PHOTOCHROMIC ANNELATED NAPHTHOPYRANE SYSTEMS WITH SPECIAL SUBSTITUENTS, FOR ATTAINING RAPID LIGHTENING SPEEDS

Abstract

The present invention relates to new photochromic, fused naphthopyran systems having specific substituents R.sub.1, which can be used to attain very rapid lightening speeds, without detriment to the depth of darkening after excitation, and also to the use thereof in plastics of all kinds.

##STR00001##

Claims

1. Photochromic fused naphthopyrans of the formula (II): ##STR00010## in which the radical R.sub.1, or R.sub.1 and R.sub.3 independently of one another, is/are the following moiety: ##STR00011## in which the radical R.sub.13 is hydrogen or a methyl radical and the radical R.sub.14 is a substituent selected from hydrogen, a (C.sub.1-C.sub.6)-alkyl radical, an acetyl radical, a benzoyl radical, a phenyl radical, a benzyl radical, a biphenylyl radical, a naphthyl radical, a tert-butyldimethylsilyl radical or a tert-butyldiphenylsilyl radical; n is an integer from 0 to 1, and p is an integer from 3 to 50; or, if R.sub.13 is a methyl radical, R.sub.14 may also be the moiety —(CH.sub.2—CH.sub.2).sub.q—OR.sub.15, in which case the radical R.sub.15 may be selected from hydrogen, a (C.sub.1-C.sub.6)-alkyl radical, a phenyl radical, a benzyl radical or a biphenylyl radical, and q is an integer from 1 to 20; and the radicals R.sub.2, R.sub.3 and R.sub.4 in each case independently of one another are a substituent selected from hydrogen, bromine, chlorine, fluorine, a (C.sub.1-C.sub.6)-alkyl radical, a (C.sub.3-C.sub.7)-cycloalkyl radical, a (C.sub.1-C.sub.6)-thioalkyl radical, a (C.sub.1-Cis)-alkoxy radical, a hydroxyl radical, a tert-butyldimethylsilyloxy radical, a tert-butyldiphenylsilyloxy 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 biphenylyl radical, a diphenylyloxy radical, a naphthyl radical, a naphthoxy radical, a mono-(C.sub.1-C.sub.6)-alkylamino radical, a di-(C.sub.1-C.sub.6)-alkylamino radical, a phenylamino radical, a (C.sub.1-C.sub.6)-alkyl-phenylamino radical, a diphenylamino radical, a (4-methoxyphenyl)amino radical, a ((C.sub.1-C.sub.6)-alkyl)-(4-methoxyphenyl)amino radical, a bis(4-methoxyphenyl)amino radical, a piperidyl radical, a 3,5-dimethylpiperidyl radical, an indolinyl radical, a morpholinyl radical, a 2,6-dimethylmorpholinyl radical, a thiomorpholinyl radical, an azacycloheptyl radical, a phenothiazinyl radical, a phenoxazinyl radical, a 1,2,3,4-tetrahydroquinolyl radical, a 1,2,3,4-tetrahydroisoquinolyl radical, a phenazinyl radical, a carbazolyl radical, a 1,2,3,4-tetrahydrocarbazolyl radical or a 10,11-dihydrodibenz[b,f]azepinyl radical; or the two adjacent radicals R.sub.2 and R.sub.3 are the moiety —V—(CH.sub.2).sub.r—W—, in which case V and W independently of one another are selected from the moieties —O—, —S—, —N(C.sub.1-C.sub.6)-alkyl-, —NC.sub.6H.sub.5—, —CH.sub.2—, —C(CH.sub.3).sub.2—, —C(C.sub.2H.sub.5).sub.2— or —C(C.sub.6H.sub.5).sub.2—; r is an integer from 1 to 3; with the proviso that if this numerical value is 2 or 3, there may also be a benzene ring fused to two adjacent CH.sub.2 groups; V or W, together with the respectively adjacent CH.sub.2 group, may also be a fused benzene ring; or R.sub.3 is the same moiety as R.sub.1; the radicals R.sub.5, R.sub.8, R.sub.9, R.sub.10, R.sub.11 and R.sub.12 each independently of one another are a substituent selected from hydrogen, a (C.sub.1-C.sub.6)-alkyl radical, a (C.sub.3-C.sub.7)-cycloalkyl radical, a phenyl radical, a benzyl radical, a biphenylyl radical or a naphthyl radical; where m is an integer from 1 to 3; or two adjacent radicals R.sub.5 form a fused benzene ring, which may be unsubstituted or mono- or disubstituted, in which case the substituents may be selected from hydrogen, a (C.sub.1-C.sub.6)-alkyl radical, a (C.sub.1-C.sub.6)-alkoxy radical, a phenyl radical, a benzyl radical, a biphenylyl radical or a naphthyl radical; or two adjacent radicals R.sub.5 form a fused benzofuran ring, a fused benzothiophene ring, a fused 2H-chromene ring, a fused 3,3-dimethylindene ring or a fused dioxane ring; or the radicals R.sub.8 and R.sub.9 together form the moiety —(CH.sub.2).sub.s—, in which case s is an integer from 1 to 3; with the proviso that if this numerical value is 2 or 3, there may also be a benzene ring fused to two adjacent CH.sub.2 groups.

