U.S. patent application number 09/738356 was filed with the patent office on 2002-11-21 for novel aromatic substituted naphthopyrans.
Invention is credited to Lin, Jibing.
Application Number | 20020173667 09/738356 |
Document ID | / |
Family ID | 27055773 |
Filed Date | 2002-11-21 |
United States Patent
Application |
20020173667 |
Kind Code |
A1 |
Lin, Jibing |
November 21, 2002 |
NOVEL AROMATIC SUBSTITUTED NAPHTHOPYRANS
Abstract
Described are photochromic 2H-naphtho[1,2-] pyrans characterized
by having an aromatic substituent in the 5 position. The aromatic
group at 5-position of the naphthopyran is a substituted or
unsubstituted aryl group or other substituted or unsubstituted
aromatic group. These compounds may be represented by the following
graphic formula: 1 Also described are polymeric organic host
materials that contain or that are coated with such compounds.
Inventors: |
Lin, Jibing; (US) |
Correspondence
Address: |
PPG INDUSTRIES INC
INTELLECTUAL PROPERTY DEPT
ONE PPG PLACE
PITTSBURGH
PA
15272
US
|
Family ID: |
27055773 |
Appl. No.: |
09/738356 |
Filed: |
December 15, 2000 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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09738356 |
Dec 15, 2000 |
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09507276 |
Feb 18, 2000 |
|
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09507276 |
Feb 18, 2000 |
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08933556 |
Sep 19, 1997 |
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Current U.S.
Class: |
549/43 ; 549/389;
549/49; 549/60 |
Current CPC
Class: |
C07D 311/92 20130101;
C07D 407/04 20130101; C07D 409/04 20130101 |
Class at
Publication: |
549/43 ; 549/49;
549/60; 549/389 |
International
Class: |
C07D 49/02; C07D
333/76 |
Claims
I claim:
1. A naphthopyran of 2H-naphtho[1,2-b]pyran structure,
characterized by having in the 5 position, a group,
--Ar(R.sub.2).sub.n(COOR.sub.3).sub.p, wherein: (a) Ar is 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, dibenzofuranyl, dibenzothienyl
and fluorenyl; (b) each R.sub.2 is selected from the group
consisting of aryl, mono(C.sub.1-C.sub.6)alkoxyaryl,
di(C.sub.1-C.sub.6)alkoxyaryl, mono(C.sub.1-C.sub.6)alkylaryl,
di(C.sub.1-C.sub.6)alkylaryl, haloaryl, C.sub.3-C.sub.7
cycloalkylaryl, C.sub.3-C.sub.7 cycloalkyl, C.sub.3-C.sub.7
cycloalkyloxy, C.sub.3-C.sub.7 cycloalkyloxy(C.sub.1-C.su-
b.6)alkyl, C.sub.3-C.sub.7 cycloalkyloxy(C.sub.1-C.sub.6)alkoxy,
aryl(C.sub.1-C.sub.6)alkyl, aryl(C.sub.1-C.sub.6)alkoxy, aryloxy,
aryloxy(C.sub.1-C.sub.6)alkyl, aryloxy(C.sub.1-C.sub.6)alkoxy,
mono- and di(C.sub.1-C.sub.6)alkylaryl(C.sub.1-C.sub.6)alkyl, mono-
and di(C.sub.1-C.sub.6)alkoxyaryl(C.sub.1-C.sub.6)alkyl, mono- and
di(C.sub.1-C.sub.6)alkylaryl(C.sub.1-C.sub.6)alkoxy, mono- and
di(C.sub.1-C.sub.6)alkoxyaryl(C.sub.1-C.sub.6)alkoxy,
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 bromoalkyl, C.sub.1-C.sub.6
chloroalkyl, C.sub.1-C.sub.6 fluoroalkyl, C.sub.1-C.sub.6 alkoxy,
mono(C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.4)alkyl, and halogen,
said halo and halogen being bromo, chloro, fluoro or iodo, and n is
the integer 0, 1, 2, or 3; and (c) each R.sub.3 is selected from
the group consisting of C.sub.1-C.sub.4 alkyl, phenyl,
mono(C.sub.1-C.sub.4)alkyl substituted phenyl,
mono(C.sub.1-C.sub.4)alkoxy substituted phenyl,
phenyl(C.sub.1-C.sub.2)alkyl, mono(C.sub.1-C.sub.4)alkyl
substituted phenyl(C.sub.1-C.sub.2)alkyl,
mono(C.sub.1-C.sub.4)alkoxy substituted
phenyl(C.sub.1-C.sub.2)alkyl,
mono(C.sub.1-C.sub.4)alkoxy(C.sub.2-C.sub.3- )alkyl, and
C.sub.1-C.sub.4 haloalkyl, and p is the integer 0, 1 or 2, the sum
of n and p being 0, 1, 2 or 3 and wherein when p is 2, n is 0.
