Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2000-08-24
2002-05-21
Solda, T. A. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C359S244000, C548S418000
Reexamination Certificate
active
06392043
ABSTRACT:
The present invention relates to novel [indole]naphthopyran compounds which have, in particular, photochromic properties. The invention also relates to:
compounds, synthesis intermediates, which are useful in the preparation of said [indole]naphthopyrans;
the preparation of said synthesis intermediates and said [indole]naphthopyrans;
photochromic compositions and photochromic ophthalmic articles (lenses for example) which contain said [indole]naphthopyrans.
The photochromic compounds are capable of changing color under the influence of a poly- or mono-chromatic light (UV for example) and of returning to their initial color when the luminous irradiation ceases, or under the influence of temperature and/or a poly- or mono-chromatic light different from the first.
The photochromic compounds find applications in various fields, e. g. for the manufacture of ophthalmic lenses, contact lenses, solar protection glasses, filters, camera optics or photographic apparatus optics or other optical devices and observation devices, glazing, decorative objects, bill elements or even for information storage by optical inscription (coding).
In the field of ophthalmic optics, and in particular the spectacles trade, a photochromic lens which comprises one or more photochromic compounds must have:
a high transmission in the absence of ultraviolets,
a low transmission (high colorability) under solar irradiation,
adapted coloration and discoloration kinetics,
a tint acceptable to the consumer (gray or brown preferably) with preferably a maintenance of the chosen tint during the coloration and the discoloration of the lens,
a maintenance of the performances, the properties, within a temperature range of 0-40° C.,
a significant durability, since these objectives sought after are sophisticated corrective lenses and therefore expensive.
These lens characteristics are in fact determined by the active photochromic compounds which they contain; compounds which must furthermore be perfectly compatible with the organic or inorganic support which constitutes the lens.
Moreover, it is to be noted that obtaining a gray or brown tint may necessitate the use of at least two photochromes of different colors, i. e. having distinct maximal absorption wavelengths in the visible. This association further imposes other requirements of the photochromic compounds. In particular, the coloration and discoloration kinetics of the (two or more) associated active photochromic compounds must be essentially identical. The same applies for their stability with time and also for their compatibility with a plastic or inorganic support.
Amongst the numerous photochromic compounds described in the prior art, benzopyrans and naphthopyrans may be cited which are described in patents or patent applications U.S. Pat. Nos. 3,567,605, 3,627,690, 4,826,977, 5,200,116, 5,238,981, 5,411,679, 5,429,744, 5,451,344, 5,458,814, WO-A-95 05382, FR-A- 2,718,447, WO-A-96 14596, WO-A-97 21698 and in the Research Disclosure No. 36144, which are of the formula below:
These compounds claim to satisfy the specifications defined above. In reality, if these compounds really do have one or more of the basic properties sought after, such as a high transmission in the absence of ultraviolets and a high colorability under solar irradiation, none of the compounds described hitherto have the complete combination of the properties sought after which are necessary for the production of satisfactory articles which may be manufactured industrially. In particular, none of these compounds is intrinsically gray or brown and the necessity of using an additional photochrome in order to obtain one of these two tints does subsist.
Several compounds having two intense and more or less complementary absorption bands in the visible have been described (WO-A-96 14596). These two bands are generally situated in the yellow/orange and in the violet/blue. However, the first band (yellow) is far less intense and the stability of these compounds vis-a-vis the photochromic ageing is far from being satisfactory.
Although the general formula IA of the patent application WO-A-97 21698 includes [indole]naphthopyrans, such [indole]naphthopyrans are not described in this prior art document insofar as said document does not indicate any method of synthesizing said [indole]napthopyrans. [Indeno]naphthopyrans are effectively described in said document but no means of access to the [indole]naphthopyrans is suggested. It is to the credit of the Applicant to have proposed such a means of access (an efficient synthesis method) and to have discovered that this type of compound possesses particularly advantageous photochromic properties. More specifically, they possess a particularly intense first band in the yellow/orange, a second band of high &lgr;
max
and a high colorability, even at 40° C., associated with rapid discoloration kinetics.
Thus, the object of the present invention is [indole]naphthopyran compounds of formula (I):
in which:
R
1
and R
2
, identical or different, independently represent:
hydrogen,
a linear or branched alkyl group having 1 to 12 carbon atoms,
a cycloalkyl group having 3 to 12 carbon atoms,
an aryl or heteroaryl group having 6 to 24 carbon atoms or 4 to 24 carbon atoms respectively in its basic structure and at least one heteroatom selected from sulfur, oxygen and nitrogen; said basic structure optionally being substituted with at least one substituent selected from:
a halogen and notably fluorine, chlorine and bromine,
a linear or branched alkyl group having 1 to 12 carbon atoms,
a linear or branched alkoxy group having 1 to 12 carbon atoms,
a linear or branched haloalkyl or haloalkoxy group corresponding respectively to the (C
1
-C
12
) alkyl and (C
1
-C
12
) alkoxy groups above substituted with at least one halogen atom and notably a fluoroalkyl group of this type,
a linear or branched alkenyl group having 2 to 12 carbon atoms and notably a vinyl group or an allyl group,
an —NH
2
group,
an —NHR group, R representing a linear or branched alkyl group having 1 to 6 carbon atoms,
R′ and R″, identical or different, representing independently a linear or branched alkyl group having 1 to 6 carbon atoms or representing, together with the nitrogen atom to which they are bound, a 5- to 7-membered ring which can comprise at least one other heteroatom selected from oxygen, sulfur and nitrogen, said nitrogen optionally being substituted with an R′″ group, a linear or branched alkyl group, having 1 to 6 carbon atoms,
a methacryloyl group or an acryloyl group,
an epoxy group of formula:
in which n=1, 2 or 3,
an aralkyl or heteroaralkyl group, the linear or branched alkyl group having 1 to 4 carbon atoms and the aryl and heteroaryl groups having the definitions given above, or
said two substituents R
1
and R
2
together form an adamantyl, a norbornyl, a fluorenylidene, a di(C
1
-C
6
)alkylanthracenylidene or a spiro(C
5
-C
6
)cycloalkyl-anthracenylidene group; said group optionally being substituted with at least one of the substituents listed above for R
1
, R
2
: aryl or heteroaryl group;
R
3
and R
4
, identical or different, independently represent:
hydrogen,
a halogen, and notably fluorine, chlorine or bromine,
a linear or branched alkyl group having 1 to 12 carbon atoms (advantageously 1 to 6 carbon atoms),
a cycloalkyl group having 3 to 12 carbon atoms,
a linear or branched alkoxy group, having 1 to 12 carbon atoms (advantageously 1 to 6 carbon atoms)
a haloalkyl, a halocycloalkyl or haloalkoxy group corresponding respectively to the alkyl, cycloalkyl, alkoxy groups above, substituted with at least one halogen atom, notably selected from fluorine, chlorine and bromine,
an aryl or heteroaryl group having the same definition as that given above for R
1
, R
2
,
an aralkyl or heteroaralkyl group, the linear or branched alkyl group having 1 to 4 carbon atoms and the aryl and heteroaryl groups having the same definitions as those given ab
Bourchteine Konstantine
Breyne Olivier
Corning S.A.
Nwaneri Angela N.
Rogalskyj Peter
Solda T. A.
Wright Sonya
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