Photochromic naphthopyrans

Details Photochromic naphthopyrans Photochromic naphthopyrans

2000-05-18

2002-01-29

Rotman, Alan L. (Department: 1625)

Compositions: ceramic

Ceramic compositions

Glass compositions, compositions containing glass other than...

C546S017000, C546S018000, C549S059000, C549S341000, C549S327000, C549S049000, C549S383000, C549S384000, C548S409000

Reexamination Certificate

active

06342459

ABSTRACT:

BACKGROUND OF THE INVENTION
The present invention relates to photochromic 2H-naphtho[1,2-b]pyrans as well as to their use in synthetic resins of all types, particularly for ophthalmic purposes. In particular, the present invention relates to photochromic naphthopyran compounds, for which a further ring system is bonded to the f side of the naphthopyran.
Different classes of dyes are known which, when irradiated with light of particular wavelengths, particularly sunlight, change their color reversibly. This is due to the fact that, because energy is supplied in the form of light, these dye molecules change over into a stimulated colored state, which they leave once again when the supply of energy is interrupted in order to return to their colorless or at least hardly colored normal state. These photochromic dyes include, for example, the naphthopyrans, which have already been described with different substituents in the state of the art.
Pyrans, especially naphthopyrans and larger ring systems derived from these, are photochromic compounds, which until now have been the object of intensive investigations. Although the first patent was filed already in 1966 (U.S. Pat. No. 3,567,605), compounds, which are suitable for use in eyeglass lenses, were developed only in the 1990s.
A suitable class of pyran compounds is, for example, the 2,2-diaryl-2H-naphtho[1,2-b]pyrans. 2H-Naphtho[1,2-b]pyrans generally are orange to red photochromic compounds, which are decolorized very slowly after they have become darker, such as the Comparison Examples 4 and 5 and the Comparison Example A in U.S. Pat. No. 5,066,818.
Attempts were made to achieve improvements here by substituting the carbon atoms in the 5 and 6 positions of the naphthalene part in the naphthopyran. Compounds of this type are described, for instance, in U.S. Pat. Nos. 5,458,814, 5,573,712, 5,650,098, 5,656,206, 5,658,500 and 5,658,501 and in WO 98/04937. Since there was a need for further improvement, 2H-naphtho[1,2-b]pyran systems were described for the first time in U.S. Pat. No. 5,651,923. At the f side of the naphthopyran, that is, at the naphthalene part, these compounds have condensed benzothieno, benzofurano or indolo system, the benzothieno, benzofurano and indolo systems being bound to the naphthalene via the heterocyclic portion. It is disadvantage of the three naphthofuro[2′,3′:3,4]- and naphthofuro[3′,2′:3,4]-naphtho[1,2-b]pyrans of Examples 4, 5 and 6 in U.S. Pat. No. 5,651,923, that these decolorize very slowly and/or have a very slight photochromic efficiency (&Dgr;OD). Indolonaphthopyrans also decolorize similarly slowly. In the WO 99/20619, pentahydrophenanthro[9,10-b]pyrans and tetrahydrocyclopenta[c]naphtho[1,2-b]pyrans are described, which also have the disadvantage that their decolorizing rate is slow and therefore unsatisfactory for practical use in sunglasses.
In addition, an expensive and long synthesis route is required for the systems described. Furthermore, due to the possibility of conjugating with a further aromatic ring (system), a bathochromic shift relative to the basic absorption of the naphthopyran system may be observed, which frequently is undesirable. This applies likewise for the compounds in U.S. Pat. No. 5,645,767, which relate exclusively to indeno[2,1-f]naphtho[1,2-b]pyrans. Further continuations may be found in U.S. Pat. Nos. 5,698,141 and 5,723,072, which additionally have condensed unsubstituted, monosubstituted or disubstituted heterocyclic systems.
