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US 5,405,958 AGranted
Photochromic spiro(indoline)naphthoxazine compounds
AssigneeTransitions Optical, Inc.
InventorBarry VanGemert
Life of this patent
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Abstract
Described are novel reversible photochromic spiro(indoline) naphthoxazine compounds of improved photocolorability that may be graphically represented by the formula, ##STR1## In preferred embodiments, R.sub.1 is allyl, alkoxyalkyl, and alkyl; each R.sub.2 is alkyl or alkoxy; R.sub.3 and R.sub.4 are alkyl; R.sub.5 is alkoxycarbonyl; and R.sub.6 is hydroxy, alkoxy, or carboxy, e.g., acetoxy. 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 naphthoxazine compounds or combination thereof with complementary photochromic compounds, e.g., naphthopyran or benzopyran compounds, are also described.
Claims19
A naphthoxazine compound represented by the following graphic formula:
- ##STR4## wherein:
- (a) R.sub.1 is C.sub.1 -C.sub.8 alkyl, phen(C.sub.1 -C.sub.4)alkyl, naphth (C.sub.1 -C.sub.4)alkyl, allyl, acrylyloxy(C.sub.2 -C.sub.6 )alkyl, methacrylyloxy(C.sub.2 -C.sub.6 )alkyl, C.sub.1 -C.sub.4 acyloxy(C.sub.2 -C.sub.6 )alkyl, carboxy(C.sub.2 -C.sub.6 )alkyl, cyano(C.sub.2 -C.sub.6 )alkyl, hydroxy(C.sub.2 -C.sub.6 )alkyl, C.sub.1 -C.sub.6 alkoxy(C.sub.2 -C.sub.4)alkyl or (C.sub.2 H.sub.4 O).sub.m.CH.sub.3, wherein m is an integer from 1 to 6;
- (b) each R.sub.2 is C.sub.1 -C.sub.5 alkyl, C.sub.1 -C.sub.5 alkoxy, nitro, cyano, C.sub.1 -C.sub.8 alkoxycarbonyl, C.sub.1 -C.sub.4 acyloxy, halo, C.sub.1 -C.sub.4 monohaloalkyl or C.sub.1 -C.sub.4 polyhaloalkyl;
- (c) R.sub.3 and R.sub.4 are each C.sub.1 -C.sub.5 alkyl, benzyl, phenyl, mono- or di-substituted phenyl, said phenyl substituents being C.sub.1 -C.sub.5 alkyl or C.sub.1 -C.sub.5 alkoxy, or R.sub.3 and R.sub.4 taken together form a group selected from a cyclic ring of from 5 to 8 carbon atoms which includes the spiro carbon atom, norbornyl or adamantyl;
- (d) R.sub.5 is the group --C(O)X, X being --OR.sub.7 or --N(R.sub.8)R.sub.9, wherein R.sub.7 is allyl, C.sub.1 -C.sub.6 alkyl, benzyl, C.sub.1 -C.sub.6 alkyl substituted benzyl, C.sub.1 -C.sub.6 alkoxy substituted benzyl, C.sub.1 -C.sub.6 alkoxy(C.sub.2 -C.sub.4)alkyl, or C.sub.1 -C.sub.6 haloalkyl, and wherein R.sub.8 and R.sub.9 are each selected from hydrogen, C.sub.1 -C.sub.5 alkyl, C.sub.5 -C.sub.7 cycloalkyl, phenyl and substituted phenyl, or R.sub.8 and R.sub.9 together with the nitrogen form a substituted or unsubstituted saturated heterocyclic ring containing from 5 to 6 ring atoms, which ring includes as the hetero atom said nitrogen atom alone or one additional hetero atom of nitrogen or oxygen, said phenyl and heterocyclic ring substituents being selected from C.sub.1 -C.sub.5 alkyl and C.sub.1 -C.sub.6 alkoxy;
- (e) R.sub.6 is the group, --O--Y, wherein Y is hydrogen, C.sub.1 -C.sub.6 alkyl, benzyl, C.sub.1 -C.sub.6 alkyl substituted benzyl, C.sub.1 -C.sub.6 alkoxy substituted benzyl, C.sub.1 -C.sub.6 alkoxy (C.sub.2 -C.sub.4) alkyl, C.sub.1 -C.sub.6 haloalkyl, allyl or the group, --C(O)Z, wherein Z is C.sub.1 -C.sub.6 alkyl, phenyl, C.sub.1 -C.sub.6 alkyl substituted phenyl, C.sub.1 -C.sub.6 alkoxy substituted phenyl, C.sub.1 -C.sub.6 alkoxy, phenoxy, C.sub.1 -C.sub.6 alkyl substituted phenoxy, C.sub.1 -C.sub.6 alkoxy substituted phenoxy, C.sub.1 -C.sub.6 alkylamino, phenylamino, C.sub.1 -C.sub.6 alkyl substituted phenylamino, or C.sub.1 -C.sub.6 alkoxy substituted phenylamino;
- and
- (f) n is the integer 0, 1, or 2, said halo substituents being chloro, fluoro, iodo or bromo.
