Photochromic fluorenopyrans with defined dibenzo[B,D]pyrano fused attachment

Abstract

The present invention relates to photochromic fluorenopyrans with defined dibenzo[b,d]pyrano fusion in accordance with general formulae (I) or (II) and to their use in plastics of all kinds, particularly for ophthalmic purposes. The photochromic compounds of the invention are distinguished by two pronounced absorption bands of the open form in the visible wavelength range, meaning that with dye molecules of this kind it is possible to replace two conventional photochromic dyes each having only one discrete absorption band. The compounds of the invention, moreover, have a very good lifetime with very high performance.

Claims

1. Photochromic fluorenopyrans with defined dibenzo[b,d]pyrano fusion in accordance with the general formulae (I) or (II): ##STR00006## where for the radicals R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8 are: (i) each independently of one another are a substituent group selected from a hydrogen atom, a (C.sub.1-C.sub.6)-alkyl radical, a (C.sub.1-C.sub.6)-thioalkyl radical, a (C.sub.3-C.sub.7)-cycloalkyl radical, which optionally contain one or more heteroatoms chosen from O or S, a (C.sub.1-C.sub.6)-alkoxy radical, a hydroxyl group, a trifluoromethyl group, bromine, chlorine, fluorine, and an unsubstituted or mono- or disubstituted phenyl, phenoxy, benzyl, benzyloxy, naphthyl, or naphthoxy radical, the substituents of the mono- or disubstituted phenyl, phenoxy, benzyl, benzyloxy, naphthyl, or naphthoxy radical are chosen from (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkoxy, bromine, chlorine, or fluorine; or (ii) (a) the radicals R.sub.1 and R.sub.2 together with the carbon atom bonded to the R.sub.1 and R.sub.2 radicals form a 3- to 8-membered, carbocyclic or heterocyclic ring which optionally (1) carries one or more-substituents chosen from the group , or (2) has one to three aromatic or heteroaromatic ring systems fused thereto, the one to three aromatic or heteroaromatic ring systems being selected independently of one another from group consisting of benzene, naphthalene, phenanthrene, pyridine, quinoline, furan, thiophene, pyrrole, benzofuran, benzothiophene, indole, and carbazole, which may be substituted in turn by one or more substituents selected from group , and, if two of the substituents carried on the 3- to 8-membered carbocyclic or heterocyclic ring formed by the R.sub.1 and R.sub.2 radicals are located on the same ring carbon atom, they may in turn form a 3- to 8-membered carbocyclic or heterocyclic ring, and/or (b) the radicals R.sub.5 and R.sub.6, together with the carbon atom bonded to the R.sub.5 and R.sub.6 radicals, form a 3- to 8-membered carbocyclic or heterocyclic ring which optionally (1) carries one or more-substituents chosen from the group , or (2) has one to three aromatic or heteroaromatic ring systems fused thereto, the one to three aromatic or heteroaromatic ring systems being selected independently of one another from group consisting of benzene, naphthalene, phenanthrene, pyridine, quinoline, furan, thiophene, pyrrole, benzofuran, benzothiophene, indole, and carbazole, which may be substituted in turn by one or more substituents selected from group , and, if two of the substituents carried on the 3- to 8-membered carbocyclic or heterocyclic ring formed by the R.sub.5 and R.sub.6 radicals are located on the same ring carbon atom, they may in turn form a 3- to 8-membered carbocyclic or heterocyclic ring, and/or (c) two adjacent radicals R.sub.3 form a fused benzene ring, which may be unsubstituted or mono- or disubstituted, in which case the substituents may be selected in turn from group ; and/or (d) two adjacent radicals R.sub.7 form a fused benzene ring, which may be unsubstituted or mono- or disubstituted, in which case the substituents may be selected in turn from group ; and when any of (iia-iid) are present, the remaining R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, or R.sub.8 groups are independently chosen from ; m and n independently of one another are an integer from 1 to 4, and B and B independently of one another are selected from one of the following groups a) or b), where a) are mono-, di-, and trisubstituted aryl radicals, where the aryl radical is selected from phenyl, naphthyl, or phenanthryl; b) are unsubstituted, mono- and disubstituted heteroaryl radicals, the heteroaryl radical being selected from pyridyl, furanyl, benzofuranyl, thienyl, benzothienyl, 1,2,3,4-tetrahydrocarbazolyl or julolidinyl, the substituents of the aryl or heteroaryl radicals in a) and b) being substituents selected from the group: (i) , (ii) group consisting of amino, mono-(C.sub.1-C.sub.6)-alkylamino, di-(C.sub.1-C.sub.6)-alkylamino, mono- and diphenylamino unsubstituted or mono- or disubstituted on the phenyl ring, piperidinyl, N-substituted piperazinyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, indolinyl, morpholinyl, 2,6-dimethylmorpholinyl, thiomorpholinyl, azacycloheptyl, azacyclooctyl, unsubstituted or mono- or disubstituted phenothiazinyl, unsubstituted or mono- or disubstituted phenoxazinyl, unsubstituted or mono- or disubstituted 1,2,3,4-tetrahydroquinolinyl, unsubstituted or mono- or disubstituted 2,3-dihydro-1,4-benzoxazinyl, unsubstituted or mono- or disubstituted 1,2,3,4-tetrahydroisoquinolinyl, unsubstituted or mono- or disubstituted phenazinyl, unsubstituted or mono- or disubstituted carbazolyl, unsubstituted or mono- or disubstituted 1,2,3,4-tetrahydrocarbazolyl and unsubstituted or mono- or disubstituted 10,11-dihydrodibenzo[b,f]azepinyl, the substituent or substituents of the mono- or disubstituted groups in the group or group being independently selected from (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkoxy, bromine, chlorine, or fluorine; or (iii) where two directly adjacent substituents of the aryl or heteroaryl radicals in a) and b) are a V(CR.sub.8R.sub.9).sub.pW moiety, where p is 1, 2 or 3, the radicals R.sub.8 and R.sub.9 each independently of one another are a substituent selected from group , and V and W independently of one another may be O, S, N(C.sub.1-C.sub.6)alkyl)-, N(C.sub.6H.sub.5), CH.sub.2, C(CH.sub.3).sub.2, or C(C.sub.6H.sub.5).sub.2, optionally two or more adjacent CR.sub.8R.sub.9 units of this V(CR.sub.8R.sub.9).sub.pW moiety are part of a benzene ring fused thereto, optionally the benzene ring in each case contains in turn one or more substituents selected from group , or V or W, together with the respectively adjacent CR.sub.8R.sub.9 unit, are a fused benzene ring, which may be unsubstituted or mono- or disubstituted, the substituents thereof are selected from group .

2. The photochromic fluorenopyrans with defined dibenzo[b,d]pyrano fusion as claimed in claim 1, where the radicals R.sub.1 and R.sub.2 independently of one another are selected from a hydrogen atom, a (C.sub.1-C.sub.6)-alkyl radical, or a (C.sub.3-C.sub.7)-cycloalkyl radical.

3. The photochromic fluorenopyrans with defined dibenzo[b,d]pyrano fusion as claimed in claim 1, where R.sub.1 and R.sub.2, together with the carbon atom bonded to these radicals, form a 5- to 7-membered carbocyclic or heterocyclic ring which optionally carries one or more substituents from group .

4. The photochromic fluorenopyrans with defined dibenzo[b,d]pyrano fusion as claimed in claim 1, where R.sub.5 and R.sub.6 independently of one another are selected from a hydrogen atom, a (C.sub.1-C.sub.6)-alkyl radical, or a (C.sub.3-C.sub.7)-cycloalkyl radical.

5. The photochromic fluorenopyrans with defined dibenzo[b,d]pyrano fusion as claimed in claim 1, which have the general formula (I).

6. The photochromic fluorenopyrans with defined dibenzo[b,d]pyrano fusion as claimed in claim 1, which have the general formula (III) below: ##STR00007##

7. The photochromic fluorenopyrans with defined dibenzo[b,d]pyrano fusion as claimed in claim 1, where the radicals B and B independently of one another are selected from the group a).

8. A plastic material comprising one or more of the photochromic fluorenopyrans with defined dibenzo[b,d]pyrano fusion as claimed in claim 1.

9. The plastic material of claim 8, wherein the plastic material is an ophthalmic lens.

Description

(1) FIG. 1 shows a corresponding synthesis scheme for preparing the inventive compounds in accordance with the above formula (I).

(2) FIG. 2 shows the UV absorption spectra of specific inventive compounds in comparison to the prior art.

(3) In one embodiment of the present invention, the radicals R.sub.1 and R.sub.2 are selected independently of one another from a hydrogen atom, a (C.sub.1-C.sub.6)-alkyl radical or a (C.sub.3-C.sub.7)-cycloalkyl radical, preferably from a (C.sub.1-C.sub.6)-alkyl radical or a (C.sub.3-C.sub.7)-cycloalkyl radical.

(4) In another embodiment of the present invention, the radicals R.sub.1 and R.sub.2, together with the carbon atom bonded to these radicals, form a 5- to 7-membered carbocyclic or heterocyclic ring which optionally carries one or more substituents from the group .

(5) In a further embodiment of the present invention, the radicals R.sub.5 and R.sub.6 are selected independently of one another from a hydrogen atom, a (C.sub.1-C.sub.6)-alkyl radical or a (C.sub.3-C.sub.7)-cycloalkyl radical, preferably from a hydrogen atom or a (C.sub.1-C.sub.6)-alkyl radical.

(6) Preferred photochromic fluorenopyrans with defined dibenzo[b,d]pyrano fusion in accordance with the present invention have the formula (I).

(7) In a further-preferred embodiment of the present invention, the photochromic fluorenopyrans with defined dibenzo[b,d]pyrano fusion have the formula (III) below.

(8) ##STR00002##
where the radicals R.sub.1, R.sub.2, B, and B are as defined above.

(9) In a further preferred embodiment, the radicals B and B are selected independently of one another from group a) as defined above.

(10) The substituents of group which have nitrogen atoms or carry amine groups are bonded via said atoms or groups to the phenyl, naphthyl or phenanthryl radical of group a).

(11) If, in respect of the substituents of the V(CR.sub.8R.sub.9).sub.pW moiety group which may be bonded to the phenyl, naphthyl or phenanthryl radical of group a) for the radicals B and/or B, two or more adjacent carbon atoms of this V(CR.sub.8R.sub.9).sub.pW moiety, in each case independently of one another, are part of a benzo ring system fused thereto, this means that in that case the two methylene carbon atoms (CH.sub.2CH.sub.2) become part of a fused ring system. If, for example, two or three benzo rings are fused, then the structural units present here may then be as follows, for example, as indicated below.

(12) ##STR00003##

(13) It will be appreciated, however, that also only one benzo ring may be present, fused via two adjacent carbon atoms of this V(CR.sub.8R.sub.9).sub.pW moiety.

(14) As already observed, the compounds of the invention, relative to the photochromic 2H-naphtho[1,2-b]pyrans known in the prior art (U.S. Pat. No. 5,645,767), which have no dibenzo[b,d]pyrano fusion, surprisingly exhibit a second strong absorption band of the open form in the visible wavelength range (see FIG. 2). Consequently, the formation of this second absorption band in the case of the compounds of the invention is unexpected.

(15) To measure the spectral properties of the compounds of the invention, 350 ppm of the photochromic dye in each case were dissolved in an acrylate monomer matrix and subjected to thermal polymerization, following addition of a polymerization initiator, with the aid of a temperature program. The transmission properties in the excited state of the plastics glasses produced accordingly (2 mm thickness) were measured subsequently in accordance with DIN EN ISO 8980-3.

(16) The structures of the compounds used and investigated in FIG. 2 are evident from the table below:

(17) TABLE-US-00001 TABLE 1 Tabular comparison of the longest-wave absorption maxima in the excited state (An = anisyl, i.e., the 4-methoxyphenyl radical) unexcited (colorless) excited (colored) Apparent B max (1) max (2) color Prior art from U.S. Pat. anisyl 550 nm violet No. 5,645,767 (without the inventive dibenzo [b,d]pyrano fusion) Inventive compound 1 anisyl 450 nm 560 nm (reddish) gray Inventive compound 2 6-methoxy- 455 nm 565 nm (brownish) 2-naphthyl gray

(18) FIG. 2 shows the UV absorption spectra of inventive compounds 1 and 2 in comparison to the prior art. The formation of a double absorption band in the case of the inventive compounds in contrast to the prior art clearly shows the influence of the dibenzo[b,d]pyrano fusion on the absorption spectrumfor a molecular structure which is otherwise the same (see FIG. 2).

