Spirofluorenopyrans

Details Spirofluorenopyrans Spirofluorenopyrans

2001-03-02

2001-11-13

Lambkin, Deborah C. (Department: 1626)

Compositions

Light transmission modifying compositions

Displaying color change

C546S017000, C546S269100, C549S012000, C549S330000, C549S336000, C549S337000, C549S382000, C252S586000, C544S106000

Reexamination Certificate

active

06315928

ABSTRACT:

This application is a 371 of PCT/EP00/06156 Jun. 3, 2000.
The present invention relates to specific photochromic 3H-Naphtho[2,1-b]-pyran derivatives and their use in plastics of all types, especially for ophthalmic purposes. In particular, the present invention relates to spiro compounds with a fluorene structure derived from naphthopyrans, called spirofluorenopyrans, in which an annelated ring system is joined by a spiro bond to the central carbon atom of the fluorene structure.
Various dye classes are known that change their color reversibly upon radiation with light of specific wavelengths, especially sunlight. Therefore, this means that these dye molecules transform into an excited, colored state due to the supply of energy in the form of light, which they leave again when the energy supply is interrupted, which means they return to their colorless, or at least hardly colored, normal state. These photochromic dyes include e.g., the naphthopyrans with various substituents that have already been described in the state of the art.
Pyrans, especially naphthopyrans and larger ring systems derived from them, are photochromic compounds that are still the object of intensive studies today. Although they were first submitted for a patent in the year 1966 (U.S. Pat. No. 3,567,605), it was not until the 1990's that compounds could be developed that seemed to be suitable for use in eyeglasses.
3H-Naphthopyrans derived from 2-naphthols, and their higher analog derivatives derived from them through annelation, are a group of photochromic dyes whose longest wavelength absorption maximum of the excited form lies predominantly in the spectral range from 420 nm to 500 nm and thus provide a yellow, orange or red color effect.
In this process, the bleaching rate is influenced by steric resistance or by electronic effects. The substituents of the aryl radicals on the carbon atom that is adjacent to the pyran oxygen atom are of primary importance. The steric influence of substituents in ortho-position of such aryl radicals is described, e.g., in U.S. Pat. No. 5,066,818. The electronic influence of substituents on these aryl rings or on the naphthalene radical itself affects both the absorption maximum and the bleaching rate. This is described e.g., in U.S. Pat. No. 5,520,853 and U.S. Pat. No. 5,623,005 as well as in WO 99/31082.
The 3H naphthopyrans derived from 2-naphthols known in the state of the art, and their higher analog derivatives derived by annelation are associated with disadvantages that, when used in sunglass lenses, significantly impair the wearing comfort of the person wearing the glasses. For one thing, the dyes known in the prior art frequently do not have a sufficient long wavelength absorption in the excited, as well as in the unexcited state. This also leads to problems in combinations with other photochromic dyes. In addition, there is also frequently too high of a temperature sensitivity with respect to the darkening, which at the same time means that bleaching occurs too slowly. Furthermore, the dyes described have an insufficient service life, as a result of which sunglasses of this type have an inadequate stability. The latter becomes noticeable from rapidly declining performance and/or a great deal of yellowing.
It is thus the object of the invention to provide new photochromic 3H-anphthopyrans that have improved properties in comparison to the compounds described in the state of the art. The photochromic compounds will be distinguished relative to similar compounds from the state of the art, in particular by faster kinetics in the excited form, i.e., a faster bleaching rate, and by better performance in durability testing. This object is achieved by the subjects identified in the claims. In particular, photochromic 3H-naphtho-[2,1-b]pyrans with the general formula (I) are provided:
