Compositions – Light transmission modifying compositions – Displaying color change
Reexamination Certificate
2001-10-29
2004-05-18
Tucker, Philip C. (Department: 1712)
Compositions
Light transmission modifying compositions
Displaying color change
C549S381000, C549S382000, C549S331000, C549S332000, C351S163000, C524S110000, C546S196000, C544S150000, C548S525000
Reexamination Certificate
active
06736998
ABSTRACT:
DESCRIPTION OF THE INVENTION
The present invention relates to certain novel naphthopyran compounds. More particularly, this invention relates to novel indeno-fused photochromic naphthopyran compounds and to compositions and articles containing such novel naphthopyran compounds. When exposed to light radiation containing ultraviolet rays, such as the ultraviolet radiation in sunlight or the light of a mercury lamp, many photochromic compounds exhibit a reversible change in color. When the ultraviolet radiation is discontinued, such a photochromic compound will return to its original color or colorless state.
Various classes of photochromic compounds have been synthesized and suggested for use in applications in which a sunlight-induced reversible color change or darkening is desired. U.S. Pat. No. 3,567,605 (Becker) describes a series of pyran derivatives, including certain benzopyrans and naphthopyrans. These compounds are described as derivatives of chromene and are reported to undergo a color change, e.g., from colorless to yellow-orange, on irradiation by ultraviolet light at temperatures below about −30° C. Irradiation of the compounds with visible light or upon raising the temperature to above about 0° C. is reported to reverse the coloration to a colorless state.
U.S. Pat. No. 5,066,818 describes various 3,3-diaryl-3H-naphtho[2,1-b]pyrans as having desirable photochromic properties, i.e., high colorability and acceptable fade, for ophthalmic and other applications. Also disclosed by way of comparative example in the '818 patent are the isomeric 2,2-diaryl-2H-naphtho[1,2-b]pyrans, which are reported to require unacceptably long periods of time to fade after activation.
U.S. Pat. No. 3,627,690 describes photochromic 2,2-di-substituted-2H-naphtho[1,2-b]pyran compositions containing minor amounts of either a base or weak-to-moderate strength acid. The addition of either an acid or base to the naphthopyran composition is reported to increase the fade rate of the colored naphthopyrans, thereby making them useful in eye protection applications such as sunglasses. It is reported therein further that the fade rate of 2H-naphtho-[1,2-b]pyrans without the aforementioned additives ranges from several hours to many days to reach complete reversion.
Indenonaphthopyrans are known and have been disclosed in U.S. Pat. Nos. 5,645,767, 5,698,141, 5,723,072, 6,113,814 and 6,146,554 and International Patent Application Publication No. WO 99/15518. In each of these disclosures, the indeno group is in a reversed position as compared to the indenonaphthopyrans of the present invention. Japan Unexamined Patent Publication P2000-327675A discloses an indenonaphthopyran in which the indeno group is substituted with fluorenyl.
The present invention relates to a naphthopyran of 2H-naphtho[1,2-b]pyran structure characterized by having a substituted or unsubstituted indeno group fused at the 2,3 positions of the group to the 1 side of the naphthopyran. The compounds also have substituents at the 3 position of the pyran ring. These compounds have unexpectedly been found to demonstrate a bathochromic shift for the wavelength in the visible spectrum at which the maximum absorption of the activated (colored) form of the photochromic compound, i.e., the lambda max (Vis), occurs, thereby resulting in activated colors ranging from yellow/brown to blue/gray. Due to the bathochromic shift, compounds of the present invention demonstrate different colors than similar compounds without an unsubstituted or substituted indeno group fused at the 2,3 position of the group to the 1 side of the napthopyran. In addition, compounds of the present invention have demonstrated a high molar absorptivity (or molar extinction coefficient) in the UV, an acceptable fade rate without the addition of acids or bases, a high activated intensity, and a high coloration rate.
