positions of the group to the 1 side of the 2H-naphthopyran. The compounds also have substituents at the 3 position of the pyran ring. Substituents may also be present at the number 5, 6, 7, 8, 9, 10, 11, 12, or 13 carbon atoms of the compounds. These compounds may be represented by the following graphic formulae: ##STR1## Also described are various substrates, e.g., paper, glass, organic polymeric materials, etc., that contain or that are coated with such compounds. Optically clear articles such as ophthalmic lenses or other plastic transparencies that incorporate the novel indenonaphthopyran compounds or combinations thereof with complementary photochromic compounds, e.g., indenonaphthopyrans, naphthopyrans, benzopyrans, oxazine-type compounds, etc., are also described.

 

We claim:

1. A naphthopyran compound represented by the following graphic formula: ##STR14##

wherein,

(a) R.sub.1 and R.sub.2 are each selected from the group consisting of:

(i) hydrogen, hydroxy, amino, mono- and di-substituted amino, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.3 -C.sub.7 cycloalkyl, allyl, benzyl, mono-substituted benzyl, halogen and the group, --C(O)W, wherein W is hydroxy, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, phenyl, C.sub.3 -C.sub.7 cycloalkyloxy, mono-substituted phenyl, phenoxy, amino, mono(C.sub.3 -C.sub.7)alkylamino, di (C.sub.1 -C.sub.6)alkylamino, morpholino, piperidino or pyrrolidyl, said amino substituents being selected from the group consisting of C.sub.1 -C.sub.6 alkyl, phenyl, benzyl and naphthyl, said benzyl and phenyl substituents being C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, piperidino, morpholino, di(C.sub.1 -C.sub.6)alkylamino or fluoro;

(ii) unsubstituted, mono- di- and tri-substituted members selected from the group consisting of phenyl, naphthyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl, benzofuranyl, thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, and indolyl, said group substituents in (a) (ii) being selected from the group consisting of halogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, morpholino, pipenidino, pyrrolidino, amino, mono- and di-substituted amino, said amino substituents being selected from the group consisting of C.sub.1 -C.sub.6 alkyl, phenyl, benzyl and naphthyl;

(iii) monosubstituted phenyl, having a substituent at the para position that is a linking group, --(CH.sub.2).sub.t -- or --O--(CH.sub.2).sub.t --, wherein t is the integer 1, 2, 3, 4, 5 or 6, connected to an aryl group, which is a member of another photochromic naphthopyran;

(iv) a group, --OR.sub.5, wherein R.sub.5 is C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 acyl, phenyl (C.sub.1 -C.sub.3)alkyl, mono (C.sub.1 -C.sub.6)alkyl substituted phenyl (C.sub.1 -C.sub.3)alkyl, mono(C.sub.1 -C.sub.6)alkoxy substituted phenyl(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 C.sub.3 -C.sub.7 cycloalkyl, C.sub.1 -C.sub.6 haloalkyl, allyl, benzoyl, monosubstituted benzoyl, naphthoyl or monosubstituted naphthoyl, said benzoyl and naphthoyl group substituents being C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 alkoxy; or R.sub.5 is the group --CH(R.sub.6)Q, wherein R.sub.6 is hydrogen or C.sub.1 -C.sub.3 alkyl and Q is --CN, --CF.sub.3, or --COOR.sub.7, and R.sub.7 is hydrogen or C.sub.1 -C.sub.3 alkyl; or R.sub.5 is the group, --C(O)V, wherein V is hydrogen, C.sub.1 -C.sub.6 alkoxy, phenoxy, mono- or di-(C.sub.1 -C.sub.6)alkyl substituted phenoxy, mono- or di-(C.sub.1 -C.sub.6)alkoxy substituted phenoxy, an unsubstituted, mono- or di-substituted aryl group, amino, mono(C.sub.1 -C.sub.6)alkylamino, di(C.sub.1 -C.sub.6)alkylamino phenylamino, mono- or di-(C.sub.1 -C.sub.6)alkyl substituted phenylamino, or mono- or di-(C.sub.1 -C.sub.6) alkoxy substituted phenylamino, said aryl group substituents being C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 alkoxy;

(v) a group, --CH(Q').sub.2, wherein Q' is --CN or --COOR.sub.8, wherein R.sub.8 is hydrogen, C.sub.1 -C.sub.6 alkyl, phenyl(C.sub.1 -C.sub.3)alkyl, mono (C.sub.1 -C.sub.6)alkyl substituted phenyl(C.sub.1 -C.sub.3)alkyl, mono(C.sub.1 -C.sub.6)alkoxy substituted phenyl(C.sub.1 -C.sub.3)alkyl, or an unsubstituted, mono- or di-substituted aryl group, each of said aryl group substituents being C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 alkoxy;

(vi) a group, --CH(R.sub.9)G, wherein R.sub.9 is hydrogen, C.sub.1 -C.sub.6 alkyl or an unsubstituted, mono- or di-substituted aryl group, and G is hydroxy, C.sub.1 -C.sub.6 alkoxy, aryloxy, amino, mono(C.sub.1 -C.sub.6)alkylamino, di(C.sub.1 -C.sub.6)alkylamino, phenylamino, mono- or di-(C.sub.1 -C.sub.6)alkyl substituted phenylamino, or mono- or di-(C.sub.1 -C.sub.6)alkoxy substituted phenylamino, --COOR.sub.8, --COR.sub.10 or --CH.sub.2 OR.sub.11, wherein R.sub.10 is hydrogen, C.sub.1 -C.sub.6 alkyl, an unsubstituted, mono- or di-substituted aryl group, amino, mono(C.sub.1 -C.sub.6)alkylamino, di(C.sub.1 -C.sub.6) alkylamino, phenylamino, mono- or di-(C.sub.1 -C.sub.6)alkyl substituted phenylamino, mono- or di-(C.sub.1 -C.sub.6)alkoxy substituted phenylamino, diphenylamino, mono- or di(C.sub.1 -C.sub.6)alkyl substituted diphenylamino, mono- or di(C.sub.1 -C.sub.6)alkoxy substituted diphenylamino, morpholino, or piperidino, wherein R.sub.11 is hydrogen, --C(O)R.sub.8, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.3 alkoxy(C.sub.1 -C.sub.6)alkyl, phenyl(C.sub.1 -C.sub.3)alkyl, mono(C.sub.1 -C.sub.6) alkoxy substituted phenyl(C.sub.1 -C.sub.3)alkyl, or an unsubstituted, mono- or di-substituted aryl group, each of said aryl group substituents being C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 alkoxy; and

(vii) a group, T, represented by the formula:

--Z[(OC.sub.2 H.sub.4).sub.x (OC.sub.3 H.sub.6).sub.y (OC.sub.4 H.sub.8).sub.z ]Z'

or

--[(OC.sub.2 H.sub.4).sub.x (OC.sub.3 H.sub.6).sub.y (OC.sub.4 H.sub.8).sub.z ]Z'

wherein --z is --C(O)-- or --CH.sub.2 --, Z' is C.sub.1 -C.sub.3 alkoxy or a polymerizable group, x, y and z are each a number between 0 and 50, and the sum of x, y and z is between 2 and 50; or

(viii) R.sub.1 and R.sub.2 together form an oxo group, a substituted or unsubstituted spiro-carbocyclic ring containing 3 to 6 carbon atoms or a substituted or unsubstituted spiro-heterocyclic group containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms including the spirocarbon atom, said spiro-carbocyclic ring and spiro-heterocyclic group being annellated with 0, 1 or 2 benzene rings, said substituents being hydrogen or C.sub.1 -C.sub.6 alkyl, provided that said spiro-carbocyclic ring is not fluoren-9-ylidene;

(b) each R.sub.3 is independently selected from the group consisting of hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, C.sub.3 -C.sub.7 cycloalkyl, phenyl, benzyl, di (C.sub.1 -C.sub.6)alkylamino, dicyclohexylamine, diphenylamino, piperidyl, morpholinyl, pyridyl, halogen, a group, T, and the group --C(O)W and n is the integer 0, 1, or 2; or when n is 2, and the R.sub.3 substituents are adjacent, each pair of substituents independently forms a first R.sub.3 and second R.sub.3 substituted or unsubstituted fused carbocyclic or heterocyclic ring selected from the group consisting of benzo, pyridino, pyrazino, pyrimidino, furano, dihydrofurano, 1,3-dioxolo, 1,4-dioxolo, 1,3-dioxino, 1,4-dioxino, thiopheno, benzofuro, benzothieno, indolo, and indeno, the substituents of said fused carbocyclic or heterocyclic ring being selected from the group consisting of halogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, amino, mono- and di-substituted amino, said amino substituents being selected from the group consisting of C.sub.1 -C.sub.6 alkyl, phenyl, benzyl and naphthyl; said first R.sub.3 ring being fused to the o, p or q side and said second R.sub.3 ring being fused to the g, h or i side of the naphthopyran;

(c) B and B' are each selected from the group consisting of:

(i) mono-T-substituted phenyl

(ii) an unsubstituted, mono-, di-, and tri-substituted aryl group;

