The invention is therefore based on the problem of avoiding the described disadvantages entailed in prior art and to provide photochromic compounds which present properties improved over those of the structures described in prior art and which, in the form excited by light, present a bathochromically shifted absorption in the longest wavelength range within the visible part of the spectrum, compared against comparable prior art compounds. Accordingly compounds had to be found which present a further bathochromic shift of their absorption maximums in the visible range by roughly 100 nm, as compared against the known compounds. Furthermore, the absorption band in the longest wavelength range, i.e. the absorption band between the red or infrared part of the light spectrum and the "absorption gap"--i.e. the point of lowest absorption in the range from 400 to 500 nm--should be as broad as possible. Another objective consisted therefore in the provision of compounds displaying absorption characteristics which offers still a 50% absorption in response to very strong obscuration (transmission at .lambda..sub.max &lt;10%) at 700 nm and at least a 10% absorption still at 750 nm.
Moreover, the preferred compounds should not present a distinct basic function because experience had shown that these lenses not only tend to add protons and result in colour distortions in the production of photochromic plastic lenses in mass-dyeing processes but in permanent use also tend to give rise to secondary reactions under the influence of light which result in the loss of the photochromic reaction.
Moreover, the method of producing the new compounds should be improved over conventional methods, with a main emphasis on a simple process control, cautious reaction conditions and sound yields.
The above-explained problem of the invention is solved by the photochromic naphthopyrane-dyes having the general formula (I) ##STR1## wherein R.sub.1 and R.sub.2
are equal or different, independently of each other, and are selected from PA1 or PA1 or PA1 is selected from PA1 or from PA1 or from PA1 are selected, independently of each other, from the group z consisting of (a) and (b), with PA1 or are selected from PA1 or PA1 or PA1 and Y PA1 (1) 6-methoxy-3-(4-methoxyphenyl)-3,13-diphenyl-13-hydroxy-benz[p]-indeno [2,1-f]naphtho[1,2-b]pyrane PA1 (2) 6-methoxy-3-(4-methoxyphenyl)-3-phenyl-13-(2,5-dimethylphenyl)-13-hydroxy- benz[p]indeno[2,1-f]naphtho[1,2-b]pyrane, PA1 (3) 3-(4-diphenyl amino phenyl)-3-phenyl-13-(2,5-dimethylphenyl)-13-hydroxy-benz[p]indeno[2,1-f]na phtho[1,2-b]pyrane, PA1 (4) 3-(4-diphenyl amino phenyl)-6-methoxy-3,13-diphenyl-13-hydroxy-indeno[2,1-f]naphtho-[1,2-b]pyr ane, PA1 (5) 3-(4-diphenyl amino phenyl)6-methoxy-3-phenyl-13-(2,5-dimethylphenyl)-13-hydroxy-indeno[2,1-f] naphtho[1,2-b]pyrane, PA1 (6) 6-methoxy-3-(4-methoxy phenyl)-3-phenyl-13-(2,5-dimethylphenyl)-13-hydroxy-indeno[2,1-f]naphtho[1 ,2-b]pyrane, PA1 (7) 6-methoxy-3-(4-methoxyphenyl)-3-phenyl-13-(1-naphthyl)-13-hydroxy-indeno [ 2,1-f]-naphtho[1,2-b]pyrane, PA1 (8) 6,11-dimethoxy-3-(4-methoxyphenyl)-3-phenyl-13-(2,5-dimethyl phenyl)-13-hydroxy-indeno[2,1-f]naphtho[1,2-b]pyrane, PA1 (9) 3-(4-methoxyphenyl)-3-phenyl-13-(2,5-dimethylphenyl)-13-hydroxy-indeno-[2, 1-f]-naphtho[1,2-b]pyrane, and PA1 (10) 6-methoxy-3-(4-methoxyphenyl)-3-phenyl-13-(3-methyl-2-thienyl)-13-hydroxy- indeno[2,1-f]naphtho[1,2-b]pyrane.