2. The naphthopyran compound of claim 1 wherein said naphthopyran
is represented by the following graphic formula: 9wherein, (a) Ar
is 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, dibenzofuranyl, dibenzothienyl
and fluorenyl; (b) each R.sub.1 is C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 alkoxy, or halogen and m is the integer 0, 1, 2 or
3; (c) each R.sub.2 is selected from the group consisting of aryl,
mono(C.sub.1-C.sub.6)alkoxyaryl, di(C.sub.1-C.sub.6) alkoxyaryl,
mono(C.sub.1-C.sub.6)alkylaryl, di(C.sub.1-C.sub.6) alkylaryl,
haloaryl, C.sub.3-C.sub.7 cycloalkylaryl, C.sub.3-C.sub.7
cycloalkyl, C.sub.3-C.sub.7 cycloalkyloxy, C.sub.3-C.sub.7
cycloalkyloxy(C.sub.1-C.sub.6)alkyl, C.sub.3-C.sub.7
cycloalkyloxy(C.sub.1-C.sub.6) alkoxy, aryl(C.sub.1-C.sub.6)alkyl,
aryl(C.sub.1-C.sub.6)alkoxy, aryloxy, aryloxy(C.sub.1-C.sub.6)
alkyl, aryloxy(C.sub.1-C.sub.6)alkoxy, mono- and
di(C.sub.1-C.sub.6)alkylaryl(C.- sub.1-C.sub.6)alkyl, mono- and
di(C.sub.1-C.sub.6)alkoxyaryl(C.sub.1-C.sub- .6)alkyl, mono- and
di(C.sub.1-C.sub.6)alkylaryl(C.sub.1-C.sub.6)alkoxy, mono- and
di(C.sub.1-C.sub.6)alkoxyaryl(C.sub.1-C.sub.6)alkoxy,
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 bromoalkyl, C.sub.1-C.sub.6
chloroalkyl, C.sub.1-C.sub.6 fluoroalkyl, C.sub.1-C.sub.6 alkoxy,
mono(C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.4)alkyl, bromo, chloro
and fluoro and n is the integer 0, 1, 2, or 3; (d) R.sub.3 is
selected from the group consisting of C.sub.1-C.sub.4 alkyl,
phenyl, mono(C.sub.1-C.sub.4)alkyl substituted phenyl,
mono(C.sub.1-C.sub.4)alkox- y substituted phenyl,
phenyl(C.sub.1-C.sub.2)alkyl, mono(C.sub.1-C.sub.4)alkyl
substituted phenyl(C.sub.1-C.sub.2)alkyl,
mono(C.sub.1-C.sub.4)alkoxy substituted
phenyl(C.sub.1-C.sub.2)alkyl,
mono(C.sub.1-C.sub.4)alkoxy(C.sub.2-C.sub.3)alkyl, and
C.sub.1-C.sub.4 haloalkyl, and p is the integer 0, 1 or 2, the sum
of n and p being 0, 1, 2 or 3 and wherein when p is 2, n is 0; and
(e) B and B' are each selected from the group consisting of: (i) an
unsubstituted, mono-, di- and tri-substituted aryl group consisting
of phenyl and naphthyl; (ii) an unsubstituted, mono- and
di-substituted heteroaromatic group consisting of pyridyl, furanyl,
benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl,
benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazolyl and
fluorenyl, each of said aryl and heteroaromatic substituents in (e)
