Compositions – Light transmission modifying compositions – Displaying color change
Reexamination Certificate
2000-12-15
2002-11-12
Lambkin, Deborah C. (Department: 1626)
Compositions
Light transmission modifying compositions
Displaying color change
C351S163000, C359S241000, C544S150000, C549S060000, C549S389000
Reexamination Certificate
active
06478989
ABSTRACT:
DESCRIPTION OF THE INVENTION
The present invention relates to substituted 2H-naphtho[1,2-b]pyran compounds. More particularly, this invention relates to novel photochromic aromatic substituted naphthopyran compounds and to compositions and articles containing such novel naphthopyran compounds. When exposed to electromagnetic 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.
U.S. Pat. No. 4,818,096 discloses purple/blue coloring photochromic benzo- or naphthopyrans having at the position alpha to the oxygen of the pyran ring a phenyl group having a nitrogen containing substituent in the ortho or para positions. U.S. Pat. No. 5,645,767 describes novel photochromic indeno-fused 2H-naphtho[1,2-b]pyran compounds, the 2,1-positions of the indeno group being fused to the f side of the naphthopyran.
The following four patents disclose related photochromic 2H-naphtho[1, 2-b]pyran compounds with certain substituents at the 2 position and certain aromatic substituents at the 5 position. U.S. Pat. No. 4,826,977 discloses naphthopyrans having an adamantane group at the 2 position, a phenyl or substituted phenyl group or a 5- or 6-membered heteroaromatic group at the 5 position. U.S. Pat. No. 4,931,221 discloses naphthopyrans having two cyclopropyl groups at the 2 position, and a phenyl or substituted phenyl group at the 5 position. U.S. Pat. No. 4,980,089 describes naphthopyrans having a norcamphor group or a tricyclodecane group at the 2 position, and a furyl group, thienyl group or phenyl or substituted phenyl group at the 5 position. U.S. Pat. No. 5,200,116 describes naphthopyrans having a cyclopropyl group along with a phenyl or substituted phenyl group, thienyl, benzothienyl group, or furyl or benzofuryl group at the 2 position and a phenyl or substituted phenyl group at the 5 position. The substituents of the 5 position phenyl groups disclosed in these four patents are C
1
-C
4
alkyl, C
1
-C
4
alkoxy, chloro or bromo.
U.S. Pat. No. 5,458,814 discloses photochromic 2H-naphtho[1,2-b]pyran compounds having certain substituents at the number 5 and 6 carbon atoms of the naphtho portion of the naphthopyran, and at the 2-position of the pyran ring. These compounds have an acceptable fade rate in addition to a high activated intensity and a high coloration rate.
The present invention relates to a naphthopyran of 2H-naphtho[1,2-b]pyran structure characterized by having and aromatic substituent in the 5 position. The compounds also have substituents at the 2 position of the pyran ring. The aromatic group at the 5-position of the naphthopyran is a substituted or unsubstituted phenyl or naphthyl group or other substituted or unsubstituted heteroaromatic group. It has unexpectedly been discovered that the compounds of the present invention are faster to fade than 2H-naphthopyrans having similar photochromic properties that are unsubstituted or have an aromatic substituent in the 5 position and a different substituent in the 6 position.
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-à-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.
In accordance with the present invention, it has now been discovered that 2H-naphtho[1,2-b]pyrans characterized by having in the 5 position, a group —Ar(R
2
)
n
(COOR
3
)
p
, that produce an activated yellow-orange color may be prepared. These compounds may be described as naphthopyrans having at the number 5 carbon atom of the naphthopyran a substituted or unsubstituted phenyl or naphthyl group or another substituted or unsubstituted heteroaromatic substituent, and substituents at the 2 position of the pyran ring. Substituents may also be present at the number 7, 8, 9 or 10 carbon atoms of the naphthopyran compound. The number 6 carbon atom of the naphthopyran compound has a hydrogen substituent.
The foregoing described naphthopyran compounds may be represented by the following graphic formula I in which the numbers 1 through 10 identify the ring atoms of the naphthopyran.
Ar in graphic formula I may be selected from the group consisting of:
(i) an aryl group consisting of phenyl and naphthyl; and
(ii) an aromatic group consisting of furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuran-4-yl, and dibenzothien-4-yl. Preferably, Ar is phenyl or thienyl.
In graphic formula I, each R
1
may be C
1
-C
6
alkyl, C
1
-C
6
alkoxy, or halogen, said halogen being bromo, chloro, fluoro or iodo and m is the integer 0, 1, 2 or 3. In one contemplated embodiment, each R
1
is C
1
-C
4
alkyl, C
1
-C
4
alkoxy, chloro or fluoro, and m is the integer 0, 1 or 2. In another contemplated embodiment, each R
1
is C
1
-C
3
alkyl or C
1
-C
3
alkoxy, and m is the integer 0 or 1.
Each R
2
in graphic formula I may be selected from the group consisting of aryl, i.e., phenyl and naphthyl, mono(C
1
-C
6
)alkoxyaryl, di(C
1
-C
6
)alkoxyaryl, mono(C
1
-C
6
)alkylaryl, di(C
1
-C
6
)alkylaryl, haloaryl, C
3
-C
7
cycloalkylaryl, C
3
-C
7
cycloalkyl, C
3
-C
7
cycloalkyloxy, C
3
-C
7
cycloalkyloxy(C
1
-C
6
)alkyl, C
3
-C
7
cycloalkyloxy(C
1
-C
6
)alkoxy, aryl(C
1
-C
6
)alkyl, aryl(C
1
-C
6
)alkoxy, aryloxy, aryloxy(C
1
-C
6
)alkyl, aryloxy(C
1
-C
6
)alkoxy, mono- and di(C
1
-C
6
)alkylaryl(C
1
-C
6
)alkyl, mono- and di(C
1
-C
6
)alkoxyaryl(C
1
-C
6
)alkyl, mono- and di(C
1
-C
6
)alkylaryl(C
1
-C
6
)alkoxy, mono- and di(C
1
-C
6
)alkoxyaryl(C
1
-C
6
)alkoxy, C
1
-C
6
alkyl, C
1
-C
6
bromoalkyl, C
1
-C
6
chloroalkyl, C
1
-C
6
fluoroalkyl, C
1
-C
6
alkoxy, mono(C
1
-C
6
)alkoxy(C
1
-C
4
)alkyl, and halogen, said halogen being bromo, chloro, fluoro or iodo, and n is the integer 0, 1, 2, or 3. In one contemplated embodiment, each R
2
i
Lambkin Deborah C.
Mallak Frank P.
Transitions Optical Inc.
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