the group f consisting of (C.sub.1 -C.sub.6)-alkyl, (C.sub.1 -C.sub.6)-alkoxy, chloro and fluoro; PA2 the group consisting of hydrogen, (C.sub.1 -C.sub.6)-cyclo-alkyl, phenyl, benzyl, dialkyl-(C.sub.1 -C.sub.6)-amino, dicyclo-hexylamino, diphenylamino, piperidyl, morpholinyl and pyridyl, with m, n=0, 1 or 2; PA2 two R.sub.1 and/or two R.sub.2 form together, independently of each other, a carbo- or hetero-cyclic ring, selected from benzene, pyridine, pyrazine, pyrimidine, furan and thiophene; PA2 the group g consisting of hydrogen, hydroxy, (C.sub.1 -C.sub.6)-alkyl, (C.sub.5 -C.sub.6)-cyclo-alkyl, (C.sub.1 -C.sub.6)-acyl, (C.sub.1 -C.sub.6)-alkoxy, phenyl, benzyl, mono-substituted phenyl, mono-substituted benzyl, with the aryl substituents being (C.sub.1 -C.sub.6)-alkyl or (C.sub.1 -C.sub.6)-alkoxy: PA2 mono-chlorine or mono-fluorine substituted phenyl, naphthyl, phenanthryl, pyrenyl, chinolyl, isochinolyl, benzofuranyl, thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl or indolyl, each in non-substituted or mono-substituted form, with the substituents being selected from the group consisting of chloro, fluoro, (C.sub.1 -C.sub.6)-alkyl, or (C.sub.1 -C.sub.6)-alkoxy; PA2 di- or tri-substituted phenyl, with the substituents being selected form the group consisting of chloro, fluoro, (C.sub.1 -C.sub.6)-alkyl, (C.sub.1 -C.sub.6)-alkoxy, (C.sub.1 -C.sub.6)-.omega.-phenylalkyl and (C.sub.1 -C.sub.6)-.omega.-phenoxy-alkyl, with the phenyl ring at the .omega.-position possibly representing again the X, X'- or R.sub.4 radical of another photochromic pyrane system; PA2 (a) the non-, mono-, di- and tri-substituted aryl groups phenyl and naphthyl; and PA2 (b) the non-, mono-, di- and tri-substituted hetero-cyclic groups pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl and benzothien-3-yl, PA2 and with the substituents in (a) and (b) being selected from PA2 the group h consisting of hydroxy, amino, mono-(C.sub.1 -C.sub.6)-alkyl-amino, di-(C.sub.1 -C.sub.6)-alkylamino, piperidino, morpholino, pyrryl, -(C.sub.1 -C.sub.6)-alkyl, -(C.sub.1 -C.sub.6)-chloro-alkyl, -(C.sub.1 -C.sub.6)-fluoro-alkyl, -(C.sub.1 -C.sub.6)-alkoxy, mono-(C.sub.1 -C.sub.6)-alkoxy-(C.sub.1 -C.sub.4)-alkyl, chloro and fluoro; or PA2 the group (a) consisting of non-basic amines such as non-substituted or substituted di-arylamino, pyrazole, imidazole, indole, pyridine, pyrazoline, imidazoline, pyrroline, phenothiazine, phenoxazine, phenazine, acridine, or carbazole, with the substituents on the non-basic amines being selected from (C.sub.1 -C.sub.6)-alkyl, (C.sub.1 -C.sub.4)-alkoxy, phenyl, fluoro, chloro and bromo; PA2 (c) (C.sub.1 -C.sub.6)-alkyl, (C.sub.1 -C.sub.6)-chloro-alkyl, (C.sub.1 -C.sub.6)-fluoro-alkyl, mono-(C.sub.1 -C.sub.6)-alkoxy-(C.sub.1 -C.sub.4)-alkyl, (C.sub.3 -C.sub.6)-cyclo-alkyl, mono-(C.sub.1 -C.sub.6)-alkoxy-(C.sub.3 -C.sub.6)-cyclo-alkyl, chloro-(C.sub.3 -C.sub.6)-cyclo-alkyl, and fluoro-(C.sub.3 -C.sub.6)-cyclo-alkyl; PA2 X and X' co-operate with the carbon atoms at the joining site with the pyrane to form a saturated C.sub.5 -C.sub.10 -monocyclic, C.sub.7 -C.sub.12 -bicyclic or C.sub.7 -C.sub.12 -tricyclic hydrocarbon ring or a fluorene-9-ylidene; PA2 either X or X' is mono- or di-substituted phenyl which is substituted, in the para position for combination with -phenyl, --(CH.sub.2).sub.p -phenyl or --O--(CH.sub.2).sub.p --O--phenyl (p=1, 2, 3, . . . , 6), with the second phenyl ring forming part of a second--not necessarily identical--photochromic pyrane; PA2 is selected from the group consisting of hydrogen, (C.sub.1 -C.sub.6)-alkyl, (C.sub.1 -C.sub.6)-acyl, non-substituted benzoyl, non-substituted naphthoyl, mono-substituted benzoyl and mono-substituted naphthoyl, with the aryl substituents being (C.sub.1 -C.sub.6)-alkyl, or (C.sub.1 -C.sub.6)-alkoxy; PA2 with the condition applying that R.sub.1 and R.sub.2 are not from the group f if R.sub.4 is from the group G and X and X' are from the group z in the event that the radicals of the group z or non-substituted or that the substituents are from the group h.
R.sub.4
X and X'
Overlapping with the closest-coming prior art (WO 96/14596 or U.S. Pat. No. 5,656,767) in terms of the substituents is thus precluded by a Disclaimer.
In accordance with one inventive variant the hetero-cycles in the group R.sub.4 in the photochromic naphthopyrane dyes may be combined via the carbo-cycle with the naphthopyrane system, which is not definitely necessary, however, in order to achieve the characteristics which can be attained with the present invention.
In correspondence with one inventive embodiment, photochromic indenoanellated naphthopyranes of the above-shown general chemical formulae are preferred, with R.sub.1, R.sub.2, R.sub.4 and Y being defined as above and with X and X' being selected from the above-identified group z, with the condition applying that R.sub.1 and R.sub.2 are not from the group f if R.sub.4 is from the group g and that X and X' are from the group z in the event that the radicals of the group z are non-substituted or that the substituents are from the group h.
