Photochromic multiple ring-fused naphthopyrans having extreme longwave absorption extending far into the visible wavelength range

Photochromic polyfused naphthopyrans having the formulae (I), (II) and (III):

• in which the R1, R2, R3, R4, R7, R8 and R10 radicals each independently represent a substituent selected from the group α consisting of a hydrogen atom, a (C1-C18)-alkyl radical, a (C3-C7)-cycloalkyl radical that may have one or more heteroatoms, a (C1-C18)-thioalkyl radical, a (C1-C18)-alkoxy radical, a hydroxyl group, a trifluoromethyl group, bromine, chlorine, fluorine, an un-, mono- or disubstituted phenyl, phenoxy, benzyl, benzyloxy, naphthyl or naphthoxy radical, where these substituents may in turn be selected from the group β consisting of a hydrogen atom, a (C1-C6)-alkyl radical, a (C3-C7)-Cycloalkyl radical, a (C1-C6)-thioalkyl radical, a (C1-C6)-alkoxy radical, a phenyl radical, a benzyl radical or a naphthyl radical;
• n represents an integer from 1 to 4;
• or the R1 and R2 radicals together with the carbon atom bonded to these radicals form a three- to eight-membered carbo- or heteromonocyclic ring which optionally bears one or more substituents from group β, and to which one to three aromatic or heteroaromatic ring systems may be fused, where the ring system(s) is/are independently selected from benzene, naphthalene, phenanthrene, pyridine, quinoline, furan, thiophene, pyrrole, benzofuran, benzothiophene, indole and carbazole, which may in turn be substituted by one or more substituents selected from group β;
• or two adjacent R4 radicals form a fused benzene ring which may be un-, mono- or disubstituted, where the substituents may be selected from group β;
• or two adjacent R4 radicals form a 1,1-dimethylindene or benzofuran ring system fused via the double bond in the five-membered ring;
• or two adjacent R4 radicals form a 2H-chromene or 1H-isochromene ring system via the double bond in the heterocyclic six-membered ring,
• the R5 and R6 radicals each independently represent a substituent selected from hydrogen, a (C1-C18)-alkyl radical, a phenyl radical, a benzyl radical or a naphthyl radical;
• m represents an integer from 1 to 4;
• or two adjacent —CR5R6— moieties form a fused benzene ring which may be un-, mono- or disubstituted, where the substituents may be selected from group β;
• the R9 radical represents a substituent selected from hydrogen, a (C1-C18)-alkyl radical, a phenyl radical, a benzyl radical or a naphthyl radical;
• X′ in the formula (I) is selected from —SO2—, —CH2—, —C(CH3)2—, —C(C2H5)2—, —C(C6H5)2—, —O—CH2—, —CH2—O—, —CH2—CH2—, —C(CH3)2—CH2— or —CH2—C(CH3)2—;
• X in the formula (II) or (III) is selected from —O—, —S—, —SO2—, —N(C1-C6)-alkyl-, —NC6H5—, —CH2—, —C(CH3)2—, —C(C2H5)2—, —C(C6H5)2—, —O—CH2—, —CH2—O—, —O—(C═O)—, —(C═O)—O—, —CH2—CH2—, —C(CH3)2—CH2— or —CH2—C(CH3)2—;
• Y and Z are independently selected from —O—, —S—, —SO2—, —N(C1-C6)-alkyl-, —NC6H5—, —CH2—, —C(CH3)2—, —C(C2H5)2— or —C(C6H5)2—, where Y or Z, optionally together with the respectively adjacent CR5R6 moiety, may form a fused benzene ring which may be un-, mono- or disubstituted, where the substituents may in turn be selected from group β, or Y or Z together with the respectively adjacent CR5R6 moiety form a fused naphthalene, 9,9-dimethylfluorene or dibenzofuran ring system which may in turn be substituted by one or more substituents selected from group β;
• and in which B and B′ are independently selected from one of the following groups a) and b), where
• a) is a mono-, di- or trisubstituted aryl radical, where the aryl radical is phenyl, naphthyl or phenanthryl, and
• b) is an un-, mono- or disubstituted heteroaryl radical, where the heteroaryl radical is selected from pyridyl, furanyl, thienyl, benzofuranyl, benzothienyl, 1,2,3,4-tetrahydrocarbazolyl or julolidinyl;
• where the substituents of the aryl and heteroaryl radicals in a) and b) are selected from group β or the —(O—CHR13—CH2)q—OR14 moiety where R13 represents hydrogen or a methyl radical, R14 represents hydrogen or a (C1-C6)-alkyl radical and q represents an integer from 1 to 50;
• or the substituents in a) and b) are selected from group x consisting of amino, mono-(C1-C18)-alkylamino, di-(C1-C18)-alkylamino, phenethenyl un-, mono- or disubstituted on the phenyl ring, un-, mono- or disubstituted (phenylimino)methylene, un-, mono- or disubstituted (phenylmethylene)imino and un-, mono- or disubstituted mono- and diphenylamino, piperidinyl, 3,5-dimethylpiperidinyl, N-substituted piperazinyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, indolinyl, morpholinyl, 2,6-dimethylmorpholinyl, thiomorpholinyl, azacycloheptyl, azacyclooctyl, un-, mono- or disubstituted phenothiazinyl, un-, mono- or disubstituted phenoxazinyl, un-, mono-, di- or trisubstituted 9,10-dihydroacridinyl, un-, mono- or disubstituted 1,2,3,4-tetrahydroquinolinyl, un-, mono- or disubstituted 2,3-dihydro-1,4-benzoxazinyl, un-, mono- or disubstituted 1,2,3,4-tetrahydroisoquinolinyl, un-, mono- or disubstituted phenazinyl, un-, mono- or disubstituted carbazolyl, un-, mono- or disubstituted 1,2,3,4-tetrahydrocarbazolyl and un-, mono- or disubstituted 10,11-dihydrodibenz[b,f]azepinyl, where the substituent(s) may in turn independently be selected from group β;
• or two directly adjacent substituents of the aryl and heteroaryl radicals in a) and b) constitute a V—(CR11R12)p—W moiety where p represents an integer from 1 to 3, the R11 and R12 radicals each independently represent a substituent selected from β, and V and W are independently selected from —O—, —S—, —N(C1-C6)-alkyl-, —NC6H5—, —CH2—, —C(CH3)2—, —C(C2H5)2— or —C(C6H5)2—;
• or two or more adjacent CR11R12 moieties are part of a fused benzene ring which may be un-, mono- or disubstituted, where the substituents may in turn be selected from group β;
• or V and/or W together with the respectively adjacent CR11R12 moiety form a fused benzene ring which may be un-, mono- or disubstituted, where the substituents may in turn be selected from group β.