Higher-molecular photochromic dyes having at least one and not more than four naphthopyran subunits and multiple polyether chains

Photochromic dyes with at least one and at most four naphthopyran subunits and multiple polyether chains according to the following formula (I):

• on the proviso (1) that at least one and at most four of the radicals R1, R2, R3, and R4, independently of one another, represent the following group A with a terminal, longer-chain polyether substituent:
• and the remaining radicals R1, R2, R3, and R4, independently of one another, represent hydrogen, a methyl radical, an ethyl radical, a phenyl radical, or the following group B with a longer-chain polyether substituent:
• wherein, in the case of only one group A in the molecule, at least one of the remaining radicals must represent the group B;
• or on the proviso (2) that at least one and at most two of the radicals R1, R2, R3, and R4, independently of one another, represent the following group C:
• and of the remaining radicals R1, R2, R3, and R4, at least two represent the group B, wherein in the case of a further remaining radical, it can be selected from hydrogen, a methyl radical, an ethyl radical, or a phenyl radical;
• wherein m, n, p, q, and r, independently of one another, represent an integer from 0 to 1, s represents an integer from 5 to 50, and t represents an integer from 0 to 3,
• wherein the radical R5 in the repeating unit of chain length s, independently of one another, represent hydrogen or a methyl radical;
• wherein the radical R6 represents a substituent selected from hydrogen, fluorine, a (C1-C6)-alkyl radical, a (C3-C7)-cycloalkyl radical, a (C1-C6)-thioalkyl radical, a (C1-C6)-alkoxy radical, a trifluoromethyl radical, a phenyl radical, a 4-methoxyphenyl radical, a phenoxy radical, a 4-methoxyphenoxy radical, a benzyl radical, a 4-methoxybenzyl radical, a benzyloxy radical, a 4-methoxybenzyloxy radical, a biphenyl radical, a biphenyloxy radical, a naphthyl radical, a naphthoxy radical, a piperidinyl radical, a 3,5-dimethylpiperidinyl radical, a morpholinyl radical, a 2,6-dimethylmorpholinyl radical, a thiomorpholinyl radical, an azacycloheptyl radical, an indolinyl radical, a 1,2,3,4-tetrahydroquinolinyl radical, a 1,2,3,4-tetrahydroisoquinolinyl radical, a diphenylamino radical, a ((C1-C6)-alkoxyphenyl)-phenylamino radical, a bis ((C1-C6)-alkoxyphenyl) amino radical, a 10,10-dimethyl-9,10-dihydroacridine radical, a phenothiazinyl radical, a phenoxazinyl radical, a phenazinyl radical, a carbazolyl radical, a 1,2,3,4-tetrahydrocarbazolyl radical, or a 10,11-dihydro-dibenz [b,f]azepinyl radical;
• wherein the stylized benzene ring inscribed “naphthopyran” represents one of the four following discrete naphthopyran subunits “1“−“4”:
• wherein the radicals R7, R8, and R10, independently of one another, represent a substituent selected from a (C1-C6)-alkyl radical or a phenyl radical;
• the radicals R9, independently of one another, represent a substituent selected from a (C1-C6)-alkyl radical, a (C3-C7)-cycloalkyl radical, a (C1-C6)-alkoxy radical, a benzyl radical, or an unsubstituted or monosubstituted phenyl radical, wherein the substituent can be selected from fluorine, a (C1-C6)-alkyl radical, or a (C1-C6)alkoxy radical;
• and wherein k represents 0, 1, or 2:
• or two adjacent R9 radicals together form an annelated benzene ring, which can be unsubstituted, monosubstituted, or disubstituted, wherein the substituents can be selected from a (C1-C6)-alkyl radical, a (C1-C6)-alkoxy radical, a phenyl radical, or a benzyl radical;
• or two adjacent R9 radicals together form an annelated naphthalene ring system, an annelated benzofuran ring system, an annelated benzothiophene ring system, an annelated 3,3-dimethylindene ring system, or an annelated 2H-chromene ring system;
• and the radicals R11 and R12, independently of one another, represent a substituent selected from hydrogen, a (C1-C6)-alkyl radical, a (C3-C7)-cycloalkyl radical, a trifluoromethyl radical, a benzyl radical, or an unsubstituted or monosubstituted phenyl radical, wherein the substituent can be selected from fluorine, a (C1-C6)-alkyl radical, or a (C1-C6)-alkoxy radical;
• or the radicals R11 and R12 together represent the group —(CH2)j—, wherein j represents an integer from 1 to 3;
• on the proviso that if this numerical value is 2 or 3, a benzene ring may also be annelated to two adjacent CH2 groups.