H-annellated benzo[f]chromenes

Organic compounds -- part of the class 532-570 series – Organic compounds – Four or more ring nitrogens in the bicyclo ring system

Reexamination Certificate

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Details

C544S111000, C252S586000, C546S196000

Reexamination Certificate

active

06686468

ABSTRACT:

The present invention relates to specific photochromic h-annellated benzo[f]chromene derivatives and their use in synthetic resins of all types, especially for ophthalmic applications. In particular, the present invention relates to photochromic compounds derived from benzo[f]chromenes, which in their open form have particularly long-wave absorption maxima making it possible to achieve violet to blue tints if used in phototropic glasses.
Various classes of dyes that reversibly change their color when irradiated with light of certain wavelengths, particularly sunlight, are known in the art. 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. When the energy supply is interrupted, they leave this state again and return to their colorless or at least hardly colored normal state. These photochromic dyes include, for instance, the naphthopyrans, which have already been described in the prior art with various substituents.
Pyrans, especially naphthopyrans and larger ring systems derived therefrom are photochromic compounds that even today are the subject of intensive investigations. Although a patent application was filed for them as early as 1966 (U.S. Pat. No. 3,567,605), it was not until the nineties that compounds that appeared suitable for use in eyeglasses were developed.
On the one hand, the prior art dyes frequently do not have sufficiently long-wave absorption in the excited or in the unexcited state. This causes problems also in combinations with other photochromic dyes. On the other hand, they are also often excessively temperature sensitive with respect to darkening and brightening is simultaneously too slow. In addition, the described dyes have an insufficiently long service life. Consequently, this type of sunglasses is not sufficiently durable. The latter is noticeable in their rapidly deteriorating performance and/or strong yellowing.
3H-naphthopyrans derived from 2-naphthols and their higher analog derivatives derived therefrom by annellation are a group of photochromic dyes whose longest-wave absorption maximum in the excited form is primarily in the spectral range of 420 nm to 500 nm. As a result they give a yellow, orange or red color impression (see U.S. Pat. No. 5,869,658 and U.S. Pat. No. 6,022,495). For neutrally darkening phototropic glasses, however, powerful violet to blue photochromic dyes are required. Violet to blue photochromic dyes that are currently available in the prior art stem from the class of the spiroxazines, fulgides or 2H-naphtho[1,2-b]pyrans. Spiroxazine dyes, however, are typically disadvantageous with respect to their high-temperature performance, while fulgide dyes do not have satisfactory properties for use in sunglasses regarding their service life and 2H-naphtho[1,2-b]pyrans regarding their brightening rate.
Thus, the object of the present invention is to provide novel photochromic dyes with improved properties compared to the compounds described in the prior art. Compared to comparable prior art compounds, the photochromic compounds are to be distinguished especially by longer-wave absorption in the excited state and at the same time are to exhibit good kinetic and service life properties, i.e., faster brightening rates and good behavior in the durability test.
This object is attained by the subjects characterized in the claims.
Specifically provided are photochromic h-annellated benzo[f]chromenes having the general formula (I):
where
n and m independently represent 0, 1 or 2,
the radicals R
1
, R
2
, R
3
and R
4
each independently represent a substituent selected from
the group &agr; consisting of a hydrogen atom, a (C
1
-C
6
) alkyl radical, a (C
3
-C
7
) cycloalkyl radical, which can have one or more heteroatoms, a (C
1
-C
6