2. Photochromic fused naphthopyrans as claimed in claim 1, in which the radical R.sub.1 represents the moiety: ##STR00012## and the radical R.sub.3 is a substituent selected from hydrogen, bromine, chlorine, fluorine, a (C.sub.1-C.sub.6)-alkyl radical, a (C.sub.3-C.sub.7)-cycloalkyl radical, a (C.sub.1-C.sub.6)-thioalkyl radical, a (C.sub.1-C.sub.18)-alkoxy radical, a hydroxyl radical, a tert-butyldimethylsilyloxy radical, a tert-butyldiphenylsilyloxy 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 biphenylyl radical, a diphenylyloxy radical, a naphthyl radical, a naphthoxy radical, a mono-(C.sub.1-C.sub.6)-alkylamino radical, a di-(C.sub.1-C.sub.6)-alkylamino radical, a phenylamino radical, a (C.sub.1-C.sub.6)-alkyl-phenylamino radical, a diphenylamino radical, a (4-methoxyphenyl)amino radical, a ((C.sub.1-C.sub.6)-alkyl)-(4-methoxyphenyl)amino radical, a bis(4-methoxyphenyl)amino radical, a piperidyl radical, a 3,5-dimethylpiperidyl radical, an indolinyl radical, a morpholinyl radical, a 2,6-dimethylmorpholinyl radical, a thiomorpholinyl radical, an azacycloheptyl radical, a phenothiazinyl radical, a phenoxazinyl radical, a 1,2,3,4-tetrahydroquinolyl radical, a 1,2,3,4-tetrahydroisoquinolyl radical, a phenazinyl radical, a carbazolyl radical, a 1,2,3,4-tetrahydrocarbazolyl radical or a 10,11-dihydrodibenz[b,f]azepinyl radical; and in which the other radicals are as defined above.

3. Photochromic fused naphthopyrans as claimed in claim 1, in which the radicals R.sub.5, R.sub.8, R.sub.9, R.sub.10, R.sub.11 and R.sub.12 each independently of one another are a substituent selected from hydrogen, a (C.sub.1-C.sub.6)-alkyl radical, a (C.sub.3-C.sub.7)-cycloalkyl radical, a phenyl radical, a benzyl radical, a biphenylyl radical or a naphthyl radical; where m is an integer from 1 to 3.