(i) and (ii) being selected from the group consisting of hydroxy,
aryl, mono(C.sub.1-C.sub.6)alkoxyaryl,
di(C.sub.1-C.sub.6)alkoxyaryl, mono(C.sub.1-C.sub.6)alkylaryl,
di(C.sub.1-C.sub.6)alkylaryl, bromoaryl, chloroaryl, fluoroaryl,
C.sub.3-C.sub.7 cycloalkylaryl, C.sub.3-C.sub.7 cycloalkyl,
C.sub.3-C.sub.7 cycloalkyloxy, C.sub.3-C.sub.7
cycloalkyloxy(C.sub.1-C.su- b.6)alkyl, C.sub.3-C.sub.7
cycloalkyloxy(C.sub.1-C.sub.6)alkoxy, aryl(C.sub.1-C.sub.6)alkyl,
aryl(C.sub.1-C.sub.6)alkoxy, aryloxy,
aryloxy(C.sub.1-C.sub.6)alkyl, aryloxy(C.sub.1-C.sub.6)alkoxy,
mono- and di-(C.sub.1-C.sub.6)alkylaryl(C.sub.1-C.sub.6)alkyl,
mono- and di-(C.sub.1-C.sub.6)alkoxyaryl(C.sub.1-C.sub.6)alkyl,
mono- and di-(C.sub.1-C.sub.6)alkylaryl(C.sub.1-C.sub.6)alkoxy,
mono- and di-(C.sub.1-C.sub.6)alkoxyaryl(C.sub.1-C.sub.6)alkoxy,
amino, mono(C.sub.1-C.sub.6)alkylamino,
di(C.sub.1-C.sub.6)alkylamino, diarylamino,
N--(C.sub.1-C.sub.6)alkylpiperazino, N-arylpiperazino, aziridino,
indolino, piperidino, arylpiperidino, morpholino, thiomorpholino,
tetrahydroquinolino, tetrahydroisoquinolino, pyrryl,
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 bromoalkyl, C.sub.1-C.sub.6
chloroalkyl, C.sub.1-C.sub.6 fluoroalkyl, C.sub.1-C.sub.6 alkoxy,
mono(C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.4)alkyl, acryloxy,
methacryloxy, bromo, chloro and fluoro; (iii) the group represented
by one of the following graphic formulae: 10wherein E is methylene
or oxygen and D is oxygen or substituted nitrogen, provided that
when D is substituted nitrogen, E is methylene, said nitrogen
substituents being selected from the group consisting of hydrogen,
C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 acyl; each R.sub.4 is
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, hydroxy, bromo,
chloro or fluoro; R.sub.5 and R.sub.6 are each hydrogen or
C.sub.1-C.sub.6 alkyl; and q is the integer 0, 1 or 2; (iv)
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 bromoalkyl, C.sub.1-C.sub.6
chloroalkyl, C.sub.1-C.sub.6 fluoroalkyl, C.sub.1-C.sub.6
alkoxy(C.sub.1-C.sub.4)alkyl; and (v) the group represented by the
following graphic formula: 11wherein X is hydrogen or
C.sub.1-C.sub.4 alkyl and Z is selected from an unsubstituted,
mono-, and di-substituted members of the group consisting of
naphthyl, phenyl, furanyl and thienyl, each of said group
substituents being C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy,
bromo, fluoro or chloro.