5 more elements
A naphthoxazine compound wherein the compound is
- (a) 1,3,3,4,5(or 1,3,3,5,6,)-pentamethyl-9'-methoxy-carbonyl-8'-hydroxy-spiro[indoline-2,3' -[3H]naphth[2,1-b][1,4]oxazine];
- (b) 1-propyl-3,3,4,5(or 3,3,5,6)-tetramethyl-9'-methoxy-carbonyl-8'-hydroxy-spiro[indoline-2,3'-[3 H]naphth[2,1-b][1,4]oxazine];
- (c) 1,3,3,4,5(or 1,3,3,5,6,)-pentamethyl-9'-methoxy-carbonyl-8'-methoxy-spiro[indoline-2,3' -[3H]naphth[2,1-b][1,4]oxazine];
- (d) 1-propyl-3,3,4,5(or 3,3,5,6)-tetramethyl-9'-methoxy-carbonyl-8'-methoxy-spiro[indoline-2,3'-[3 H]naphth[2,1-b][1,4]oxazine];
- (e) 1,3,3,4,5(or 1,3,3,5,6,)-pentamethyl-9'-methoxy-carbonyl-8'-acetoxy-spiro[indoline-2,3' -[3H]naphth[2,1-b][1,4]oxazine];
- (f) 1-propyl-3-ethyl-3-methyl-9'-methoxy-carbonyl-8'-acetoxy-spiro[indoline-2, 3'-[3H]naphth[2,1-b][1,4]oxazine];
- (g) 1-propyl-3,3-dimethyl-5-methoxy-9'-methoxy-carbonyl-8'-acetoxy-spiro[indol ine-2,3'-[3H]naphth[2,1-b][1,4]oxazine];
- (h) 1-propyl-3,3,4,5(or 3,3,5,6)-tetramethyl-9'-methoxy-carbonyl-8'-acetoxy-spiro[indoline-2,3'-[3 H]naphth[2,1-b][1,4]oxazine];
- (i) 1-methoxyethyl-3,3-dimethyl-9'-allyloxy-carbonyl-8'-benzoyloxy-spiro[indol ine-2,3,-[3H]naphth[2,1-b][1,4]oxazine];
- or
- (j) 1-allyl-3,3-spirocyclohexyl-9'-benzyloxycarbonyl-8'-chloroacetoxy-spiro[in doline-2,3,-[3H]naphth[2,1-b][1,41oxazine].