In accordance with the invention R.sub.4 may preferably also be selected from the group consisting of phenyl radicals substituted at least in the ortho-position, 1- or 2-naphthyl, 9-phenanthryl, pyrenyl and hetero-aromates such as benzo-furanyl, benzothienyl, chinolyl or isochinolyl.
It is preferred in the photochromic naphthopyrane dyes that two R.sub.1 and/or two R.sub.2, independently of each other, form a hetero-cyclic ring selected from benzene, pyridine, pyrazine, pyrimidine, furan and thiophene.
In correspondence with another embodiment of the invention at least one X or X' may be an above-defined radical from the group z, which is at least substituted with a non-basic amine from the group (a), in the naphthopyrane dyes. X and X' may be the same radicals from the group z with different substituents, e.g. from the group (a). In an alternative, the substituents at X and X' may both be identical. In such a case it is very advantageous that the inventive compounds do not have any basic function in the molecule, which means that they present a very low basicity or no basicity at all. The inventive non-basic amino groups comprise non-substituted or substituted di-aryl amino, pyrazole, imidazole, indole, pyridine, pyrazoline, imidazoline, pyrroline, phenothiazine, phenoxazine, phenazine, acridine, carbazole or the like.
The non-basic amino-substituents of the group (a) may generally be presented in a non-substituted or a mono-substituted form, with the substituents being possibly selected from the group consisting of (C.sub.1 -C.sub.4)-alkyl, (C.sub.1 -C.sub.4)-alkoxy, phenyl, fluoro, chloro and bromo. Within the general scope of the present invention it is evident to the expert that any amine whatsoever is an element of group (a), be it an open, i.e. aliphatic, amine or even a cyclic amine, as long as it does not have any distinct basic function.
In distinction from basic amino substituents, inexpedient reactions in the processing of the inventive dyes and even during long-term use under the influence of light are generally precluded when non-basic amino substituents are selected. The service life of the photochromic dyes is hence substantially prolonged, protons are not added, and undesirable colour variations due to secondary reactions do not take place. Moreover, basic amino substituents frequently result in an impairment of the surface nature of the glass during its production by means of mass dyeing, which means that on account of a reduced glass adherence so-called chipping-off occurs. By contrast, the glass adherence is not reduced in the production of mass-dyed glasses when non-basic amino substituents in accordance with the present invention are present so that the number of rejects due to such chip-off is considerably reduced.
It was surprising to find that the characteristics of the inventive naphthopyrane dyes such as absorption, migration and brightening rate may be selectively controlled by the selection of the substituents. Moreover, the molecular weight of the dye can be set and/or multiplied by an appropriate selection of the substituents.
Furthermore, one or several methoxy groups may be present at the 5-, 6-, 7- and/or 8-position of the naphthopyrane ring, i.e. on the naphthalene ring, in the inventive indeno-anellated naphthopyranes. This is a grouping producing a bathochromic effect which produces an additive effect on the groups which are already present and produce a bathochromic effect.
Surprising and unexpected properties become evident particularly when diphenyl amino groups are introduced instead of methoxy groups, for, instance, in the indeno-anellated 2,2-diaryl-2H-naphtho[1,2-b] pyranes:
In the non-substituted 3,3-diaryl-3H-naphtho[2,1-b]pyranes such as those known from the German Patent Application P 198 20 781.6, the substitution of a 4-methoxy group on one of the phenyl rings in the 3-position of the naphthopyrane induces a bathochromic shift of the absorption band in the longest wavelength range by roughly 60 nm due to a di-phenyl amino group.
When 4-methoxy groups are substituted by a di-phenyl amino group at the phenyl rings in the 2-position of the indeno-anellated 2,2-diaryl-2H-naphtho[1,2-b]-pyranes therefrom green compounds with an absorption maximum ranging around 630 nm are expected. The substitution, by contrast, produces only a bathochromic shift by barely 30 nm. In return, the absorption band gains in width substantially; it satisfies the defined absorption conditions in the red range of the visible spectrum range. A second absorption line around 440 nm undergoes a bathochromic shift by roughly 60 nm and now forms a shoulder relative to the main band.
Other particularly preferred photochromic naphthopyrane dyes display the following chemical formula (II): ##STR2## wherein R.sub.1, R.sub.2, m and n have the same definitions as above, R.sub.5 represents the substituents defined for R.sub.4 =phenyl with o=0, 1, 2 or 3, and R.sub.3 is a non-basic amine from the above-defined group (a).
In formula (II) the non-basic amino substituent is preferably a non-substituted or substituted diaryl amino, wherein at least one aryl ring may be mono-, di- or tri-substituted. The substituents coming into question here are (C.sub.1 -C.sub.4)-alkyl, (C.sub.1 -C.sub.4)-alkoxy, phenyl, fluoro, chloro or bromo.
Preferred inventive naphthopyrane dyes are: