Compositions – Light transmission modifying compositions – Displaying color change
Reexamination Certificate
2000-11-03
2002-06-04
Tucker, Philip (Department: 1712)
Compositions
Light transmission modifying compositions
Displaying color change
C351S163000, C549S389000, C549S382000, C549S383000, C549S384000, C549S024000, C549S025000
Reexamination Certificate
active
06398987
ABSTRACT:
This application claims the benefit of priority of French Application Serial Number 99 13790 filed Nov. 4, 1999 entitled Naphthopyrans having a Perfluoroalkyl Substituent in Position 5, Preparation and Compositions and Matrices Containing Them of Breyne et al.
The present invention relates to novel naphthopyran-type compounds which have, in particular, photochromic properties. The invention also relates to photochromic compositions and photochromic ophthalmic articles (lenses for example) which contain said naphthopyrans. The invention also covers the preparation of these novel compounds.
The photochromic compounds are capable of changing colour under the influence of a poly- or mono-chromatic light (UV for example) and of returning to their initial colour 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 colourability) under solar irradiation,
adapted coloration and discoloration kinetics,
a tint acceptable to the consumer (grey 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, even hybrid support which constitutes the lens.
Moreover, it is to be noted that obtaining a grey or brown tint may necessitate the use of at least two photochromes of different colours, i.e. having distinct maximal absorption wavelengths in the visible. This combination further imposes other requirements of the photochromic compounds. In particular, the coloration and discoloration kinetics of the (two or more) combined 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. No. 3,567,605, U.S. Pat. No. 3,627,690, U.S. Pat. No. 4,826,977, U.S. Pat. No. 5,200,116, U.S. Pat. No. 5,238,981, U.S. Pat. No. 5,411,679, U.S. Pat. No. 5,429,744, U.S. Pat. No. 5,451,344, U.S. Pat. No. 5,458,814, U.S. Pat. No. 5,514,817, U.S. Pat. No. 5,651,923, U.S. Pat. No. 5,645,767, U.S. Pat. No. 5,698,141, U.S. Pat. No. 5,783,116, WO-A-95 05382, FR-A-2,718,447, WO-A-96 14596, WO-A-97 21698, WO-A-98 42693, WO-A-98 42695, and WO-A-98 57943 which are of the reduced formulae below:
It is well known to the person skilled in the art that the R
3
substituents in the &agr; position of the pyran ring enables the discoloration kinetics of the photochromes to be accelerated.
Research disclosure RD 36144 describes naphthopyrans of the following general structure:
U.S. Pat. No. 5,656,206 describes naphthopyrans of the following general structure:
U.S. Pat. No. 5,783,116 describes naphthopyrans of the following general structure:
U.S. Pat. No. 5,458,814 describes naphthopyrans of the following general structure:
U.S. Pat. No. 5,888,432 of the Applicant describes naphthopyrans of the following general formula:
In general, the groups in the R
3
position are alkyl groups, ester groups, aryl groups or alkyl groups substituted with a hydroxy.
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. In particular, none of these compounds is intrinsically grey or brown and the necessity of using an additional photochrome in order to obtain one of these two tints does subsist.
Although the general formula of several patents cited contain “haloalkyl” groups, thus including perfluoroalkyls in the various positions of the naphthyl ring of the naphthopyrans, no access route is suggested and even no perfluoroalkylated product is specifically described. Classically, the access to the naphthopyrans sought after necessitates an intermediate of the <<1-naphthol>> type with a hydrogen in position 2 and a fluoroalkyl in position 3. In the literature, only two products are found which are of this definition, these products are obtained by difficult and costly routes (product A: Taguchi et al. Tetrahedron Lett. 1988, 29, 5765 and product B: U.S. Pat. No. 5,420,333).
In this context, it is to the credit of the inventors:
to have selected compounds of the naphthopyran type, which have a perfluoroalkyl group in the a position of the pyran ring (group X of the formula (I) below) and which possess particularly advantageous photochromic properties. Said compounds possess rapid discoloration kinetics and &lgr;
max
values in the UV and/or the visible which are lower than those of the analogous compounds;
to propose a simple and not very costly access to said compounds, as well in fact as an access route to certain intermediates of naphthol type (compounds of structure II below).
Thus, according to a first of its aspects, the present invention relates to compounds of the following formula (I):
in which:
X is a linear or branched perfluoroalkyl comprising 1 to 6 carbon atoms;
R
1
and R
2
, which are identical or different, independently represent:
hydrogen,
a linear or branched alkyl group comprising 1 to 12 carbon atoms,
a cycloalkyl group comprising 3 to 12 carbon atoms,
an aryl or heteroaryl group comprising in its basic structure 6 to 24 carbon atoms or 4 to 24 carbon atoms respectively and at least one heteroatom selected from sulphur, oxygen and nitrogen; said basic structure being optionally substituted with at least one substituent selected from the whole of the substituents given below:
a halogen, and notably fluorine, chlorine and bromine,
a hydroxy,
a linear or branched alkyl group comprising 1 to 12 carbon atoms,
a linear or branched alkoxy group comprising 1 to 12 carbon atoms,
a haloalkyl or haloalkoxy group corresponding to the (C
1
-C
12
) alkyl or alkoxy groups above respectively which are substituted with at least one halogen atom, and notably a fluoroalkyl group of this type,
a phenoxy or naphthoxy group optionally substituted with at least one linear or branched alkyl or alkoxy group comprising 1 to 12 carbon atoms,
a linear or branched alkenyl group comprising 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 comprising 1 to 6 carbon atoms, or a phenyl group optionally substituted with at least one linear or branched alkyl group comprising 1 to 6 carbon atoms,
a
group, R′ and R″, which are identical or different, representing independently a linear or branched alkyl group comprising 1 to 6 carbon atoms, or a phenyl group optionally substituted with at least one linear or branched alkyl group comprising 1 to 6 carbon atoms, or representing together with the nitrogen atom to which they are bo
Breyne Olivier
Chan You-Ping
Jean Patrick
Corning S.A.
Nwaneri Angela N.
Rogalskyj Peter
Tucker Philip
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