8 more elements
A photochromic article comprising a polymeric host material and a photochromic amount of a naphthoxazine compound represented by the following graphic formula:
- ##STR5## wherein:
- (a) R.sub.1 is C.sub.1 -C.sub.8 alkyl, phen(C.sub.1 -C.sub.4)alkyl, naphth(C.sub.1 -C.sub.4)alkyl, allyl, acrylyloxy(C.sub.2 -C.sub.6)alkyl, methacrylyloxy(C.sub.2 -C.sub.6)alkyl, C.sub.1 -C.sub.4 acyloxy(C.sub.2 -C.sub.6)alkyl, carboxy(C.sub.2 -C.sub.6)alkyl, cyano(C.sub.2 -C.sub.6)alkyl, hydroxy(C.sub.2 -C.sub.6)alkyl, C.sub.1 -C.sub.6 alkoxy(C.sub.2 -C.sub.4)alkyl or (C.sub.2 H.sub.4 O).sub.m.CH.sub.3, wherein m is an integer from 1 to 6;
- (b) each R.sub.2 is C.sub.1 -C.sub.5 alkyl, C.sub.1 -C.sub.5 alkoxy, nitro, cyano, C.sub.1 -C.sub.8 alkoxycarbonyl, C.sub.1 -C.sub.4 acyloxy, halo, C.sub.1 -C.sub.4 monohaloalkyl or C.sub.1 -C.sub.4 polyhaloalkyl;
- (c) R.sub.3 and R.sub.h are each C.sub.1 -C.sub.5 alkyl, benzyl, phenyl, mono- or di-substituted phenyl, said phenyl substituents being C.sub.1 -C.sub.5 alkyl or C.sub.1 -C.sub.5 alkoxy, or R.sub.3 and R.sub.4 taken together form a group selected from a cyclic ring of from 5 to 8 carbon atoms which includes the spiro carbon atom, norbornyl or adamantyl;
- (d) t{.sub.5 is the group --C(O)X, X being --OR.sub.7 or --N(R.sub.8)R.sub.9, wherein R.sub.7 is allyl, C.sub.1 -C.sub.6 alkyl, benzyl, C.sub.1 -C.sub.6 alkyl substituted benzyl, C.sub.1 -C.sub.6 alkoxy substituted benzyl, C.sub.1 -C.sub.6 alkoxy(C.sub.2 -C.sub.4)alkyl, or C.sub.1 -C.sub.6 haloalkyl, and wherein R.sub.8 and R.sub.9 are each selected from hydrogen, C.sub.1 -C.sub.5 alkyl, C.sub.5 -C.sub.7 cycloalkyl, phenyl and substituted phenyl, or R.sub.8 and R.sub.9 together with the nitrogen form a substituted or unsubstituted saturated heterocyclic ring containing from 5 to 6 ring atoms, which ring includes as the hetero atom said nitrogen atom alone or one additional hetero atom of nitrogen or oxygen, said phenyl and heterocyclic ring substituents being selected from C.sub.1 -C.sub.5 alkyl and C.sub.1 -C.sub.6 alkoxy;
- (e) R.sub.6 is the group, --O--Y, wherein Y is hydrogen, C.sub.1 -C.sub.6 alkyl, benzyl, C.sub.1 -C.sub.6 alkyl substituted benzyl, C.sub.1 -C.sub.6 alkoxy substituted benzyl, C.sub.1 -C.sub.6 alkoxy (C.sub.2 -C.sub.4) alkyl, C.sub.1 -C.sub.6 haloalkyl, allyl or the group, --C(O)Z, wherein Z is C.sub.1 -C.sub.6 alkyl, phenyl, C.sub.1 -C.sub.6 alkyl substituted phenyl, C.sub.1 -C.sub.6 alkoxy substituted phenyl, C.sub.1 -C.sub.6 alkoxy, phenoxy, C.sub.1 -C.sub.6 alkyl substituted phenoxy, C.sub.1 -C.sub.6 alkoxy substituted phenoxy, C.sub.1 -C.sub.6 alkylamino, phenylamino, C.sub.1 -C.sub.6 alkyl substituted phenylamino, or C.sub.1 -C.sub.6 alkoxy substituted phenylamino;
- and
- (f) n is the integer 0, 1, or 2, said halo substituents being chloro, fluoro, iodo or bromo.