DETAILED DESCRIPTION OF THE INVENTION
In recent years, photochromic plastic materials, particularly plastic materials for optical applications, have been the subject of considerable attention. In particular, photochromic ophthalmic plastic lenses have been investigated because of the weight advantage they offer, vis-a-vis, glass lenses. Moreover, photochromic transparencies for vehicles, such as cars and airplanes, have been of interest because of the potential safety features that such transparencies offer.
Other than in the operating examples, or where otherwise indicated, all values, such as those expressing wavelengths, quantities of ingredients, ranges or reaction conditions, used in this description and the accompanying claims are understood as modified in all instances by the term “about” which means close to or near.
As used herein, the terms “halo” and “halogen” are defined to include chloro, fluoro, bromo and iodo and chlorine, fluorine, bromine and iodine, respectively. The term “aryl” is defined herein to include phenyl and naphthyl.
The disclosures of the patents and articles cited herein describing photochromic imbibition processes and compositions, procedures for making polymerizable and nonpolymerizable compounds of the present invention, complementary photochromic compounds, polymeric coatings and methods of applying such coatings, polymeric organic host materials and polymerizates are incorporated herein, in toto, by reference.
In accordance with the present invention, it has now been discovered that novel 2H-naphtho[1,2-b]pyran structures characterized by having a substituted or unsubstituted indeno group fused at the 2,3 positions of the group to the 1 side of the naphthopyran and demonstrating activated colors ranging from yellow/brown to blue/gray, an acceptable fade rate, high activated intensity and a high coloration rate may be prepared. These compounds may be described as indeno[3′,2′:3,4]naphtho[1,2-b]pyrans having substituents at the 3 position of the pyran ring. Substituents may also be present at the number 5, 6, 7, 8, 9, 10, 11, 12, or 13 carbon atoms of the compounds. The indeno group may be represented by the following graphic formula I′ in which numbers 1 through 9 represent the ring atoms of the indeno group.
A typical 2H-naphtho[1,2-b]pyran structure is represented by the following graphic formula I″, in which the letters a through n represent the sides and X represents potential substituents known in the art.
The compounds of the present invention may be represented by the following graphic formula I in which the letters a through u represent the sides of the indenonaphthopyran rings, and the numbers represent the numbers of the ring atoms of the indenonaphthopyran.
The indenonaphthopyran of the present invention is a naphthopyran compound of 2H-naphtho[1,2-b]pyran structure, such as represented by graphic formula I″, characterized by having fused to the 1 side of the 2H-naphthopyran a group represented by graphic formula I′ at the 2,3 positions of group I′. The group represented by graphic formula I′ may be unsubstituted such as when R
1
and R
2
are each hydrogen and equals 0 or may be substituted with substituents known in the art for use on photochromic compounds. Different embodiments of the compounds of the present invention are contemplated based on photochromic activity.
In graphic formulae I′, R
1
and R
2
may each be selected from the group consisting of:
(i) hydrogen, hydroxy, amino, mono- and di-substituted amino, C
1
-C
6
alkyl, C
1
-C
6
haloalkyl, C
3
-C
7
cycloalkyl, allyl, benzyl, mono-substituted benzyl, halogen and the group, —C(O)W, wherein W is hydroxy, C
1
-C
6
alkyl, C
1
-C
6
alkoxy, C
3
-C
7
cycloalkyloxy, phenyl, mono-substituted phenyl, phenoxy, amino, mono(C
1
-C
6
)alkylamino, di(C
1
-C
6
)alkylamino, morpholino, piperidino or pyrrolidyl, said amino substituents being selected from the group consisting of C
1
-C
6
alkyl, phenyl, benzyl and naphthyl, said benzyl and phenyl substituents being C
1
-C
6
alkyl, C
1
-C
6
alkoxy, pi
Kumar Anil
Petrovskaia Olga G.
Mallak Frank P.
Transitions Optical Inc.
Tucker Philip C.
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