3. The naphthopyran of claim 2 wherein, (a) each R.sub.1 is
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy, chloro or fluoro,
and m is the integer 0, 1 or 2; (b) Ar is phenyl or thienyl; (c)
each R.sub.2 is selected from the group consisting of aryl,
aryloxy, aryl(C.sub.1-C.sub.3)alkyl, C.sub.1-C.sub.3 alkyl,
C.sub.1-C.sub.3 chloroalkyl, C.sub.1-C.sub.3 fluoroalkyl,
C.sub.1-C.sub.3 alkoxy,
mono(C.sub.1-C.sub.3)alkoxy(C.sub.1-C.sub.3)alkyl, fluoro and
chloro and n is the integer 0, 1 or 2; (d) R.sub.3 is
C.sub.1-C.sub.3 alkyl and p is the integer 0 or 1, wherein when p
is 1, n is 0; and (e) B and B' are each selected from the group
consisting of: (i) phenyl, mono-substituted phenyl and
di-substituted phenyl; (ii) an unsubstituted, mono-substituted and
di-substituted heteroaromatic groups furanyl, benzofuran-2-yl,
thienyl, benzothien-2-yl, dibenzofuran-2-yl, and dibenzothien-2-yl,
each of said phenyl and heteroaromatic substituents in (e) (i) and
(ii) being selected from the group consisting of hydroxy, aryl,
aryloxy, aryl(C.sub.1-C.sub.3)alkyl, amino,
mono(C.sub.1-C.sub.3)alkylamino, di(C.sub.1-C.sub.3)alkylamino,
N--(C.sub.1-C.sub.3)alkylpiperazino, indolino, piperidino,
morpholino, pyrryl, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3
chloroalkyl, C.sub.1-C.sub.3 fluoroalkyl, C.sub.1-C.sub.3 alkoxy,
mono(C.sub.1-C.sub.3)alkoxy(C.sub.1-C.sub.3)alkyl, fluoro and
chloro; (iii) the group represented by one of the following graphic
formula: 12wherein E is methylene and D is oxygen, R.sub.4 is
C.sub.1-C.sub.3 alkyl or C.sub.1-C.sub.3 alkoxy, R.sub.5 and
R.sub.6 are each hydrogen or C.sub.1-C.sub.4 alkyl; and q is the
integer 0 or 1; (iv) C.sub.1-C.sub.4 alkyl; and (v) the group
represented by the following graphic formula: 13wherein X is
hydrogen or methyl and Z is phenyl or mono-substituted phenyl, said
phenyl substituent being selected from the group consisting of
C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 alkoxy and fluoro.
4. The naphthopyran of claim 3 wherein: (a) R.sub.1 is
C.sub.1-C.sub.3 alkyl or C.sub.1-C.sub.3 alkoxy, and m is the
integer 0 or 1; (b) Ar is phenyl or thienyl; (c) R.sub.2 is
C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 alkoxy, aryl, fluoro and
chloro, and n is the integer 0 or 1; (d) R.sub.3 is C.sub.1-C.sub.3
alkyl and p is the integer 0 or 1, wherein when p is 1, n is 0; and
(e) B and B' are each selected from the group consisting of: (i)
phenyl, mono-substituted and di-substituted phenyl; (ii) an
unsubstituted, mono-, and di-substituted heteroaromatic groups
furanyl, benzofuran-2-yl, thienyl and benzothien-2-yl, each of said
phenyl and heteroaromatic substituents in (e) (i) and (ii) being
selected from the group consisting of hydroxy, C.sub.1-C.sub.3
alkyl, C.sub.1-C.sub.3 alkoxy, aryl, indolino, fluoro and chloro;
and (iii) the group represented by the following graphic formula:
14wherein E is methylene and D is oxygen, R.sub.4 is
C.sub.1-C.sub.3 alkyl or C.sub.1-C.sub.3 alkoxy, R.sub.5 and
R.sub.6 are each hydrogen or C.sub.1-C.sub.3 alkyl, and q is the
integer 0 or 1.