(iii) 9-julolidinyl and an unsubstituted, mono- or di-substituted heteroaromatic group selected from the group consisting of pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazoyl, benzopyridyl, indolinyl and fluorenyl, each of said aryl and heteroaromatic substituents in (c) (ii) and (iii) being selected from the group consisting of hydroxy, aryl, hydroxy, aryl, mono(C.sub.1 -C.sub.6)alkoxyaryl, di(C.sub.1 -C.sub.6)alkoxyaryl, mono(C.sub.1 -C.sub.6)alkylaryl, di(C.sub.1 -C.sub.6)alkylaryl, haloaryl, C.sub.3 -C.sub.7 cycloalkylaryl, C.sub.3 -C.sub.7 cycloalkyl, C.sub.3 -C.sub.7 cycloalkyloxy, C.sub.3 -C.sub.7 cycloalkyloxy(C.sub.1 -C.sub.6)alkyl, C.sub.3 -C.sub.7 cycloalkyloxy(C.sub.1 -C.sub.6)alkoxy, aryl(C.sub.1 -C.sub.6)alkyl, aryl (C.sub.1 -C.sub.6)alkoxy, aryloxy, aryloxy(C.sub.1 -C.sub.6)alkyl, aryloxy(C.sub.1 -C.sub.6)alkoxy, mono- and di-(C.sub.1 -C.sub.6)alkylaryl(C.sub.1 -C.sub.6)alkyl mono- and di-(C.sub.1 -C.sub.6)alkoxyaryl(C.sub.1 -C.sub.6)alkyl, mono- and di-(C.sub.1 -C.sub.6)alkylaryl(C.sub.1 -C.sub.6)alkoxy, mono- and di-(C.sub.1 -C.sub.6)alkoxyaryl(C.sub.1 -C.sub.6)alkoxy, amino, mono(C.sub.1 -C.sub.6)alkylamino, di(C.sub.1 -C.sub.6)alkylamino, diarylamino, piperazino, N--(C.sub.1 -C.sub.6)alkylpiperazino, N-arylpiperazino, aziridino, indolino, piperidino, morpholino, thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino, pyrryl, pyrrolidyl, 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;

(iv) an unsubstituted or mono-substituted member selected from the group consisting of pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolinyl, phenothiazinyl, phenoxazinyl, phenazinyl and acridinyl, each of said substituents being selected from the group consisting of C.sub.1 -C.sub.6 alkyl, C.sub.1 C.sub.6 alkoxy, phenyl, and halogen;

(v) monosubstituted phenyl, having a substituent at the para position that is a linking group, --(CH.sub.2).sub.t -- or --O--(CH.sub.2).sub.t --, wherein t is the integer 1, 2, 3, 4, 5 or 6, connected to an aryl group, which is a member of another photochromic naphthopyran;

(vi) a group represented by one of the following graphic formula: ##STR15##

wherein A is methylene or oxygen and D is oxygen or substituted nitrogen, provided that when D is substituted nitrogen, A is methylene, said nitrogen substituents 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.12 is C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, hydroxy, or halogen; R.sub.13 and R.sub.14 are each hydrogen or C.sub.1 -C.sub.6 alkyl; and q is the integer 0, 1, or 2;

(vii) 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, halo(C.sub.3 -C.sub.6)cycloalkyl, and C.sub.4 -C.sub.12 bicycloalkyl; and

(viii) a group represented by the following graphic formula: ##STR16##

wherein L is hydrogen or C.sub.1 -C.sub.4 alkyl and M is selected from the unsubstituted, mono-, and di-substituted members of the group consisting of naphthyl, phenyl, furanyl, and thienyl, each of said group substituents being C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, or halogen; or

(d) B and B' taken together form fluoren-9-ylidene, mono-, or di-substituted fluoren9-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, each of 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, and halogen; said halogen or halo group herein being bromo, chloro, fluoro or iodo and said aryl groups herein being phenyl or naphthyl.

2. A naphthopyran compound of claim 1 wherein,

(a) R.sub.1 and R.sub.2 are each selected from the group consisting of:

(i) hydrogen, hydroxy, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, di-substituted amino, C.sub.3 -C.sub.7 cycloalkyl, benzyl, mono-substituted benzyl, and the group, --C(O)W, wherein W is C.sub.1 -C.sub.6 alkoxy, di(C.sub.1 -C.sub.6)alkylamino, morpholino, or piperidino, said amino substituents being C.sub.1 -C.sub.6 alkyl, said benzyl substituents being C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 alkoxy;

(ii) mono- di- and tri-substituted members selected from the group consisting of phenyl, naphthyl, and dibenzofuranyl, said group substituents in (a) (ii) being selected from the group consisting of C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, di-substituted amino, said amino substituents being C.sub.1 -C.sub.6 alkyl;

(iii) mono-substituted phenyl, having a substituent at the para position that is a linking group, --O--(CH.sub.2).sub.t --, wherein t is the integer 3, 4, or 5, connected to an aryl group, which is a member of another photochromic naphthopyran;

(iv) a group, --OR.sub.5, wherein R.sub.5 is C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 acyl, C.sub.1 -C.sub.6 alkoxy(C.sub.2 -C.sub.4)alkyl, benzoyl, or mono-substituted benzoyl, said benzoyl group substituents being C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 alkoxy; or R.sub.5 is the group --CH(R.sub.6)Q, wherein R.sub.6 is hydrogen and Q is --COOR.sub.7, and R.sub.7 is C.sub.1 -C.sub.3 alkyl; or R.sub.5 is the group, --C(O)V, wherein V is C.sub.1 -C.sub.6 alkoxy, or di(C.sub.1 -C.sub.6)alkylamino;

(v) a group, --CH(Q').sub.2, wherein Q' is --COOR.sub.8, wherein R.sub.8 is C.sub.1 -C.sub.6 alkyl, or phenyl(C.sub.1 -C.sub.3)alkyl;

(vi) a group, --CH(R.sub.9)G, wherein R.sub.9 is (C.sub.1 -C.sub.6)alkyl, and G is C.sub.1 -C.sub.6 alkoxy, --COOR.sub.8, or --CH.sub.2 OR.sub.11, wherein R.sub.10 is C.sub.1 -C.sub.6 alkyl, di(C.sub.1 C.sub.6)alkylamino, morpholino, or piperidino, wherein R.sub.11 is C.sub.1 -C.sub.6 alkyl, or C.sub.1 -C.sub.3 alkoxy(C.sub.1 -C.sub.6)alkyl; and

(vii) a group, T, represented by the formula:

--[(OC.sub.2 H.sub.4).sub.x (OC.sub.3 H.sub.6).sub.y (OC.sub.4 H8).sub.z ]Z'

wherein Z' is C.sub.1 -C.sub.3 alkoxy or a polymerizable group, x, y and z are each a number between 0 and 50, and the sum of x, y and z is between 2 and 50; or

(viii) R.sub.1 and R.sub.2 together form an oxo group, or a substituted or unsubstituted spiro-heterocyclic group containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms including the spirocarbon atom, said spiro-heterocyclic group being annellated with 1 or 2 benzene rings, said substituents being or C.sub.1 -C.sub.6 alkyl;

(b) each R.sub.3 is independently selected from the group consisting of hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, di(C.sub.1 -C.sub.6)alkylamino, piperidyl, morpholinyl, pyrrolidyl, halogen, a group, T, and the group --C(O)W and n is the integer 0, 1, or 2, or when n is 2, and the R.sub.3 substituents are adjacent, a pair of substituents independently forms a substituted or unsubstituted fused carbocyclic or heterocyclic R.sub.3 ring selected from the group consisting of benzo, dihydrofurano and benzofuro, the substituents of said fused carbocyclic or heterocyclic ring being selected from the group consisting of C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, and di-substituted amino, said amino substituents being C.sub.1 -C.sub.6 alkyl; said R.sub.3 ring being fused to the o, p or q side of the naphthopyran;

(c) B and B' are each selected from the group consisting of:

(i) a mono-, or di-substituted phenyl group;

(ii) an unsubstituted, mono- or di-substituted heteroaromatic group selected from the group consisting of furanyl, benzofuran-2-yl, thienyl, benzothien-2-yl, and dibenzofuranyl, each of said phenyl and heteroaromatic substituents in (c) (i) and (ii) being selected from the group consisting of hydroxy, amino, mono(C.sub.1 -C.sub.6)alkylamino, di(C.sub.1 -C.sub.6)alkylamino, piperidino, morpholino, pyrryl, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 chloroalkyl, C.sub.1 C.sub.3 fluoro-alkyl, C.sub.1 C.sub.3 alkoxy, mono(C.sub.1 -C.sub.3)alkoxy(C.sub.1 -C.sub.3)alkyl, fluoro and chloro;

(iii) a group represented by one of the following graphic formula: ##STR17##

wherein A is methylene and D is oxygen; each R.sub.12 is C.sub.1 -C.sub.3 alkyl, or C.sub.1 -C.sub.3 alkoxy; R.sub.13 and R.sub.14 are each hydrogen or C.sub.1 -C.sub.4 alkyl; and q is the integer 0, or 1;

(iv) C.sub.1 -C.sub.4 alkyl,

(v) a group represented by the following graphic formula: ##STR18##

wherein L is hydrogen or methyl and M is phenyl or selected mono-, substituted phenyl, said phenyl substituent being C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 alkoxy, or fluoro; or

(d) B and B' taken together form fluoren-9-ylidene, mono-substituted fluoren-9-ylidene or a member selected from the group consisting of saturated C.sub.3 -C.sub.8 spiro-monocyclic hydrocarbon rings, saturated C.sub.7 -C.sub.10 spiro-bicyclic hydrocarbon rings, and saturated C.sub.7 -C.sub.10 spiro-tricyclic hydrocarbon rings, said fluoren-9-ylidene substituent being selected from the group consisting of C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 alkoxy, fluoro and chloro.

3. A naphthopyran compound of claim 2 wherein:

(a) R.sub.1 and R.sub.2 are each selected from the group consisting of:

(i) hydrogen, hydroxy, C.sub.1 -C.sub.3 alkyl, and the group, --C(O)W, wherein W C.sub.1 -C.sub.6 alkoxy, or morpholino;

(ii) unsubstituted, and mono-substituted phenyl, said phenyl substituents in (a) (ii) being selected from the group consisting of C.sub.1 -C.sub.6 alkoxy, and di-substituted amino, said amino substituents being of C.sub.1 -C.sub.3 alkyl,

(iii) monosubstituted phenyl, having a substituent at the para position that is a linking group, --O--(CH.sub.2).sub.t -- wherein t is the integer 3, connected to an aryl group, which is a member of another photochromic naphthopyran;

(iv) a group, --OR.sub.5, wherein R.sub.5 is C.sub.1 -C.sub.6 alkyl, C.sub.1 C.sub.6 alkoxy(C.sub.2 -C.sub.4)alkyl the group --CH(R.sub.6)Q, wherein R.sub.6 is hydrogen or C.sub.1 C.sub.3 alkyl and Q is --COOR.sub.7, and R.sub.7 is C.sub.1 -C.sub.3 alkyl; or R.sub.5 is the group, --C(O)V, wherein V is C.sub.1 -C.sub.6 alkoxy;

(v) a group, --CH(Q').sub.2, wherein Q' is --COOR.sub.8, wherein R.sub.8 is C.sub.1 -C.sub.6 alkyl.

(vi) a group, --CH(R.sub.9)G, wherein R.sub.9 is C.sub.1 -C.sub.6 alkyl and G is C.sub.1 -C.sub.6 alkoxy, --COOR.sub.8, --COR.sub.10 or --CH.sub.2 OR.sub.11, wherein R.sub.10 and R.sub.11 are each C.sub.1 -C.sub.6 alkyl; and

(vii) a group, T, represented by the formula:

--[(OC.sub.2 H.sub.4).sub.x (OC.sub.3 H.sub.6).sub.y (OC.sub.4 H.sub.8).sub.z ]Z'

wherein Z' is C.sub.1 -C.sub.3 alkoxy or a polymerizable group, x, y and z are each a number between 0 and 50, and the sum of x, y and z is between 2 and 50; or

(viii) R.sub.1 and R.sub.2 together form an oxo group, a substituted or unsubstituted spiro-heterocyclic group containing 1 oxygen atom and 6 carbon atoms including the spirocarbon atom, said spiro-heterocyclic group being annellated with 2 benzene rings, said substituents being C.sub.1 -C.sub.3 alkyl;

(b) each R.sub.3 is independently selected from the group consisting of hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, morpholinyl, a group, T, and the group --C(O)W and n is the integer 0, 1, or 2, or when n is 2, and the R.sub.3 substituents are adjacent, the pair of substituents independently forms a substituted or unsubstituted fused carbocyclic or heterocyclic R.sub.3 ring selected from the group consisting of benzo, and benzofuro, the substituents of said fused carbocyclic or heterocyclic ring being C.sub.1 -C.sub.6 alkoxy; said R.sub.3 ring being fused to the p side of the naphthopyran;

(c) B and B' are each selected from the group consisting of:

(i) an unsubstituted, mono-, or di-substituted phenyl group;

(ii) an unsubstituted, mono- or di-substituted heteroaromatic group selected from the group consisting of furanyl, benzofuran-2-yl, thienyl, benzothien-2-yl, and dibenzofuranyl, each of said phenyl and heteroaromatic substituents in (c) (i) and (ii) being selected from the group consisting of hydroxy, piperidino, morpholino, C.sub.1 -C.sub.3 alkyl, and C.sub.1 -C.sub.3 alkoxy;

(iii) a group represented by the following graphic formula: ##STR19##

wherein A is methylene and D is oxygen; each R.sub.12 is C.sub.1 -C.sub.3 alkyl, or C.sub.1 -C.sub.3 alkoxy; R.sub.13 and R.sub.14 are each hydrogen or C.sub.1 -C.sub.3 alkyl; and q is the integer 0, or 1; or

(d) B and B' taken together form fluoren-9-ylidene, adamantylidene, bornylidene, norbornylidene, or bicyclo nonan-9-ylidene.

4. A naphthopyran compound selected from:

(a) 3,3,9-triphenyl-3H-9H -indeno[3'2':3,4]naphtho[1,2-b]pyran;

(b) 3,3-di (4-methoxyphenyl)-9-phenyl-3H-9H-indeno[3',2':3,4]naphtho[1,2b]pyran;

(c) 3-(4-methoxyphenyl)-3, 9-diphenyl-3H-9H-indeno[3',2':3,4]naphtho[1,2-b]pyran;

(d) 3-(4morpholinophenyl)-3, 9-diphenyl-3H-9H-indeno[3',2':3,4]naphtho[1,2b]pyran;

(e) 3,3-di(4-methoxyphenyl)-9-(3-methoxyphenyl)-11-methoxy-3H-9H-indeno[3',2': 3,4]naphtho[1,2-b]pyran;

(f) 3-(4-methoxyphenyl)-3-phenyl-9-(3-methoxyphenyl)-11-methoxy-3H-9H-indeno[3 ',2':3,4]naphtho[1,2-b]pyran;

(g) 3-(4-methoxyphenyl)-3-phenyl-9-methyl-11-methoxy-9-(3-methoxyphenyl)-3H-9H -indeno[3',2':3,4]naptho[1,2-b]pyran;

(h) 3,3di-(4-methoxyphenyl)-9-methyl-11-methoxy-9-(3-methoxyphenyl)-3H-9H-inde no[3',2':3,4]naptho[1,2-b]pyran;

(i) 3,3-di(4-methoxyphenyl)-9-methyl-11-methoxy-3H-9H-indeno[3',2': 3,4]naphtho[1,2-b]pyran;

(j) 3,3-di(4-methoxyphenyl)-9,9-dimethyl-11-methoxy-3H-9H-indeno[3',2': 3,4]naphtho[1,2-b]pyran;

(k) 3-(4-methoxyphenyl)-3-phenyl-9,9-dimethyl-11-methoxy-3H-9H-indeno[3',2': 3,4]naphtho[1,2-b]pyran;

(l) 3,3di-(4-methoxyphenyl)-9,9-dimethyl-7,11-dimethoxy-3H-9H-indeno[3',2': 3,4]naphtho[1,2--b]pyran;

(m) 3-(4-methoxyphenyl)-3-phenyl-9,9-dimethyl-7,11-dimethoxy-3H-9H-indeno[3',2 ':3,4]naphtho[1,2-b]pyran;

(n) 3-(4-morpholinophenyl)-3-phenyl-9,9-dimethyl-7,11-dimethoxy-3H-9H-indeno[3 ',2':3,4]naphtho[1,2-b]pyran;

(o) 3,3-di(4-methoxyphenyl)-9-methyl-11,13-dimethoxy-3H-9H-indeno[3',2': 3,4]naphtho[1,2-b]pyran;

(p) 3-(4-methoxyphenyl)-3-phenyl-9-methyl-11,13-dimethoxy-3H-9H-indeno[3',2': 3,4]naphtho[1,2-b]pyran;

(q) 3-(4-methoxyphenyl)-3-phenyl-9,9-dimethyl-3H-9H-benzo[4",5"]indeno[3',2': 3,4]naphtho[2-b]pyran; and

(r) 3,3-di(4-methoxyphenyl-9,9-dimethyl-11-fluoro3H-9H-indeno[3',2': 3,4]naphtho[1,2-b]pyran.

5. A photochromic article comprising a polymeric organic host material and a photochromic amount of the naphthopyran compound of claim 1.

6. The photochromic article of claim 5 wherein the polymeric organic host material is selected from the group consisting of poly(C.sub.1 -C.sub.12 alkyl methacrylates), poly(oxyalkylene dimethacrylates), poly(alkoxylated phenol methacrylates), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidene chloride), thermoplastic polycarbonates, polyesters, polyurethanes, polythiourethanes, poly (ethylene terephthalate), polystyrene, poly(alpha methylstyrene), copoly(styrene-methylmethacrylate) copoly(styrene-acrylonitrile), polyvinylbutyral and polymers of members of the group consisting of bis(allyl carbonate) monomers, polyfunctional acrylate monomers, polyfunctional methacrylate monomers, diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers, ethoxylated bisphenol A dimethacrylate monomers, ethylene glycol bismethacrylate monomers, poly(ethylene glycol) bismethacrylate monomers, ethoxylated phenol bismethacrylate monomers, alkoxylated polyhydric alcohol acrylate monomers, styrene monomers, urethane acrylate monomers, glycidyl acrylate monomers, glycidyl methacrylate monomers and diallylidene pentaerythritol monomers.

7. The photochromic article of claim 6 wherein the polymeric organic host material is a solid transparent polymer selected from the group consisting of poly (methyl methacrylate), poly(ethylene glycol bismethacrylate), poly(ethoxylated bisphenol A dimethacrylate), thermoplastic polycarbonate, poly(vinyl acetate), polyvinylbutyral, polyurethane, polythiourethane and polymers of members of the group consisting of diethylene glycol bis(allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, ethoxylated phenol bismethacrylate monomers, dilsopropenyl benzene monomers and ethoxylated trimethylol propane triacrylate monomers.

8. The photochromic article of claim 7 wherein the photochromic compound is present in an amount of from 0.05 to 2.0 milligram per square centimeter of organic host material surface to which the photochromic substance(s) is incorporated or applied.

9. The photochromic article of claim 8 wherein said article is a lens.

10. A photochromic article comprising a polymeric organic host material selected from the group consisting of poly(methyl methacrylate), poly(ethylene glycol bismethacrylate), poly(ethoxylated bisphenol A dimethacrylate), thermoplastic polycarbonate, poly(vinyl acetate), polyvinylbutyral, polyurethane, polythiourethane and polymers of members of the group consisting of diethylene glycol bis(allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, ethoxylated phenol bismethacrylate monomers, diisopropenyl benzene monomers and ethoxylated trimethylol propane triacrylate monomers, and a photochromic amount of the naphthopyran compound of claim 2.

11. A photochromic article comprising a polymeric organic host material selected from the group consisting of poly(methyl methacrylate), poly(ethylene glycol bismethacrylate), poly(ethoxylated bisphenol A dimethacrylate), thermoplastic polycarbonate, poly(vinyl acetate), polyvinylbutyral, polyurethane, polythiourethane and polymers of members of the group consisting of diethylene glycol bis(allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, ethoxylated phenol bismethacrylate monomers, diisopropenyl benzene monomers and ethoxylated trimethylol propane triacrylate monomers, and a photochromic amount of the naphthopyran compound of claim 3.

12. A photochromic article comprising a polymerizate of an optical organic resin monomer and a photochromic amount of the naphthopyran compound of claim 1.

13. The photochromic article of claim 12 wherein the refractive index of the polymerizate is from about 1.48 to about 1.75.

14. The photochromic article of claim 12 wherein the polymerizate is an optical element.

15. The photochromic article of claim 14 wherein said optical element is an ophthalmic lens or a contact lens.

16. A photochromic article comprising, in combination, a solid transparent polymeric organic host material, and a photochromic amount of each of (a) at least one naphthopyran compound of claim 1, and (b) at least one other organic photochromic compound having at least one activated absorption maxima within the range of between about 400 and 700 nanometers.

17. The photochromic article of claim 16 wherein the polymeric organic host material is a solid transparent homopolymer or copolymer selected from the group consisting of poly(methyl methacrylate), poly(ethylene glycol bis-methacrylate), poly(ethoxylated bisphenol A dimethacrylate), thermoplastic polycarbonate, poly(vinyl acetate), polyvinylbutyral, polyurethane, polythiourethane and polymers of members of the group consisting of diethylene glycol bis(allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, ethoxylated phenol bismethacrylate monomers, diisopropenyl benzene monomers and ethoxylated trimethylol propane triacrylate monomers.

18. The photochromic article of claim 16 wherein the organic photochromic compound (b) is selected from the group consisting of naphthopyrans, benzopyrans, phenanthropyrans, indenonaphthopyrans, oxazines, organo-metal dithizonates, fulgides, fulgimides, spiro(indoline)pyrans and mixtures thereof.

19. The photochromic article of claim 18 wherein the total amount of photochromic compound present is from 0.05 to 1.0 milligram per square centimeter of organic host material surface to which the photochromic substance(s) is incorporated or applied.

20. The photochromic article of claim 19 wherein the article is an ophthalmic lens on a contact lens.

21. A photochromic article comprising, in combination, a polymeric organic host material selected from the group consisting of poly(methyl methacrylate), poly(ethylene glycol bismethacrylate), poly(ethoxylated bisphenol A dimethacrylate), thermoplastic polycarbonate, poly(vinyl acetate), polyvinylbutyral, polyurethane, polythiourethane and polymers of members of the group consisting of diethylene glycol bis(allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, ethoxylated phenol bismethacrylate monomers, diisopropenyl benzene monomers and ethoxylated trimethylol propane triacrylate monomers, and a photochromic amount of each of (a) at least one naphthopyran compound of claim 3, and (b) at least one other organic photochromic compound having at least one activated absorption maxima within the range of between about 400 and 700 nanometers.

DESCRIPTION OF THE INVENTION

The present invention relates to certain novel naphthopyran compounds. More particularly, this invention relates to novel indeno-fused photochromic naphthopyran compounds and to compositions and articles containing such novel naphthopyran compounds. When exposed to light radiation containing ultraviolet rays, such as the ultraviolet radiation in sunlight or the light of a mercury lamp, many photochromic compounds exhibit a reversible change in color. When the ultraviolet radiation is discontinued, such a photochromic compound will return to its original color or colorless state.

Various classes of photochromic compounds have been synthesized and suggested for use in applications in which a sunlight-induced reversible color change or darkening is desired. U.S. Pat. No. 3,567,605 (Becker) describes a series of pyran derivatives, including certain benzopyrans and naphthopyrans. These compounds are described as derivatives of chromene and are reported to undergo a color change, e.g., from colorless to yellow-orange, on irradiation by ultraviolet light at temperatures below about -30.degree. C. Irradiation of the compounds with visible light or upon raising the temperature to above about 0.degree. C. is reported to reverse the coloration to a colorless state.

U.S. Pat. No. 5,066,818 describes various 3,3-diaryl-3H-naphtho[2,1-b]pyrans as having desirable photochromic properties, i.e., high colorability and acceptable fade, for ophthalmic and other applications. Also disclosed by way of comparative example in the '818 patent are the isomeric 2,2-diaryl-2H-naphtho[1,2-b]pyrans, which are reported to require unacceptably long periods of time to fade after activation.

U.S. Pat. No. 3,627,690 describes photochromic 2,2-di-substituted-2H-naphtho[1,2-b]pyran compositions containing minor amounts of either a base or weak-to-moderate strength acid. The addition of either an acid or base to the naphthopyran composition is reported to increase the fade rate of the colored naphthopyrans, thereby making them useful in eye protection applications such as sunglasses. It is reported therein further that the fade rate of 2H-naphtho-[1,2-b]pyrans without the aforementioned additives ranges from several hours to many days to reach complete reversion.

Indenonaphthopyrans are known and have been disclosed in U.S. Pat. Nos. 5,645,767, 5,698,141, 5,723,072, 6,113,814 and 6,146,554 and International Patent Application Publication No. WO 99/15518. In each of these disclosures, the indeno group is in a reversed position as compared to the indenonaphthopyrans of the present invention. Japan Unexamined Patent Publication P2000-327675A discloses an indenonaphthopyran in which the indeno group is substituted with fluorenyl.

The present invention relates to a naphthopyran of 2H-naphtho[1,2-b]pyran structure characterized by having a substituted or unsubstituted indeno group fused at the 2,3 positions of the group to the 1 side of the naphthopyran. The compounds also have substituents at the 3 position of the pyran ring. These compounds have unexpectedly been found to demonstrate a bathochromic shift for the wavelength in the visible spectrum at which the maximum absorption of the activated (colored) form of the photochromic compound, i.e., the lambda max (Vis), occurs, thereby resulting in activated colors ranging from yellow/brown to blue/gray. Due to the bathochromic shift, compounds of the present invention demonstrate different colors than similar compounds without an unsubstituted or substituted indeno group fused at the 2,3 position of the group to the 1 side of the napthopyran. In addition, compounds of the present invention have demonstrated a high molar absorptivity (or molar extinction coefficient) in the UV, an acceptable fade rate without the addition of acids or bases, a high activated intensity, and a high coloration rate.

DETAILED DESCRIPTION OF THE INVENTION

In recent years, photochromic plastic materials, particularly plastic materials for optical applications, have been the subject of considerable attention. In particular, photochromic ophthalmic plastic lenses have been investigated because of the weight advantage they offer, vis-a-vis, glass lenses. Moreover, photochromic transparencies for vehicles, such as cars and airplanes, have been of interest because of the potential safety features that such transparencies offer.