(19) The present invention provides a class of new photochromic double absorption dyes which includesaccording to the choice of substituents R.sub.1 and R.sub.2not only compounds featuring extremely deep darkening and a slow lightening rate (for phototropic outdoor products and relatively high temperatures) but also compounds with a quicker lightening rate (for phototropic everyday glasses).

(20) For the synthesis of the inventive compounds, suitably substituted methylidenesuccinic anhydrides are subjected in a first step to a Friedel-Crafts reaction with suitably substituted dibenzo[b,d]pyrano derivatives (step (i)). The COOH group of the resultant intermediate is subsequently protected and this intermediate is subjected to a Michael addition with correspondingly substituted aryl-Grignard compounds (step (ii)). Following removal of the protecting group on the carboxyl, correspondingly substituted derivatives are formed via intramolecular cyclization by means of phosphoric acid (step (iii)). These substituted derivatives are subsequently reacted with suitably substituted 2-propyn-1-ol derivatives in accordance with step (iv) to give the inventive compounds. The synthesis scheme above is reproduced in FIG. 1. For preparing inventive compounds having the formula (II), the corresponding structurally isomeric dibenzopyrano derivatives are used in the course of the Friedel-Crafts reaction.

(21) The compounds of the invention can be used in plastics materials or plastics articles of any kind and form for a multiplicity of end uses for which photochromic behavior is important. It is possible here to use one dye according to the present invention, or a mixture of such dyes. By way of example, the inventive photochromic fluorenopyran dyes can be used in lenses, more particularly ophthalmic lenses, lenses for eyewear of all kinds, such as ski goggles, sunglasses, motorcycle goggles, visors of crash helmets, and the like. Furthermore, for example, the inventive photochromic fluorenopyrans with defined dibenzo[b,d]pyrano fusion may also be used as sun protection in vehicles and living spaces, in the form of windows, protective screens, covers, roofs or the like.

(22) For the production of photochromic articles of these kinds, the inventive photochromic fluorenopyrans with defined dibenzo[b,d]pyrano fusion may be applied to or embedded in a polymer material, such as an organic plastics material, by various methods described in the prior art, as already indicated in WO 99/15518.

(23) A distinction is drawn here between bulk coloring and surface coloring methods. A bulk coloring method comprises, for example, the dissolution or dispersion of the photochromic compound or compounds in accordance with the present invention in a plastics material, by the addition of the photochromic compound(s) to a monomeric material prior to polymerization, for example. Another option for producing a photochromic article is the penetration of the plastics material or materials with the photochromic compound(s) by immersion of the plastics material into a hot solution of the photochromic dye or dyes in accordance with the present invention, or else a thermal transfer method, for example. The photochromic compound(s) may also, for example, be provided in the form of a separate layer between adjacent layers of the plastics material, as part of a polymeric film, for example. Also possible, furthermore, is the application of the photochromic compound(s) as part of a coating present on the surface of the plastics material. The expression penetration in this context is intended to mean the migration of the photochromic compound(s) into the plastics material, by means, for example, of the solvent-supported transfer of the photochromic compound(s) into a polymer matrix, vapor phase transfer, or other such surface diffusion processes. Advantageously it is possible for such photochromic articles, such as eyewear lenses, for example, to be produced not only by means of the customary bulk coloring, but also, in the same way, by means of surface coloringin the case of the latter variant it is possible to achieve a surprisingly lower migration tendency. This is advantageous in particular in the case of subsequent finishing steps, sincefor example, in the case of an antireflection coating, as a result of the lesser back-diffusion under reduced pressurethere are drastic reductions in instances of layer detachment and similar defects.

(24) Overall, on the basis of the inventive photochromic fluorenopyrans with defined dibenzo[b,d]pyrano fusion, it is possible to apply or embed colorations, i.e., dyes, of any desired compatibility (compatible from a chemical point of view and in terms of color) to or in the plastics material, in order to satisfy not only esthetic considerations but also medical or fashion considerations. Accordingly, the dye or dyes specifically selected may vary as a function of the intended effects and requirements.