5. A naphthopyran compound selected from the group consisting of:
(a)
2,2-diphenyl-5-(2-methoxycarbonylphenyl)-2H-naphtho[1,2-b]pyran;
(b)
2,2-diphenyl-5-(4-methoxycarbonylphenyl)-2H-naphtho[1,2-b]pyran;
(c) 2,2-diphenyl-5-(thien-2-yl)-2H-naphtho[1,2-b]pyran; (d)
2,2-diphenyl-5-(phenyl)-2H-naphtho[1,2-b]pyran;. (e) 2-phenyl,
2-(4-methoxyphenyl)-5-phenyl-2H-naphtho[1,2-b]pyran; (f)
2,2-di(4-methoxyphenyl)-5-phenyl-2H-naphtho[1,2-b]pyran; (g)
2-phenyl, 2-(4-morpholinophenyl)-5-phenyl-2H-naphtho[1,2-b]pyran;
(h)
2,2-di(4-methoxyphenyl)-9-methoxy-5-phenyl-2H-naphtho[1,2-b]pyran;
(i) 2-phenyl, 2-(4-morpholinophenyl)-9-methoxy-5-phenyl-2H-
naphtho[1,2-b]pyran; (j)
2,2-di(4-methoxyphenyl)-5-(4-methylphenyl)-2H-na-
phtho[1,2-b]pyran; (k) 2-phenyl,
2-(4-methoxyphenyl)-5-(4-methylphenyl)-2H- -naphtho[1,2-b]pyran;
and (l) 2,2-di(4-methoxyphenyl)-9-methoxy-5-(4-methy-
lphenyl)-2H-naphtho[1,2-b]pyran.
6. A photochromic article comprising a polymeric organic host
material and a photochromic amount of the naphthopyran compound of
claim 1.
7. The photochromic article of claim 6 wherein the polymeric
organic host material is selected from the group consisting of
polyacrylates, polymethacrylates, poly(C.sub.1-C.sub.12) alkyl
methacrylates, polyoxy(alkylene methacrylates), poly (alkoxylated
phenol methacrylates), cellulose acetate, cellulose triacetate,
cellulose acetate propionate, cellulose acetate butyrate,
poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride),
poly(vinylidene chloride), thermoplastic polycarbonates,
polyesters, polyurethanes, polythiourethanes, poly(ethylene
terephthalate), polystyrene, poly(alpha methylstyrene),
copoly(styrene-methylmethacrylate), copoly(styrene-acrylonitrile),
polyvinylbutyral and polymers of members of the group consisting of
polyol(allyl carbonate) monomers, polyfunctional acrylate monomers,
polyfunctional methacrylate monomers, diethylene glycol
dimethacrylate monomers, diisopropenyl benzene monomers,
alkoxylated polyhydric alcohol monomers and diallylidene
pentaerythritol monomers.
8. The photochromic article of claim 6 wherein the naphthopyran
compound is present in an amount of from 0.05 to 2.0 milligram per
square centimeter of polymeric organic host material surface to
which the photochromic substance(s) is incorporated or applied.
9. The photochromic article of claim 6 wherein said polymeric
organic host material is an optical element.
10. The photochromic article of claim 9 wherein said optical
element is a lens.
11. A photochromic article comprising a polymeric organic host
material selected from the group consisting of poly(methyl
methacrylate), poly(ethylene glycol bismethacrylate),
poly(ethoxylated bisphenol A dimethacrylate), thermoplastic
polycarbonate, poly(vinyl acetate), polyvinylbutyral, polyurethane,
polythiourethane and polymers of members of the group consisting of
diethylene glycol bis(allyl carbonate) monomers, diethylene glycol
dimethacrylate monomers, ethoxylated phenol bismethacrylate
monomers, diisopropenyl benzene monomers and ethoxylated
trimethylol propane triacrylate monomers, and a photochromic amount
of the naphthopyran compound of claim 2.