Other than in the operating examples, or where otherwise indicated, all values, such as those expressing wavelengths, quantities of ingredients, ranges or reaction conditions, used in this description and the accompanying claims are understood as modified in all instances by the term "about" which means close to or near.

As used herein, the terms "halo" and "halogen" are defined to include chloro, fluoro, bromo and iodo and chlorine, fluorine, bromine and iodine, respectively. The term "aryl" is defined herein to include phenyl and naphthyl.

The disclosures of the patents and articles cited herein describing photochromic imbibition processes and compositions, procedures for making polymerizable and nonpolymerizable compounds of the present invention, complementary photochromic compounds, polymeric coatings and methods of applying such coatings, polymeric organic host materials and polymerizates are incorporated herein, in toto, by reference.

In accordance with the present invention, it has now been discovered that novel 2H-naphtho[1,2-b]pyran structures characterized by having a substituted or unsubstituted indeno group fused at the 2,3 positions of the group to the 1 side of the naphthopyran and demonstrating activated colors ranging from yellow/brown to blue/gray, an acceptable fade rate, high activated intensity and a high coloration rate may be prepared. These compounds may be described as indeno[3',2':3,4]naphtho[1,2-b]pyrans having substituents at the 3 position of the pyran ring. Substituents may also be present at the number 5, 6, 7, 8, 9, 10, 11, 12, or 13 carbon atoms of the compounds. The indeno group may be represented by the following graphic formula I' in which numbers 1 through 9 represent the ring atoms of the indeno group. ##STR2##

A typical 2H-naphtho[1,2-b]pyran structure is represented by the following graphic formula I", in which the letters a through n represent the sides and X represents potential substituents known in the art. ##STR3##

The compounds of the present invention may be represented by the following graphic formula I in which the letters a through u represent the sides of the indenonaphthopyran rings, and the numbers represent the numbers of the ring atoms of the indenonaphthopyran. ##STR4##

The indenonaphthopyran of the present invention is a naphthopyran compound of 2H-naphtho[1,2-b]pyran structure, such as represented by graphic formula I", characterized by having fused to the 1 side of the 2H-naphthopyran a group represented by graphic formula I' at the 2,3 positions of group I'. The group represented by graphic formula I' may be unsubstituted such as when R.sub.1 and R.sub.2 are each hydrogen and equals 0 or may be substituted with substituents known in the art for use on photochromic compounds. Different embodiments of the compounds of the present invention are contemplated based on photochromic activity.

In graphic formulae I', R.sub.1 and R.sub.2 may each be selected from the group consisting of:

(i) hydrogen, hydroxy, amino, mono- and di-substituted amino, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.3 -C.sub.7 cycloalkyl, allyl, benzyl, mono-substituted benzyl, halogen and the group, --C(O)W, wherein W is hydroxy, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, C.sub.3 -C.sub.7 cycloalkyloxy, phenyl, mono-substituted phenyl, phenoxy, amino, mono(C.sub.1 -C.sub.6)alkylamino, di(C.sub.1 -C.sub.6)alkylamino, morpholino, piperidino or pyrrolidyl, said amino substituents being selected from the group consisting of C.sub.1 -C.sub.6 alkyl, phenyl, benzyl and naphthyl, said benzyl and phenyl substituents being C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, piperidino, morpholino, di(C.sub.1 -C.sub.6)alkylamino or fluoro;

(ii) unsubstituted, mono- di- and tri-substituted members selected from the group consisting of phenyl, naphthyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl, benzofuranyl, thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, and indolyl, said group substituents being selected from the group consisting of halogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, morpholino, piperidino, pyrrolidino, amino, mono- and di-substituted amino, said amino substituents being selected from the group consisting of C.sub.1 -C.sub.6 alkyl, phenyl, benzyl and naphthyl;

(iii) monosubstituted phenyl, having a substituent at the para position that is a linking group, --(CH.sub.2).sub.t -- or --O--(CH.sub.2).sub.t --, wherein t is the integer 1, 2, 3, 4, 5 or 6, connected to an aryl group, which is a member of another photochromic naphthopyran;

(iv) a group, --OR.sub.5, wherein R.sub.5 is C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 acyl, phenyl(C.sub.1 -C.sub.3)alkyl, mono(C.sub.1 -C.sub.6)alkyl substituted phenyl(C.sub.1 -C.sub.3)alkyl, mono(C.sub.1 -C.sub.6)alkoxy substituted phenyl(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 C.sub.3 -C.sub.7 cycloalkyl, C.sub.1 -C.sub.6 haloalkyl, allyl, benzoyl, monosubstituted benzoyl, naphthoyl or monosubstituted naphthoyl, said benzoyl and naphthoyl group substituents being C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 alkoxy; or R.sub.5 is the group --CH(R.sub.6)Q, wherein R.sub.6 is hydrogen or C.sub.1 -C.sub.3 alkyl and Q is --CN, --CF.sub.3, or --COOR.sub.7, and R.sub.7 is hydrogen or C.sub.1 -C.sub.3 alkyl; or R.sub.5 is the group, --C(O)V, wherein V is hydrogen, C.sub.1 -C.sub.6 alkoxy, phenoxy, mono- or di-(C.sub.1 -C.sub.6)alkyl substituted phenoxy, mono- or di-(C.sub.1 -C.sub.6)alkoxy substituted phenoxy, an unsubstituted, mono- or di-substituted aryl group, amino, mono(C.sub.1 -C.sub.6)alkylamino, di(C.sub.1 -C.sub.6)alkylamino, phenylamino, mono- or di-(C.sub.1 -C.sub.6)alkyl substituted phenylamino, or mono- or di-(C.sub.1 -C.sub.6)alkoxy substituted phenylamino, said aryl group substituents being C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 alkoxy;

(v) a group, --CH(Q').sub.2, wherein Q' is --CN or --COOR.sub.8, wherein R.sub.8 is hydrogen, C.sub.1 -C.sub.6 alkyl, phenyl(C.sub.1 -C.sub.3)alkyl, mono(C.sub.1 -C.sub.6)alkyl substituted phenyl(C.sub.1 -C.sub.3)alkyl, mono(C.sub.1 -C.sub.6)alkoxy substituted phenyl(C.sub.1 -C.sub.3)alkyl, or an unsubstituted, mono- or di-substituted aryl group, each of said aryl group substituents being C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 alkoxy;

(vi) a group, --CH(R.sub.9)G, wherein R.sub.9 is hydrogen, C.sub.1 -C.sub.6 alkyl or an unsubstituted, mono- or di-substituted aryl group, and G is hydroxy, C.sub.1 -C.sub.6 alkoxy, aryloxy, amino, mono(C.sub.1 -C.sub.6)alkylamino, di(C.sub.1 -C.sub.6)alkylamino, phenylamino, mono- or di-(C.sub.1 -C.sub.6)alkyl substituted phenylamino, or mono- or di-(C.sub.1 -C.sub.6)alkoxy substituted phenylamino, --COOR.sub.8, --COR.sub.10 or --CH.sub.2 OR.sub.11, wherein R.sub.10 is hydrogen, C.sub.1 -C.sub.6 alkyl, an unsubstituted, mono- or di-substituted aryl group, amino, mono(C.sub.1 -C.sub.6)alkylamino, di(C.sub.1 -C.sub.6)alkylamino, phenylamino, mono- or di-(C.sub.1 -C.sub.6)alkyl substituted phenylamino, mono- or di-(C.sub.1 -C.sub.6)alkoxy substituted phenylamino, diphenylamino, mono- or di(C.sub.1 -C.sub.6)alkyl substituted diphenylamino, mono- or di(C.sub.1 -C.sub.6)alkoxy substituted diphenylamino, morpholino, or piperidino, wherein R.sub.11 is hydrogen, --C(O)R.sub.8, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.3 alkoxy(C.sub.1 -C.sub.6)alkyl, phenyl(C.sub.1 -C.sub.3)alkyl, mono(C.sub.1 -C.sub.6)alkoxy substituted phenyl(C.sub.1 -C.sub.3)alkyl, or an unsubstituted, mono- or di-substituted aryl group, each of said aryl group substituents being C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 alkoxy; and

(vii) a group, T, represented by the formula:

--Z[(OC.sub.2 H.sub.4).sub.x (OC.sub.3 H.sub.6).sub.y (OC.sub.4 H.sub.8).sub.z ]Z'

or

--[(OC.sub.2 H.sub.4).sub.x (OC.sub.3 H.sub.6).sub.y (OC.sub.4 H.sub.8).sub.z ]Z'

wherein --Z is --C(O)-- or --CH.sub.2 --, Z' is C.sub.1 -C.sub.3 alkoxy or a polymerizable group i.e., any functional group capable of participating in a polymerization reaction. Polymer forming methods in which the polymerizable compounds of the present invention may participate include radical polymerization, and such other polymerization processes as are described in Ullmann's Encyclopedia of Industrial Chemistry, "Polymerization Processes", Vol. 21A, pp 305 to 428. The polymerizable groups may be selected from the group consisting of hydroxy, (meth)acryloxy, vinyl, isocyanate and epoxy, e.g., oxiranylmethyl. When there are 2 or more polymerizable groups on the naphthopyran, they may be the same or different, x, y and z are each a number between 0 and 50, and the sum of x, y and z is between 2 and 50; or

(viii) R.sub.1 and R.sub.2 may together form a substituted or unsubstituted spiro-carbocyclic ring containing 3 to 6 carbon atoms or a substituted or unsubstituted spiro-heterocyclic group containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms including the spirocarbon atom, said spiro-carbocyclic ring and spiro-heterocyclic group being annellated with 0, 1 or 2 benzene rings, said substituents being hydrogen or C.sub.1 -C.sub.6 alkyl, provided that said spiro-carbocyclic ring is not fluoren-9-ylidene.