wherein
the radicals R
1
, R
2
, R
3
and R
4
each independently represent a substituent selected from the group A, consisting of a hydrogen atom, a (C
1
-C
6
)-alkyl radical, a (C
1
-C
6
)-alkoxy radical, a (C
3
-C
7
)-cycloalkyl radical, which may contain one or more heteroatoms, a phenyl radical, a hydroxy group, bromine, chlorine and fluorine; the structural unit S together with the central spiro carbon atom, represents a saturated and/or unsaturated ring element with 5 to 8 carbon atoms, of which a maximum of one can be replaced by a heteroatom selected from the group consisting of O, S and NR
5
, wherein the radical R
5
is a straight-chain or branched-chain (C
1
-C
5
)-alkyl radical, a substituted or unsubstituted (C
5
-C
7
)-cycloalkyl radical, a substituted or unsubstituted phenyl radical or a substituted or unsubstituted benzyl radical, wherein at least one aromatic or heteroaromatic ring system is annelated to the ring element, wherein the ring system is selected from the group E, consisting of benzene, naphthalene, phenanthrene, pyridine, quinoline, furan, thiophene, pyrrole, benzofuran, benzothiophene, indole and carbazole, and the ring system can have one or more substituents from the group A; B and B′, independently of each other, are selected from one of the following groups a), b), c) or d), wherein
a) includes monosubstituted, disubstituted and trisubstitutierted aryl radicals, wherein the aryl radical is phenyl or naphthyl;
b) includes unsubstituted, monosubstituted and disubstituted heteroaryl radicals, wherein the heteroaryl radical is pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothiene-2-yl or benzothiene-3-yl;
wherein the substituents of the aryl or heteroaryl radicals in a) and b) are selected from the group consisting of hydroxy, amino, mono-(C
1
-C
6
)-alkylamino, di-(C
1
-C
6
)-alkylamino, monophenyl and diphenylamino which are unsubstituted or monosubsituted in the aromatic rings, piperidinyl, morpholinyl, carbazolyl, unsubstituted, monosubstituted and disubstituted pyrryl, (C
1
-C
6
)-alkyl, (C
1
-C
6
)-alkoxy, bromine, chlorine and fluorine, wherein said aromatic and heteroaromatic ring systems can be substituted with (C
1
-C
6
)-alkyl, (C
1
-C
6
)-alkoxy, bromine, chlorine and fluorine;
c) includes structural units with the following formulas (V) and (W):
wherein
Y and Z are independently O, S, CH, CH
2
or NR
9
, wherein the R
9
radical is selected from the group D, consisting of (C
1
-C
6
)-alkyl, (C
1
-C
6
)-acyl and hydrogen, the radicals R
6
and R
7
independently represent hydrogen and/or a (C
1
-C
6
)-alkyl radical, and the radical R
8
is a substituent from the group A, wherein n is 1, 2 or 3, with the proviso that if Y in formula (V) is NR
9
, Z is carbon, or
d) B and B′ together form an unsubstituted, monosubstituted or disubstituted fluorene-9-xylene radical or a saturated hydrocarbon radical, which is C
3
-C
12
spiromonocyclic, C
7
-C
12
spirobicyclic and/or C
7
-C
12
spirotricyclic, wherein the fluorene substituents are selected from the group A.
In a preferred embodiment, the structural unit S in the foregoing formula (I), together with the central spirocarbon atom, forms a substituted or unsubstituted fluorene, xanthene, thioxanthene or dihydroanthracene unit.
Preferred photochromic 3H-naphtho[2,1-b]pyrans have the following general formulas (II):
wherein R
1
, R
2
, R
3
and R
4
are defined as above, and X stands for —CH
2
—, —O—, —S— or a C—C single bond between the phenyl rings.
In an especially preferred embodiment, B and B′ in the formula (II) set forth above are independently monosubstituted, disubstituted and trisubstituted aryl radicals wherein the aryl radical is a phenyl radical or a naphthyl radical in each case.
Especially preferred compounds according to the invention include:
Spiro-9-fluoreno-13′-[6-methoxy-2-(4-methoxyphenyl)-2-phenyl-indeno[2,1-f]-naphtho[2,1-b]pyran],
Spiro-9-xantheno-13′-[6-methoxy-2-(4-methoxyphenyl)-2-phenyl-indeno[2,1-f]-naphtho[2,1-b]pyran],
Spiro-9-thioxantheno-13′-[6-methoxy-2-(4-methoxyphenyl)-2-phenyl-indeno[2,1-f]-naphtho[

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