4. Photochromic fused naphthopyrans as claimed in claim 1, in which the radical R.sub.1 represents the following moiety: ##STR00013## in which the radical R.sub.13 is hydrogen or a methyl radical and the radical R.sub.14 is a substituent selected from hydrogen, a (C.sub.1-C.sub.6)-alkyl radical, an acetyl radical, a benzoyl radical, a phenyl radical, a benzyl radical, a biphenylyl radical, a naphthyl radical, a tert-butyldimethylsilyl radical or a tert-butyldiphenylsilyl radical; n is an integer from 0 to 1, and p is an integer from 3 to 50; or, if R.sub.13 is a methyl radical, R.sub.14 may also be the moiety —(CH.sub.2—CH.sub.2).sub.q—OR.sub.15, in which case the radical R.sub.15 may be selected from hydrogen, a (C.sub.1-C.sub.6)-alkyl radical, a phenyl radical, a benzyl radical or a biphenylyl radical, and q is an integer from 1 to 20; and the radical R.sub.3 is a substituent selected from hydrogen, bromine, chlorine, fluorine, a (C.sub.1-C.sub.6)-alkyl radical, a (C.sub.3-C.sub.7)-cycloalkyl radical, a (C.sub.1-C.sub.6)-thioalkyl radical, a (C.sub.1-C.sub.18)-alkoxy radical, a hydroxyl radical, a tert-butyldimethylsilyloxy radical, a tert-butyldiphenylsilyloxy 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 biphenylyl radical, a diphenylyloxy radical, a naphthyl radical, a naphthoxy radical, a mono-(C.sub.1-C.sub.6)-alkylamino radical, a di-(C.sub.1-C.sub.6)-alkylamino radical, a phenylamino radical, a (C.sub.1-C.sub.6)-alkyl-phenylamino radical, a diphenylamino radical, a (4-methoxyphenyl)amino radical, a ((C.sub.1-C.sub.6)-alkyl)-(4-methoxyphenyl)amino radical, a bis(4-methoxyphenyl)amino radical, a piperidyl radical, a 3,5-dimethylpiperidyl radical, an indolinyl radical, a morpholinyl radical, a 2,6-dimethylmorpholinyl radical, a thiomorpholinyl radical, an azacycloheptyl radical, a phenothiazinyl radical, a phenoxazinyl radical, a 1,2,3,4-tetrahydroquinolyl radical, a 1,2,3,4-tetrahydroisoquinolyl radical, a phenazinyl radical, a carbazolyl radical, a 1,2,3,4-tetrahydrocarbazolyl radical or a 10,11-dihydrodibenz[b,f]azepinyl radical, preferably selected from hydrogen, a (C.sub.1-C.sub.6)-alkyl radical, a (C.sub.3-C.sub.7)-cycloalkyl radical, a (C.sub.1-C.sub.6)-thioalkyl radical, a (C.sub.1-C.sub.6)-alkoxy radical, a hydroxyl radical, a tert-butyldimethylsilyloxy radical, a tert-butyldiphenylsilyloxy 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 or a 4-methoxybenzyloxy radical.

5. The use of one or more of the photochromic fused naphthopyrans as claimed in claim 1 in plastics of all kinds, more particularly for ophthalmic purposes, in optical lenses and lenses for eyewear of all kinds, such as, for example, corrective spectacles, driver's glasses, ski goggles, sunglasses, motorcycle goggles, for visors of protective helmets and the like, and for sun protection in vehicles and in the architectural sector, in the form of windows, protective shades, covers, roofs and the like.

Description

[0030] FIG. 1 shows the kinetic comparison of compounds of the general formula (I) of the invention, more specifically having the formula (III) below, with corresponding compounds from the prior art from EP 2 788 340.

[0031] FIG. 2 shows the kinetic comparison of compounds of the general formula (II) of the invention, more specifically having the formula (IV) below, with corresponding compounds from the prior art from EP 3 010 924.

[0032] The specific molecular structures of the compounds shown in FIGS. 1 and 2 are set out in table 1. The compounds 1 and 2 of the invention are described in table 1 below by the formula (III), compounds 3 and 4 of the invention by the formula (IV).

[0033] FIGS. 1 and 2 show illustratively the clear effect of the specific substituents R.sub.1 of the invention on the lightening speed, without detriment to the depth of darkening.