In one contemplated embodiment, R.sub.1 and R.sub.2 are each selected from the group consisting of:

(i) hydrogen, hydroxy, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, di-substituted amino, C.sub.3 -C.sub.7 cycloalkyl, benzyl, mono-substituted benzyl and the group, --C(O)W, wherein W is C.sub.1 -C.sub.6 alkoxy, di(C.sub.1 -C.sub.6)alkylamino, morpholino or piperidino, said amino substituents being C.sub.1 -C.sub.6 alkyl, said benzyl substituents being C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 alkoxy;

(ii) mono- and di and tri-substituted members selected from the group consisting of phenyl, naphthyl and dibenzofuranyl, said group substituents being selected from the group consisting of C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, and di-substituted amino, said amino substituents being C.sub.1 -C.sub.6 alkyl;

(iii) monosubstituted phenyl, having a substituent at the para position that is a linking group, --O--(CH.sub.2).sub.t --, wherein t is the integer 3, 4 or 5 connected to an aryl group, which is a member of another photochromic naphthopyran;

(iv) a group, --OR.sub.5, wherein R.sub.5 is C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 acyl, C.sub.1 -C.sub.6 alkoxy (C.sub.2 -C.sub.4) alkyl, benzoyl or monosubstituted benzoyl, said benzoyl substituents being C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 alkoxy; or R.sub.5 is the group --CH(R.sub.6)Q, wherein R.sub.6 is hydrogen and Q is --COOR.sub.7, and R.sub.7 is C.sub.1 -C.sub.3 alkyl; or R.sub.5 is the group, --C(O)V, wherein V is C.sub.1 -C.sub.6 alkoxy or di(C.sub.1 -C.sub.6)alkyl amino;

(v) a group, --CH(Q').sub.2, wherein Q' is --COOR.sub.8, wherein R.sub.8 is C.sub.1 -C.sub.6 alkyl, or phenyl(C.sub.1 -C.sub.3)alkyl;

(vi) a group, --CH(R.sub.9)G, wherein R.sub.9 is C.sub.1 -C.sub.6 alkyl, and G is C.sub.1 -C.sub.6 alkoxy, --COOR.sub.8 --COR.sub.10, or --CH.sub.2 OR.sub.11, wherein R.sub.10 is C.sub.1 -C.sub.6 alkyl, di(C.sub.1 -C.sub.6)alkylamino, morpholino or piperidino; wherein R.sub.11 is C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.3 alkoxy(C.sub.1 -C.sub.6) alkyl, and

(vii) a group, T, represented by the formula:

[(OC.sub.2 H.sub.4).sub.x (OC.sub.3 H.sub.6).sub.y (OC.sub.4 H.sub.8).sub.z ]Z'

wherein Z' is C.sub.1 -C.sub.3 alkoxy or a polymerizable group, x, y and z are each a number between 0 and 50, and the sum of x, y and z is between 2 and 50; or

(viii) R.sub.1 and R.sub.2 may together form an oxo group or a substituted or unsubstituted spiro-heterocyclic group containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms including the spirocarbon atom, said spiro-heterocyclic ring being annellated with 1 or 2 benzene rings, said substituent being C.sub.1 -C.sub.6 alkyl.

In another contemplated embodiment, R.sub.1 and R.sub.2 are each selected from the group consisting of:

(i) hydrogen, hydroxy, C.sub.1 -C.sub.3 alkyl and the group, --C(O)W, wherein W is C.sub.1 -C.sub.6 alkoxy,;

(ii) unsubstituted, and mono-substituted phenyl, said phenyl substituents being selected from the group consisting of C.sub.1 -C.sub.6 alkoxy, and di-substituted amino, said amino substituents being C.sub.1 -C.sub.3 alkyl;

(iii) monosubstituted phenyl, having a substituent at the para position that is a linking group, --O--(CH.sub.2).sub.t --, wherein t is the integer 3, connected to an aryl group, which is a member of another photochromic naphthopyran;

(iv) a group, --OR.sub.5, wherein R.sub.5 is C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy(C.sub.2 -C.sub.4)alkyl, the group --CH(R.sub.6)Q, wherein R.sub.6 is hydrogen or C.sub.1 -C.sub.3 alkyl and Q is --COOR.sub.7, and R.sub.7 is C.sub.1 -C.sub.3 alkyl or R.sub.5 is the group, --C(O)V, wherein V is C.sub.1 -C.sub.6 alkoxy;

(v) a group, --CH(Q').sub.2, wherein Q' is --COOR.sub.8, wherein R.sub.8 is C.sub.1 -C.sub.6 alkyl;

(vi) a group, --CH(R.sub.9)G, wherein R.sub.9 is C.sub.1 -C.sub.6 alkyl, and G is C.sub.1 -C.sub.6 alkoxy, --COOR.sub.8, --COR.sub.10 or --CH.sub.2 OR.sub.11 wherein R.sub.10 and R.sub.11 are each C.sub.1 -C.sub.6 alkyl; and

(vii) a group, T, represented by the formula:

--[(OC.sub.2 H.sub.4).sub.x (OC.sub.3 H.sub.6).sub.y (OC.sub.4 H.sub.8).sub.z ]Z'

wherein Z' is C.sub.1 -C.sub.3 alkoxy or a polymerizable group, x, y and z are each a number between 0 and 50, and the sum of x, y and z is between 2 and 50; or

(viii) R.sub.1 and R.sub.2 may together form a substituted or unsubstituted spiro-heterocyclic group containing 1 oxygen atom and 6 carbon atoms including the spirocarbon atom, said spiro-heterocyclic ring being annellated with 2 benzene rings, said substituents being C.sub.1 -C.sub.3 alkyl.

R.sub.3 may be selected from the group of substituents known in the art for use on photochromic compounds. Each R.sub.3 in graphic formula I may independently be selected from the group consisting of hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, C.sub.3 -C.sub.7 cycloalkyl, phenyl, benzyl, di(C.sub.1 -C.sub.6)alkylamino, dicyclohexylamino, diphenylamino, piperidyl, morpholinyl, pyridyl, halogen, a group, T, and the group --C(O)W and n is the integer 0, 1, or 2; or when n is at least 2, and the R.sub.3 substituents are adjacent, the pair of substituents forms a substituted or unsubstituted fused carbocyclic or heterocyclic ring selected from the group consisting of benzo, pyridino, pyrazino, pyrimidino, furano, dihydrofurano, 1,3-dioxolo, 1,4-dioxolo, 1,3-dioxino, 1,4-dioxino, thiopheno, benzofuro, benzothieno, indolo, and indeno, the substituents of said fused carbocyclic or heterocyclic ring being selected from the group consisting of halogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, amino, mono- and di-substituted amino, said amino substituents being selected from the group consisting of C.sub.1 -C.sub.6 alkyl, phenyl, benzyl and naphthyl; said first R.sub.3 ring being fused to the o, p or q side and said second R.sub.3 ring being fused to the g, h, or i side of the naphthopyran.

In one contemplated embodiment, each R.sub.3 is selected from the group consisting of hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, di(C.sub.1 -C.sub.6)alkylamino, piperidyl, morpholinyl, pyrrolidyl, halogen, a group, T, or the group, --C(O)W and n is the integer 0, 1, or 2; or when n is 2, and the R.sub.3 substituents are adjacent, a pair of substituents forms a substituted or unsubstituted fused carbocyclic or heterocyclic ring selected from the group consisting of benzo, dihydrofurano and benzofuro, the substituents of said fused carbocyclic or heterocyclic ring being selected from the group consisting of C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, and di-substituted amino, said amino substituents being C.sub.1 -C.sub.6 alkyl; said R.sub.3 ring being fused to the o, p or q sides of the naphthopyran.

In another contemplated embodiment, each R.sub.3 is selected from the group consisting of hydrogen C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, morpholinyl, a group, T, and the group --C(O)W, and when m is 2 and the R.sub.3 substituents are adjacent, the pair of substituents forms a substituted or unsubstituted fused carbocyclic or heterocyclic ring selected from the group consisting of benzo and benzofuro, the substituents of said fused carbocyclic or heterocyclic ring being C.sub.1 -C.sub.6 alkoxy; said R.sub.3 ring being fused to the p side of the naphthopyran.