5 more elements
A photochromic article comprising a solid transparent polymerized organic host material and a photochromic amount of each of (a) a first photochromic substance wherein said first photochromic substance is a spiro(indoline)naphthopyran, spiro (indoline)benzopyran, spiro (indoline) pyridobenzoxazine, spiro(indoline)benzoxazine or a chromene, and (b) a naphthoxazine compound represented by the following graphic formula:
- ##STR6## wherein:
- (a) R.sub.1 is C.sub.1 -C.sub.8 alkyl, phen(C.sub.1 -C.sub.4)alkyl, naphth(C.sub.1 -C.sub.4)alkyl, allyl, acrylyloxy(C.sub.2 -C.sub.6)alkyl , methacrylyloxy(C.sub.2 -C.sub.6)alkyl, C.sub.1 -C.sub.4 acyloxy(C.sub.2 -C.sub.6)alkyl, carboxy(C.sub.2 -C.sub.6)alkyl, cyano(C.sub.2 -C.sub.6)alkyl, hydroxy(C.sub.2 -C.sub.6)alkyl, C.sub.1 -C.sub.6 alkoxy(C.sub.2 -C.sub.4)alkyl or (C.sub.2 H.sub.4 O).sub.m.CH.sub.3, wherein m is an integer from 1 to 6;
- (b) each R.sub.2 is C.sub.1 -C.sub.5 alkyl, C.sub.1 -C.sub.5 alkoxy, nitro, cyano, C.sub.1 -C.sub.8 alkoxycarbonyl, C.sub.1 -C.sub.4 acyloxy, halo, C.sub.1 -C.sub.4 monohaloalkyl or C.sub.1 -C.sub.4 polyhaloalkyl;
- (c) R.sub.3 and R.sub.4 are each C.sub.1 -C.sub.5 alkyl, benzyl, phenyl, mono- or di-substituted phenyl, said phenyl substituents being C.sub.1 -C.sub.5 alkyl or C.sub.1 -C.sub.5 alkoxy, or R.sub.3 and R.sub.4 taken together form a group selected from a cyclic ring of from 5 to 8 carbon atoms which includes the spiro carbon atom, norbornyl or adamantyl;
- (d) R.sub.5 is the group --C(O)X, X being --OR.sub.7 or --N(R.sub.8)R.sub.9, wherein R.sub.7 is allyl, C.sub.1 -C.sub.6 alkyl, benzyl, C.sub.1 -C.sub.6 alkyl substituted benzyl, C.sub.1 -C.sub.6 alkoxy substituted benzyl, C.sub.1 -C.sub.6 alkoxy(C.sub.2 -C.sub.4)alkyl, or C.sub.1 -C.sub.6 haloalkyl, and wherein R.sub.8 and R.sub.9 are each selected from hydrogen, C.sub.1 -C.sub.5 alkyl, C.sub.5 -C.sub.7 cycloalkyl, phenyl and substituted phenyl, or R.sub.8 and R.sub.9 together with the nitrogen form a substituted or unsubstituted saturated heterocyclic ring containing from 5 to 6 ring atoms, which ring includes as the hetero atom said nitrogen atom alone or one additional hetero atom of nitrogen or oxygen, said phenyl and heterocyclic ring substituents being selected from C.sub.1 -C.sub.5 alkyl and C.sub.1 -C.sub.6 alkoxy;
- (e) R.sub.6 is the group, --O--Y, wherein Y is hydrogen, C.sub.1 -C.sub.6 alkyl, benzyl, C.sub.1 -C.sub.6 alkyl substituted benzyl, C.sub.1 -C.sub.6 alkoxy substituted benzyl, C.sub.1 -C.sub.6 alkoxy (C.sub.2 -C.sub.4) alkyl, C.sub.1 -C.sub.6 haloalkyl, allyl or the group, --C(O)Z, wherein Z is C.sub.1 -C.sub.6 alkyl, phenyl, C.sub.1 -C.sub.6 alkyl substituted phenyl, C.sub.1 -C.sub.6 alkoxy substituted phenyl, C.sub.1 -C.sub.6 alkoxy, phenoxy, C.sub.1 -C.sub.6 alkyl substituted phenoxy, C.sub.1 -C.sub.6 alkoxy substituted phenoxy, C.sub.1 -C.sub.6 alkylamino, phenylamino, C.sub.1 -C.sub.6 alkyl substituted phenylamino, or C.sub.1 -C.sub.6 alkoxy substituted phenylamino;
- and
- (f) n is the integer 0, 1, or 2, said halo substituents being chloro, fluoro, iodo or bromo.
5 more elements
Dependencies are inferred from the claim text.