) alkoxy radical, a hydroxy group, a trifluoromethyl group, bromine, chlorine and fluorine; the group &bgr; consisting of an unsubstituted, monosubstituted or disubstituted phenyl, phenoxy, benzyl, benzyloxy, naphthyl or naphthoxy radical, wherein the substituents may be selected from the group &agr; and phenyl;
the group &khgr; wherein the radicals R
1
and R
2
or R
3
and R
4
each form an —A—(CH
2
)
k
—B— group bound to the aromatic ring where k=1 or 2, wherein A and B independently are selected from oxygen, sulfur, CH
2
, C(CH
3
)
2
or C(C
6
H
5
)
2
, and wherein a benzo ring may in turn be annellated to said —A—(CH
2
)
k
—B— group;
the group &dgr; consisting of an unsubstituted, monosubstituted or disubstituted amino group, wherein the amine substituents may be selected from a (C
1
-C
6
) alkyl radical, a (C
3
-C
7
) cycloalkyl radical, a phenyl or benzyl radical unsubstituted or substituted with one or more substituents from the group &agr;, an N-morpholine group, an N-thiomorpholine group, an N-piperidine group, an N-azacycloheptane group, an N-piperazine group, an N-(N′-(C
1
-C
6
-alkyl)piperazine group, an N-pyrrolidine group, an N-imidazolidine group, an N-pyrazolidine group, an N-aziridine group, an N-azetidine group, an N-indoline group, an N-carbazole group, an N-phenothiazine group, an N-phenazine group, an N-phenoxazine group, an N-tetrahydroquinoline group, and an N-tetrahydroisoquinoline group,
the group &egr;, wherein the radicals R
1
and R
2
, i.e., R
1
/R
2
, or R
3
and R
4
, i.e., R
3
/R
4
, respectively, together form a —D—(CH
2
)
k
—E— group bound to the benzo ring where k=1 or 2, wherein independently D is selected from N(CH
3
) or N(C
6
H
5
) and E from oxygen, sulfur, CH
2
, C(CH
3
)
2
, C(C
6
H
5
)
2
, N(CH
3
) or N(C
6
H
5
), and wherein a benzo ring may in turn be annellated to this —D—(CH
2
)
k
—E— group, or
the group &phgr; wherein the radicals R
1
and R
2
or R
3
and R
4
, respectively, form a julolidinyl unit together with the benzene ring to which they are bound,
provided that within the radicals R
1
, R
2
, R
3
and R
4
or within R
1
/R
2
and R
3
/R
4
at least one is selected from the aforementioned groups &dgr;, &egr; and &phgr;, i.e., at least one of the radicals R
1
, R
2
, R
3
and R
4
or R
1
/R
2
and R
3
/R
4
is an electron-donating substituent from the class of the nitrogen donor substituents;
the radicals R
5
, R
6
, R
7
and R
8
, respectively, independently are selected from the group &agr; and phenyl, or the radicals R
5
and R
6
together with the radical R
3
of the directly adjacent benzo ring form an unsubstituted, monosubstituted or disubstituted benzo or pyrido ring annellated thereto, whose substituents may be selected from the group &agr; and phenyl, or, if m or n is 2, the directly adjacent radicals R
5
and R
6
of two adjacent CR
5
R
6
units or the directly adjacent radicals R
7
and R
8
of two adjacent CR
7
R
8
units together form an annellated, unsubstituted, monosubstituted or disubstituted benzo or pyrido ring whose substituents may be selected from the group &agr; and phenyl, or the radicals R
5
and R
6
and/or the radicals R
7
and R
8
together represent a (C
3
-C
7
) cycloalkyl radical, which can have one or more heteroatoms, such as, for instance, oxygen, nitrogen or sulfur, wherein a benzo ring may be annellated to this cycloalkyl radical;
X is selected from O, S, CR
9
R
10
or NR
11
, wherein the radical R
11
can be hydrogen, cyano, (C
1
-C
6
) alkyl, (C
3
-C
7
) cycloalkyl or phenyl, and the radicals R
9
and R
10
independently are selected from the group &agr; and phenyl, or the radicals R
9
and R
10
together represent a (C
3
-C
7
) cycloalkyl radical, which can have one or more heteroatoms, or, if X is CR
9
R
10
, the radicals R
9
and R
10
together with the radicals R
5
and R
6
or R
7
and R
8
of a directly adjacent CR
5
R
6
unit or CR
7
R
8
unit can also stand for an unsubstituted, monosubstituted or disubstituted benzo or pyrido ring annellated to the X—C(R
5
R
6
) or X—C(R
7
R
8
) bond whose substituents may be selected from the group &agr; and phenyl;
B and B′ independently are selected from one of the following groups a), b), c) or d), wherein they
a)

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