TABLE-US-00001 TABLE 1 Molecular structures of the compounds presented in FIGS. 1 and 2 (III) [00004] (IV) [00005] R.sub.1 in formula (III) R.sub.3 in (III) R.sub.1 in formula (IV) R.sub.3 in (IV) Compound 1 from prior art (EP 2 788 340) OMe (=methoxy) OMe Compound 1 of the invention [00006]   Me = methyl; p ≈ 16 (Gaussian distribution) OMe Compound 2 of the invention [00007]   Et = ethyl; p ≈ 17 OMe Compound 2 OMe Me from prior art (=methyl) (EP 3 010 924) Compound 3 of the invention [00008]   Me = methyl; p ≈ 16 (Gaussian distribution) Me Compound 4 of the invention [00009]   Et = ethyl; p ≈ 17 Me

[0034] The compounds 1 and 3 of the invention have a linear polyethyleneoxy chain in the substituent R.sub.1, with an average chain length of about 16. Starting material for the synthesis is commercially available polyethylene glycol monomethyl ether having an average molecular weight of 750. Here there is a Gaussian distribution of different chain lengths, with a maximum at about 16 ethyleneoxy units.

[0035] The compounds 2 and 4 of the invention have a linear polypropyleneoxy chain in the substituent R.sub.1, with an average chain length of about 17. Starting material for the synthesis is commercially available polypropylene glycol having an average molecular weight of 1000. Here again there is a Gaussian distribution of different chain lengths, with a maximum at about 17 propyleneoxy units. The 2-ethoxyethyl end group is introduced by means of a conventional Williamson ether synthesis using 2-bromoethyl ethyl ether.

[0036] The effect of the acceleration of the lightening speed is observable not only for the chain lengths described above; shorter chains with fewer than 10 units likewise display the effect.

[0037] According to the synthesis scheme in FIG. 3, the compounds of the invention are then prepared from these. The method is the same for both types of formula—in FIG. 3, therefore, only the pyran ring with the two aryl substituents is shown (n refers to the formula of the substituent R.sub.1 in claim 1). If n is 1, the aforementioned longer-chain starting compounds are attached covalently to the photochromic dye molecule by means of an ester synthesis. The carboxyl group in the succinyl unit is activated using CDI (carbonyldiimidazole), which permits a very mild ester synthesis. If n is 0, the longer-chain starting compound must first be activated in the form of tosylate (Ts). This is followed by the covalent attachment to the photochromic dye molecule by means of a conventional Williamson ether synthesis.

[0038] Where the compounds of the invention are employed in plastics of all kinds, the photochromic properties can be improved further by means of additives. Preferred additives are compounds constructed from the same structural units as substituent R.sub.1 and therefore able to configure the chemical environment of the photolabile dye molecules in a similar way to substituent R.sub.1, but they are not fixed in a diffusion-stable way. Preferred examples are therefore linear polyethylene glycols of various chain lengths, linear polypropylene glycols of various chains lengths, oligomers constructed in alternation of ethyleneoxy and propyleneoxy units, and also block copolymers composed of ethyleneoxy and propyleneoxy units. End groups used, other than hydroxyl groups, may also be alkyl radicals or other groups.

[0039] A further subject of the present invention concerns the use of one or more of the photochromic fused naphthopyran systems of the invention in plastics of all kinds, more particularly for ophthalmic purposes, in optical lenses and lenses for eyewear of all kinds, such as, for example, corrective spectacles, driver's glasses, ski goggles, sunglasses, motorcycle goggles, for visors of protective helmets and the like, and for sun protection in vehicles and in the architectural sector, in the form of windows, protective shades, covers, roofs and the like. In the case of use in plastics of all kinds, adjuvants of all kinds may be used together with the compounds of the invention. Preference, as already set out above, is given to linear polyethylene glycols, linear polypropylene glycols, oligomers composed in alternation of ethyleneoxy and propyleneoxy units, and also block copolymers composed of ethyleneoxy and propyleneoxy units. End groups of the oligomer additives, other than hydroxyl groups, may also be alkyl groups or other groups.