In graphic formula I, R.sub.1, R.sub.2 and each R.sub.3 are the same as described hereinbefore for graphic formula I'. In the definitions of R.sub.1, R.sub.2, R.sub.3, B and B', like substituents have like meanings.

B and B' in graphic formula I may each be selected from the group of substituents known in the art for use on photochromic compounds. Specifically, B and B' may each be selected from the group consisting of:

(i) mono-T-substituted phenyl

(ii) an unsubstituted, mono-, di-, and tri-substituted aryl group;

(iii) 9-julolidinyl and an unsubstituted, mono- or di-substituted heteroaromatic group selected from the group consisting of pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazoyl, benzopyridyl, indolinyl and fluorenyl, each of said aryl and heteroaromatic substituents in (ii) and (iii) being selected from the group consisting of hydroxy, aryl, i.e., phenyl and naphthyl, mono(C.sub.1 -C.sub.6)alkoxyaryl, di(C.sub.1 -C.sub.6)alkoxyaryl, mono(C.sub.1 -C.sub.6)alkylaryl, di(C.sub.1 -C.sub.6)alkylaryl, haloaryl, C.sub.3 -C.sub.7 cycloalkylaryl, C.sub.3 -C.sub.7 cycloalkyl, C.sub.3 -C.sub.7 cycloalkyloxy, C.sub.3 -C.sub.7 cycloalkyloxy(C.sub.1 -C.sub.6)alkyl, C.sub.3 -C.sub.7 cycloalkyloxy(C.sub.1 -C.sub.6)alkoxy, aryl(C.sub.1 -C.sub.6)alkyl, aryl(C.sub.1 -C.sub.6)alkoxy, aryloxy, aryloxy(C.sub.1 -C.sub.6)alkyl, aryloxy(C.sub.1 -C.sub.6)alkoxy, mono- and di-(C.sub.1 -C.sub.6)alkylaryl(C.sub.1 -C.sub.6)alkyl, mono- and di-(C.sub.1 -C.sub.6)alkoxyaryl(C.sub.1 -C.sub.6)alkyl, mono- and di-(C.sub.1 -C.sub.6)alkylaryl(C.sub.1 -C.sub.6)alkoxy, mono- and di-(C.sub.1 -C.sub.6)alkoxyaryl(C.sub.1 -C.sub.6)alkoxy, amino, mono(C.sub.1 -C.sub.6)alkylamino, di(C.sub.1 -C.sub.6)alkylamino, diarylamino, aryl(C.sub.1 -C.sub.6 alkyl)amino, piperazino, N-(C.sub.1 -C.sub.6)alkylpiperazino, N-arylpiperazino, aziridino, indolino, piperidino, morpholino, thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino, pyrryl, pyrrolidyl, 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;

(iv) an unsubstituted or mono-substituted member selected from the group consisting of pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolinyl, phenothiazinyl, phenoxazinyl, phenazinyl and acridinyl, each of said substituents being selected from the group consisting of C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, phenyl, and halogen;

(v) monosubstituted phenyl, having a substituent at the para position that is a linking group, --(CH.sub.2).sub.t -- or --O--(CH.sub.2).sub.t --, wherein t is the integer 1, 2, 3, 4, 5 or 6, connected to an aryl group, which is a member of another photochromic naphthopyran;

(vi) a group represented by one of the following graphic formula IIA or IIB: ##STR5##

wherein A is methylene or oxygen and D is oxygen or substituted nitrogen, provided that when D is substituted nitrogen, A is methylene, said nitrogen substituents 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.12 is C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, hydroxy, or halogen; R.sub.13 and R.sub.14 are each hydrogen or C.sub.1 -C.sub.6 alkyl; and q is the integer 0, 1, or 2;

(vii) 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, halo(C.sub.3 -C.sub.6)cycloalkyl, and C.sub.4 -C.sub.12 bicycloalkyl; and

(viii) a group represented by the following graphic formula IIC: ##STR6##

wherein L is hydrogen or C.sub.1 -C.sub.4 alkyl and M is selected from the unsubstituted, mono-, and di-substituted members of the group consisting of naphthyl, phenyl, furanyl, and thienyl, each of said group substituents being C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, or halogen.

Alternatively, B and B' may together form fluoren-9-ylidene, mono-, or di-substituted fluoren-9-ylidene or form a member selected from the group consisting of saturated C.sub.3 -C.sub.12 spiro-monocyclic hydrocarbon rings, e.g., cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene, cyclononylidene, cyclodecylidene cycloundecylidene, cyclododecylidene; saturated C.sub.7 -C.sub.12 spiro-bicyclic hydrocarbon rings, e.g., bicyclo[2.2.1]heptylidene, i.e., norbornylidene, 1,7,7-trimethyl bicyclo[2.2.1]heptylidene, i.e., bornylidene, bicyclo[3.2.1]octylidene, bicyclo[3.3.1]nonan-9-ylidene, bicyclo[4.3.2]undecane, and saturated C.sub.7 -C.sub.12 spiro-tricyclic hydrocarbon rings, e.g., tricyclo[2.2.1.0.sup.2,6 ]heptylidene, tricyclo[3.3.1.1.sup.3,7 ]decylidene, i.e., adamantylidene, and tricyclo[5.3.1.1.sup.2,6 ]dodecylidene, each of 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, and halogen.

In one contemplated embodiment, B and B' are each selected from the group consisting of: (i) phenyl, mono-substituted phenyl, and di-substituted phenyl, preferably substituted in the meta and/or para positions; (ii) the unsubstituted, mono- and di-substituted aromatic heterocyclic groups furanyl, benzofuran-2-yl, thienyl, benzothien-2-yl and dibenzofuranyl, each of said phenyl and aromatic heterocyclic substituents being selected from the group consisting of hydroxy, amino, mono(C.sub.1 -C.sub.3)alkylamino, di(C.sub.1 -C.sub.3)alkylamino, piperidino, morpholino, pyrryl, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 chloroalkyl, C.sub.1 -C.sub.3 fluoroalkyl, C.sub.1 -C.sub.3 alkoxy, mono(C.sub.1 -C.sub.3)alkoxy(C.sub.1 -C.sub.3)alkyl, fluoro and chloro; (iii) the groups represented by the graphic formulae IIA and IIB, wherein A is methylene and D is oxygen, R.sub.12 is C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 alkoxy, R.sub.13 and R.sub.14 are each hydrogen or C.sub.1 -C.sub.4 alkyl; and q is the integer 0 or 1; (iv) C.sub.1 -C.sub.4 alkyl; and (v) the group represented by the graphic formula IIC wherein L is hydrogen or methyl and M is phenyl or mono-substituted phenyl, said phenyl substituent being selected from the group consisting of C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 alkoxy, and fluoro; or (vi) B and B' taken together form fluoren-9-ylidene, mono-substituted fluoren-9-ylidene or a member selected from the group consisting of saturated C.sub.3 -C.sub.8 spiro-monocyclic hydrocarbon rings, saturated C.sub.7 -C.sub.10 spiro-bicyclic hydrocarbon rings, and saturated C.sub.7 -C.sub.10 spiro-tricyclic hydrocarbon rings, said fluoren-9-ylidene substituent being selected from the group consisting of C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 alkoxy, fluoro and chloro.

In another contemplated embodiment, B and B' are each selected from the group consisting of (i) phenyl, mono- and di-substituted phenyl, (ii) the unsubstituted, mono- and di-substituted aromatic heterocyclic groups furanyl, benzofuran-2-yl, thienyl, benzothien-2-yl and dibenzofuranyl, each of said phenyl and aromatic heterocyclic substituents being selected from the group consisting of hydroxy, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 alkoxy, piperidino and morpholino; and (iii) the group represented by graphic formula IIA, wherein A is methylene and D is oxygen, R.sub.12 is C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 alkoxy, R.sub.13 and R.sub.14 are each hydrogen or C.sub.1 -C.sub.3 alkyl, and q is the integer 0 or 1; or (iv) B and B' taken together form fluoren-9-ylidene, adamantylidene, bornylidene, norbornylidene, or bicyclo[3.3.1]nonan-9-ylidene.

Compounds represented by graphic formula I having certain of the substituents R.sub.1 -R.sub.3, B and B' described hereinbefore, may be prepared by the following Reactions A through G. Methods for the preparation of compounds wherein R.sub.1, R.sub.2, B and/or B' is the polyalkoxylated group T are described in U.S. Pat. No. 5,961,892. Methods for the preparation of compounds wherein R.sub.1, R.sub.2, B and/or B' is the polymerizable polyalkoxylated group T are described in U.S. Pat. No. 6,113,814.

With reference to the following reactions, compounds represented by graphic formula V or VA are either purchased or prepared by Friedel-Crafts methods shown in Reaction A using an appropriately substituted or unsubstituted benzoyl chloride of graphic formula IV with a commercially available substituted or unsubstituted benzene compound of graphic formula III. See the publication Friedel-Crafts and Related Reactions, George A. Olah, Interscience Publishers, 1964, Vol. 3, Chapter XXXI (Aromatic Ketone Synthesis), and "Regioselective Friedel-Crafts Acylation of 1,2,3,4-Tetrahydroquinoline and Related Nitrogen Heterocycles: Effect on NH Protective Groups and Ring Size" by Ishihara, Yugi et al, J. Chem. Soc., Perkin Trans. 1, pages 3401 to 3406, 1992.