The known compounds are however associated with disadvantages, which affect the wearing comfort of the eyeglasses when these photochromic dyes are used in sunglass lenses. The known dyes have an inadequate long-wave absorption in the excited as well as in the not-excited state. This leads to problems even when these compounds are combined with other photochromic dyes. The temperature sensitivity with respect to the darkening is too high. At the same time, the decolorization frequently is too slow. In addition, the dyes described have an inadequate service life and, with that, in insufficient durability in sunglass lenses. The latter becomes noticeable in a rapidly abating efficiency and/or in severe yellowing. Moreover, the synthesis of the compounds, described in the state of the art, usually is expensive and lengthy and generally does not permit further optically interesting properties, such as a nonlinearity, to be incorporated into the respective structures.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to make available new photochromic compounds, which have improved properties in comparison to the structures described in the state of the art. The photochromic compounds are to be distinguished particularly owing to the fact that they have faster kinetics in the light-stimulated state, than do comparable compounds from the state of the art, and exhibit a better behavior in the service life test.
This objective is accomplished by the objects, characterized in the claims. In particular, photochromic 2H-naphtho-[1,2-b]pyrans of the general formula (I) are made available
wherein
X represents a ring element with 2 to 4 saturated and/or unsaturated carbon atoms, of which not more than one can be replaced by a hetero atom, selected from the group comprising O, S and NR
4
, R
4
being a linear or branched C
1
to C
6
alkyl group, a substituted or unsubstituted C
5
to C
7
cycloalkyl group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group;
R
1
is a substituent, selected from group A, comprising a C
1
to C
6
alkyl group, a C
1
to C
6
alkoxy group, a C
3
to C
7
cycloalkyl group, which may have one or more hetero atoms, a phenyl group, a hydroxy group, bromine, chlorine and fluorine, n being 0, 1 or 2;
R
2
, R
3
independently of one another are groups, selected from group G, comprising hydrogen, hydroxy, a C
1
to C
6
alklyl group, a C
1
to C
6
alkoxy group, a C
3
to C
7
cycloalkyl group, an unsubstituted, monosubstituted and disubstituted phenyl group and an unsubstituted, monosubstituted and disubstituted naphthyl group and the aromatic groups, selected from group C, comprising benzene, naphthalene, phenanthrene, pyridine, quinoline, furan, thiophene, pyrrol, benzofuran, benzothiophene, indol and carbazol, the substituent or substituents of the aforementioned aromatic groups being selected from group A;
or R
2
and R
3
together, with inclusion of the spiro carbon atom, form a 5-membered to 11-membered ring, to which one or several aromatic or heteroaromatic ring systems may be annellated, the aromatic or heteroaromatic ring system or systems being one of the aforementioned group C;
or R
2
and R
3
together represent an oxygen atom with formation of a carbonyl group;
with the proviso that, when X is —(CH
2
)
2
— or —(CH
2
)
3
— and R
2
and R
3
are not at the same time hydrogen;
B, B′ are selected independently of one another from the following groups a), b) or c), wherein
a) are mono-, di- and trisubstituted aryl groups, the aryl group being phenyl or naphthyl;
b) are unsubstituted, mono- and disubstituted heteroaryl groups, the heteroaryl group being pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl or benzothien-3-yl; the substituents of the aryl groups or the heteroaryl groups in a) and b) being selected from a group comprising hydroxy, amino, mono-(C
1
to C
6
)-alkylamino, di-(C
1
to C
6
)-alkylamino, mono- and diphenylamino, unsubstituted, monosubstituted or disubstituted at the aromatic ring, piperidinyl, morpholinyl, carbazolyl, unsubstituted, monosubstituted and disubstituted pyrryl, C
1
to C
6
alkyl, C
1
to C
6
alkoxy, bromine, chlorine and fluorine, wherein the aforementioned aromatic and heteroaromatic ring systems can be substituted with C
1
to C
6
alkyl, C
1
to C
6
alkoxy, bromine, chlorine and fluorine;
c) are structure units with the following for

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