Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
1997-12-15
2003-10-07
Stockton, Laura L. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C252S586000, C524S099000, C524S109000, C524S110000
Reexamination Certificate
active
06630597
ABSTRACT:
DESCRIPTION OF THE INVENTION
The present invention relates to certain novel naphthopyran compounds. More particularly, this invention relates to novel photochromic 6-aryl substituted 3H-naphtho[2,1-b]pyran 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. 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.
Certain photochromic naphtho[2,1-b]pyrans having a nitrogen-containing group at the 6 position of the naphthyl portion of the naphthopyran compound have been disclosed. U.S. Pat. No. 5,552,090 describes photochromic naphtho[2,1-b]pyrans substituted at the 6 position of the naphthyl portion of the naphthopyran compound with a nitrogen-containing heterocyclic ring. Photochromic naphtho[2,1-b]pyrans substituted at the 6 position of the naphthyl portion with an alkoxy group or aryloxy group are described in U.S. Pat. No. 5,520,853. U.S. Pat. No. 5,623,005 discloses naphtho[2,1-b]pyrans substituted at the 6 position of the naphthyl portion of the naphthopyran compound with an amino group.
The present invention relates to novel 6-aryl substituted 3H-naphtho[2,1-b]pyran compounds having certain substituents at the 3-position of the pyran ring. Other substituents may also be present optionally at the number 7, 8, 9 or 10 carbon atoms. The naphthopyrans of the present invention have unexpectedly been found to demonstrate a hypsochromic wavelength shift 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 to orange. Photochromic compounds of the present invention include compounds that exhibit acceptable photochromic performance properties, i.e., activated intensity, coloration rate and fade 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.
In accordance with the present invention, it has now been discovered that certain novel 6-aryl substituted 3H-naphtho[2,1-b]pyrans having activated colors ranging from yellow to orange may be prepared. These compounds may be described as 6-aryl substituted 3H-naphtho[2,1-b]pyrans having certain substituents at the 3 position of the pyran ring. Certain substituents may also be present at the number 7, 8, 9 or 10 carbon atoms of the naphtho portion of the compounds. These compounds may be represented by the following graphic formula I in which the numbers 1 through 10 within the depicted ring-system represent the numbers of the ring atoms of the naphthopyran:
In graphic formula I, each R
1
and each R
2
may be C
1
-C
6
alkyl, C
1
-C
6
alkoxy, chloro or fluoro; and m and n are each the integers 0, 1, or 2. When m and n are 2, each R
1
and R
2
may be the same or different. More preferably, each R
1
and each R
2
are C
1
-C
3
alkyl, C
1
-C
3
alkoxy, or fluoro. Most preferably, R
1
and R
2
are each C
1
-C
3
alkyl or C
1
-C
3
alkoxy.
Ar in graphic formula I may be phenyl, naphthyl, thienyl, benzothienyl, furanyl, benzofuranyl or pyridyl. Preferably Ar is phenyl or naphthyl.
B and B′ in graphic formula I may each be selected from the group consisting of: (i) the unsubstituted, mono-, di-, and tri-substituted aryl groups, phenyl and naphthyl; (ii) the unsubstituted, mono- and di-substituted heteroaromatic groups pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, each of said aryl and heteroaromatic substituents in parts (i) and (ii) being selected from the group consisting of di(C
1
-C
6
)alkylamino, piperidino, morpholino, pyrryl, C
1
-C
6
alkyl, 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, acryloxy, methacryloxy, chloro and fluoro; (iii) the groups represented by the following graphic formulae:
wherein A may be carbon or oxygen and D may be oxygen or substituted nitrogen, provided that when D is substituted nitrogen, A is carbon, said nitrogen substituents being selected from the group consisting of hydrogen, C
1
-C
6
alkyl, and C
2
-C
6
acyl; each R
3
is C
1
-C
6
alkyl, C
1
-C
6
alkoxy, hydroxy, chloro or fluoro; R
4
and R
5
are each hydrogen or C
1
-C
6
alkyl; and p is the integer 0, 1, or 2; (iv) C
1
-C
6
alkyl, C
1
-C
6
chloroalkyl, C
1
-C
6
fluoroalkyl, C
1
-C
6
alkoxy(C
1
-C
4
)alkyl, C
3
-C
6
cycloalkyl, mono(C
1
-C
6
) alkoxy(C
3
-C
6
)cycloalkyl, mono(C
1
-C
6
)alkyl(C
3
-C
6
)cycloalkyl, chloro(C
3
-C
6
)cycloalkyl, and fluoro(C
3
-C
6
)cycloalkyl; and (v) the group represented by the following graphic formula:
wherein X in graphic formula IIC may be hydrogen or C
1
-C
4
alkyl and Z in graphic formula IIC may be selected from the unsubstituted, mono-, and di-substituted members of the group consisting of naphthyl, phenyl, furanyl, and thienyl, each of said group substituents in this part (v) being C
1
-C
4
alkyl, C
1
-C
4
alkoxy, fluoro, or chloro; or (vi) B and B′ taken together form fluoren-9-ylidene, mono-, or di-substituted fluoren-9-ylidene or form a member selected from the group consisting of saturated C
3
-C
12
spiro-monocyclic hydrocarbon rings, e.g., cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene, cyclononylidene, cyclodecylidene cycloundecylidene, cyclododecylidene; saturated C
7
-C
12
spiro-bicyclic
Gemert Barry Van
Lin Jibing
Mallak Frank P.
Stockton Laura L.
Transitions Optical Inc.
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