In Reaction A, the compounds represented by graphic formulae III and IV are dissolved in a solvent, such as carbon disulfide or methylene chloride, and reacted in the presence of a Lewis acid, such as aluminum chloride or tin tetrachloride, to form the corresponding substituted benzophenone represented by graphic formula V (VA in Reaction B). R and R' represent possible substituents, as described hereinbefore with respect to B and B' of graphic formula I. ##STR7##

In Reaction B, the substituted or unsubstituted ketone represented by graphic formula VA, in which B and B' may represent groups other than substituted or unsubstituted phenyl, as shown in graphic formula V, is reacted with sodium acetylide in a suitable solvent, such as anhydrous tetrahydrofuran (THF), to form the corresponding propargyl alcohol represented by graphic formula VI. Propargyl alcohols having B or B' groups other than substituted and unsubstituted phenyl may be prepared from commercially available ketones or ketones prepared via reaction of an acyl halide with a substituted or unsubstituted benzene, naphthalene or heteroaromatic compound, e.g., 9-julolidinyl. Propargyl alcohols having a B or B' group represented by graphic formula IIC may be prepared by the methods described in U.S. Pat. No. 5,274,132, column 2, lines 40 to 68. ##STR8##

In Reaction C, a substituted or unsubstituted .alpha.-methoxy naphthalene represented by graphic formula VII is reacted with a benzoyl chloride (IV) in the presence of anhydrous aluminum chloride to form a naphthophenone represented by graphic formula VIII. Compound VIII is reacted with an organometallic compound containing R.sub.1 to give a carbinol compound represented by graphic formula IX. Compound IX is heated with phosphoric acid to produce the ketone represented by graphic formula X. Compound X is aromatized by reaction with a base such as KOH in a water/ethanol mixture to produce the indeno-fused naphthol of graphic formula XI. ##STR9##

In Reaction D, an ortho bromo acetophenone represented by graphic formula XII is reacted with ethyl, .alpha.-benzoylacetate represented by graphic formula XIII in the presence of sodium hydride and cuprous bromide to form a naphthol represented by graphic formula XIV. Naphthol XIV is then hydrolyzed with aqueous base followed by cyclization in strong acid such as phosphoric acid to produce the indeno-fused naphthol represented by graphic formula XV. ##STR10##

In Reaction E, the naphthol represented by graphic formula XI is coupled with a propragyl alcohol (VI) in the presence of a catalytic amount of a acid such as p-dodecylbenzene sulfonic acid to form an indenonaphthopyran represented by graphic formula IA. Compound IA is reacted with a strong base such as butyl lithium or KOH and followed by reaction with alkyl halide to produce the indenonaphthopyran represented by graphic formula IB. ##STR11##

In Reaction F, the naphthol represented by graphic formula XV is coupled with propargyl alcohol to give the indenonaphthopyran represented by graphic formula XVI. Compound XVI is reacted with an organo metallic compound to produce the indenonaphthopyran of graphic formula IC. The hydroxy group on compound IC is alkylated with alcohol to form an ether substituent on the indenonaphthopyran of graphic formula ID. ##STR12##

In Reaction G, the ortho bromoacetophenone represented by graphic formula XII is reacted with diethyl malonate represented by graphic formula XVII in the presence of sodium hydride and cuprous bromide to form a dihydroxy naphthalene represented by graphic formula XVIII. Compound XVIII is coupled with a propargyl alcohol (VI) to produce the naphthopyran represented by graphic formula IXX. Compound IXX is methylated with methyl iodide in the presence of potassium carbonate to form the naphthopyran represented by graphic formula XX. The reaction of the aryl Grignard reagent represented by graphic formula XXI with compound XX produces the naphthopyran represented by graphic formula XXII. Compound XXII is reacted with alkyl lithium to produce a carbinol derivative represented by graphic formula XXIII. Cyclization of Compound XXIII with acid forms the desired indenonaphthopyran represented by graphic formula IE. ##STR13##

Compounds represented by graphic formula I may be used in those applications in which organic photochromic substances may be employed, such as optical lenses, e.g., vision correcting ophthalmic lenses, contact lenses and plano lenses, face shields, goggles, visors, camera lenses, windows, automotive windshields, aircraft and automotive transparencies, e.g., T-roofs, sidelights and backlights, plastic films and sheets, textiles and coatings, e.g., coating compositions As used herein, coating compositions are defined herein to include polymeric coating compositions prepared from materials such as polyurethanes, epoxy resins and other resins used to produce synthetic polymers; paints, i.e., a pigmented liquid or paste used for the decoration, protection and/or the identification of a substrate; and inks, i.e., a pigmented liquid or paste used for writing and printing on substrates. Potential substrates for coating compositions containing the compounds of the present invention include paper, glass, ceramics, wood, masonry, textiles, metals and polymeric organic materials.

Coating compositions may be used to produce coatings on optical elements, verification marks on security documents, e.g., documents such as banknotes, passport and drivers' licenses, for which authentication or verification of authenticity may be desired. The indenonaphthopyrans represented by graphic formula I exhibit color changes from colorless to colors ranging from yellow/brown to blue/gray.

Examples of indenonaphthopyran compounds within the scope of the invention are the following:

(a) 3,3,9-triphenyl-3H-9H-indeno[3',2':3,4]naphtho[1,2-b]pyran;

(b) 3,3-di(4-methoxyphenyl)-9-phenyl-3H-9H-indeno[3',2': 3,4]naphtho[1,2-b]pyran;

(c) 3-(4-methoxyphenyl)-3,9-diphenyl-3H-9H-indeno[3',2': 3,4]naphtho[1,2-b]pyran;

(d) 3-(4-morpholinophenyl)-3,9-diphenyl-3H-9H-indeno[3',2': 3,4]naphtho[1,2-b]pyran;

(e) 3,3-di(4-methoxyphenyl)-9-(3-methoxyphenyl)-11-methoxy-3H-9H-indeno[3',2': 3,4]naphtho[1,2-b]pyran;

(f) 3-(4-methoxyphenyl)-3-phenyl-9-(3-methoxyphenyl)-11-methoxy-3H-9H-indeno[3 ',2':3,4]naphtho[1,2-b]pyran;

(g) 3-(4-methoxyphenyl)-3-phenyl-9-methyl-11-methoxy-9-(3-methoxyphenyl)-3H-9H -indeno[3',2':3,4]naphtho[1,2-b]pyran;

(h) 3,3-di(4-methoxyphenyl)-9-methyl-11-methoxy-9-(3-methoxyphenyl)-3H-9H-inde no[3',2':3,4]naphtho[1,2-b]pyran;

(i) 3,3-di(4-methoxyphenyl)-9-methyl-11-methoxy-3H-9H-indeno[3',2': 3,4]naphtho[1,2-b]pyran;

(j) 3,3-di(4-methoxyphenyl)-9,9-dimethyl-11-methoxy-3H-9H-indeno[3',2': 3,4]naphtho[1,2-b]pyran;

(k) 3-(4-methoxyphenyl)-3-phenyl-9,9-dimethyl-11-methoxy-3H-9H-indeno[3',2': 3,4]naphtho[1,2-b]pyran;

(l) 3,3-di(4-methoxyphenyl)-9,9-dimethyl-7,11-dimethoxy-3H-9H-indeno[3',2': 3,4]naphtho[1,2-b]pyran;

(m) 3-(4-methoxyphenyl)-3-phenyl-9,9-dimethyl-7,11-dimethoxy-3H-9H-indeno[3',2 ':3,4]naptho[1,2-b]pyran;

(n) 3-(4-morpholinophenyl)-3-phenyl-9,9-dimethyl-7,11-dimethoxy-3H-9H-indeno[3 ',2':3,4]naphtho[1,2-b]pyran;

(o) 3,3-di(4-methoxyphenyl)-9-methyl-11,13-dimethoxy-3H-9H-indeno[3',2': 3,4]naphtho[1,2-b]pyran;

(p) 3-(4-methoxyphenyl)-3-phenyl-9-methyl-11,13-dimethoxy-3H-9H-indeno[3',2': 3,4]naphtho[1,2-b]pyran;

(q) 3-(4-methoxyphenyl)-3-phenyl-9,9-dimethyl-3H-9H-benzo[4",5"]indeno[3',2': 3,4]naphtho[1,2-b]pyran; and

(r) 3,3-di(4-methoxyphenyl-9,9-dimethyl-11-fluoro-3H-9H-indeno[3',2': 3,4]naphtho[1,2-b]pyran.

It is contemplated that the photochromic indenonaphthopyrans of the present invention may each be used alone or in combination with other indenonaphthopyrans of the present invention. Alternatively, the photochromic indenonaphthopyrans of the present invention may be