Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2001-07-10
2003-12-09
Shah, Mukund J. (Department: 1624)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Heterocyclic carbon compounds containing a hetero ring...
C514S453000, C514S468000, C549S382000, C549S432000, C549S381000
Reexamination Certificate
active
06660727
ABSTRACT:
The present invention relates to photochromic indenochromene derivatives and the use thereof in plastics of all types, particularly for ophthalmic applications. In particular, the present invention relates to specific photochromic heterocyclically annellated indeno[2,1-f]chromene derivatives and specific photochromic,\ heterocyclically annellated indeno[1,2-h]chromene derivatives.
There are various known classes of dyes that reversibly change their color when irradiated with light of certain wavelengths, particularly sun light. This is due to the fact that these dye molecules change into an excited colored state when supplied with energy in the form of light. They leave this state again when the energy supply is interrupted, and thereby return to their colorless or at least their hardly colored normal state. These photochromic dyes include, for instance, naphthopyrans with various substituents, which have previously been described in the prior art.
Pyrans, especially naphthopyrans and larger ring systems derived therefrom, are photochromic compounds, which to this day continue to be the subject of intensive research. Although a first patent application (U.S. Pat. No. 3,567,605) was filed as early as 1966, it was not until the nineties that compounds, which appeared suitable for the use in eyeglasses, were developed.
Heterocyclically annellated benzopyrans are known, for instance, from U.S. Pat. No. 5,631,720. Relatively minor structural changes in the heterocycle have an enormous influence on the lightening rate (a factor of about 5). The compounds described in U.S. Pat. No. 5,631,720, however, have the drawback that they only cover the range from about 430 to 450 nm (absorption maximum of the excited form), i.e., only orange to red tints may be obtained.
WO 98/28289 describes compounds that supply dull red to red-violet tints, but the bathochromic effect of the substitution compared to 2 methyl groups is low at 25 nm. The influence on the lightening kinetics is negative, with the lightening rate being slightly retarded in all cases. The specified structure allows only substitutions that have hardly any effect on the lightening rate. Fluoreno- and naphthopyrans, which provide red-violet to green tints are known, for instance, from WO 99/15518 and DE 198 24 278 or DE 199 02 771. They are distinguished by their excellent long-term stability and good temperature stability (little dependence of the darkening depth on the temperature). The possible substitutions described therein, however, allow comparatively little latitude with respect to the lightening rate.
The introduction of a heterocyclic component by replacing the central C atom of the fluorene structure by N-R as proposed in WO 99/23071 results in compounds whose absorption maximum in the non-excited state is around or above 400 nm, i.e., clearly within the visible range. However, since the absorption extends beyond the maximum far into the violet and blue spectral region, compounds with a strong yellow tint in their non-excited state are obtained. They are therefore not suitable for use in eyeglasses.
Likewise disadvantageous is the introduction of a heterocyclic unit on the two benzene rings of the indenonapththopyran structure as described in U.S. Pat. No. 5,698,141 and U.S. Pat. No. 5,723,072. The darkening depth of these compounds (usually given as colorability A
0
) is low compared to the compounds of U.S. Pat. No. 5,631,720. In addition, compounds with very many annellated rings are obtained, which for the most part clearly absorb in the visible range in their non-excited state, i.e., the compounds are yellow in their non-excited state. Insofar as the compounds in their excited state show an absorption maximum in the range of 576-600 nm, i.e., a blue excitation color, green compounds are obtained, which are generally not very suitable for use in eyeglasses.
U.S. Pat. No. 5,645,767 and U.S. Pat. No. 5,869,658 describe the positive effect on the photochromic properties of indeno fusing to the f-side of the naphthopyran system. The compounds generally show longerwave absorption and increased darkening performance. EP-A-0 987 260 and DE 199 30 290 describe systems in which the indene unit is integrated in a spiro structure. These compounds are distinguished by excellent durability and rapid lightening rates with simultaneous good darkening performance.
The darkening tint of the aforementioned systems described in the prior art depends primarily on the substituents at the 3-position in 3H-naphtho[2,1-b]pyrans or, on the substituents at the 2-position in 2H-naphtho[1,2-b]pyrans. For technical applications, cosmetically neutral darkening tints, such as brown or gray, are preferred. The aforementioned compound systems have strong tints, however, so that only mixtures of different dyes can be used.
Thus, the object of the present invention is to provide novel photochromic systems, which, in contrast to the compounds thus far available in the prior art, should have broader absorption bands for duller tints, i.e., they should, in particular, exhibit cosmetically neutral darkening tones. In addition, these compounds should exhibit rapid lightening with simultaneous good darkening performance and good durability.
This object is achieved by the substances characterized in the claims. In particular, photochromic heterocyclically annellated indeno[1,2-h]chromenes having the general formula (I) and indeno[2,1-f]chromenes having the general formula (II) are provided:
wherein
the groups R
1
and R
2
independently from each other represent a substituent selected from group A consisting of hydrogen, fluorine, chlorine, bromine, a hydroxy group, a (C
1
-C
6
) alkyl group, a (C
1
-C
6
) alkoxy group, a (C
3
-C
7
) cycloalkyl group which may have one or more heteroatoms, a (C
1
-C
6
) acyl group, an unsubstituted or monosubstituted phenyl group and an unsubstituted or monosubstituted benzyl group, wherein their substituents are selected from the group consisting of a (C
1
-C
6
) alkyl group and a (C
1
-C
6
) alkoxy group;
or the groups R
1
and R
2
together represent an annellated, unsubstituted, monosubstituted or disubstituted benzo or pyrido ring whose substituents are selected from group A;
group R
3
represents a substituent selected from among hydrogen, a (C
1
-C
6
) alkyl group and —OM, wherein M is a substituent selected from group A;
group R
4
is a substituent selected from among hydrogen, a hydroxy group, a (C
1
-C
6
) alkyl group, a (C
1
-C
6
) alkoxy group, a (C
3
-C
7
) cycloalkyl group, a (C
1
-C
6
) acyl group, a respectively unsubstituted, mono-, di- or trisubstituted phenyl group, benzyl group, naphthyl group, phenanthryl group, pyrenyl group, quinolyl group, isoquinolyl group, benzofuranyl group, thienyl group, benzothienyl group, dibenzofuranyl group, dibenzothienyl group, carbazolyl group or indolyl group, wherein their substituents are selected from group A, a (C
1
-C
6
)-&ohgr;-phenylalkyl group and a (C
1
-C
6
)-&ohgr;-phenoxyalkyl group, wherein the phenyl ring in the &ohgr;-position in turn may be part of another photochromic pyran system;
or the groups R
3
and R
4
including the central spiro carbon atom together represent a saturated and/or unsaturated ring member with 5 to 8 carbon atoms of which maximally one may be substituted by a heteroatom selected from the group consisting of O, S and NR
5
, wherein group R
5
is selected from group A, and wherein at least one aromatic or heteroaromatic ring system is fused to the ring member, wherein the ring system is selected from group E consisting of benzene, naphthalene, phenanthrene, pyridine, quinoline, furan, thiophene, pyrrole, benzofuran, benzothiophene, indole and carbazole, and the ring system may have one or more substituents from group A;
the annellated heterocycle (Het) represents a 5 or 6-membered heteroaromatic ring cycle corresponding to the following general formulas:
wherein Y is selected from among oxygen, sulfur and NR
5
, and Z, U, V and W independently from each other are
Mann Claudia
Melzig Manfred
Weigand Udo
Crowell & Moring LLP
Patel Sudhaker B.
Rodenstock GmbH
Shah Mukund J.
LandOfFree
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