12. A photochromic article comprising a polymeric organic host
material selected from the group consisting of poly(methyl
methacrylate), poly(ethylene glycol bismethacrylate),
poly(ethoxylated bisphenol A dimethacrylate), thermoplastic
polycarbonate, poly(vinyl acetate), polyvinylbutyral, polyurethane,
polythiourethane and polymers of members of the group consisting of
diethylene glycol bis(allyl carbonate) monomers, diethylene glycol
dimethacrylate monomers, ethoxylated phenol bismethacrylate
monomers, diisopropenyl benzene monomers and ethoxylated
trimethylol propane triacrylate monomers, and a photochromic amount
of the naphthopyran compound of claim 4.
13. A photochromic article comprising, in combination, a solid
substrate and a photochromic amount of each of (a) at least one
naphthopyran compound of claim 1, and (b) at least one other
organic photochromic compound having at least one activated
absorption maxima within the range of between 400 and 700
nanometers.
14. A photochromic article comprising a polymerizate of an optical
organic resin monomer and a photochromic amount of the naphthopyran
compound of claim 1.
15. The photochromic article of claim 14 wherein the refractive
index of the polymerizate is from about 1.48 to about 1.75.
16. The photochromic article of claim 14 wherein the polymerizate
is an optical element.
17. The photochromic article of claim 16 wherein said optical
element is a lens.
18. A photochromic article comprising, in combination, a solid
substrate and on at least one surface thereof a cured coating of a
coating composition having a photochromic amount of the
naphthopyran compound of claim 1.
19. The photochromic article of claim 18 wherein said coating
composition is selected from the group consisting of a polymeric
coating composition, paint and ink.
20. The photochromic article of claim 18 wherein the substrate is
selected from the group consisting of glass, masonry, textiles,
ceramics, metals, wood, paper and polymeric organic materials.
21. A photochromic article comprising, in combination, a solid
substrate and on at least one surface thereof a cured coating of a
coating composition having a photochromic amount of the
naphthopyran compound of claim 2.
22. A photochromic article comprising, in combination, a solid
substrate and on at least one surface thereof a cured coating of a
coating composition having a photochromic amount of the
naphthopyran compound of claim 4.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part of U.S.
application Ser. No. 09/507,276, filed Feb. 18, 2000, which is a
continuation-in-part of U.S. application Ser. No. 08/933,556, filed
Sep. 19, 1997, now abandoned.
DESCRIPTION OF THE INVENTION
[0002] 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.
[0003] 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.degree. C. Irradiation of the compounds with visible light or
upon raising the temperature to above about 0.degree. C. is
reported to reverse the coloration to a colorless state.
[0004] 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.
[0005] 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.
[0006] 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.
[0007] 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.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 alkoxy, chloro or bromo.
[0008] 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.
[0009] 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
[0010] 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--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.
[0011] 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.sub.2).sub.n(COOR.sub.3).sub.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.
[0012] 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. 2
[0013] Ar in graphic formula I may be selected from the group
consisting of:
[0014] (i) an aryl group consisting of phenyl and naphthyl; and
[0015] (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.
[0016] In graphic formula I, each R.sub.1 may be C.sub.1-C.sub.6
alkyl, C.sub.1-C6 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.sub.1 is C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 alkoxy, chloro or fluoro, and m is the integer 0, 1
or 2. In another contemplated embodiment, each R.sub.1 is
C.sub.1-C.sub.3 alkyl or C.sub.1-C.sub.3 alkoxy, and m is the
integer 0 or 1.
[0017] Each R.sub.2 in graphic formula I may be selected from the
group consisting of aryl, i.e., phenyl and naphthyl,
mono(C.sub.1-C.sub.6)alkox- yaryl, di(C.sub.1-C.sub.6)alkoxyaryl,
mono(C.sub.1-C.sub.6)alkylaryl, di(C.sub.1-C.sub.6)alkylaryl,
haloaryl, C.sub.3-C.sub.7 cycloalkylaryl, C.sub.3-C.sub.7
cycloalkyl, C.sub.3-C.sub.7 cycloalkyloxy, C.sub.3-C.sub.7
cycloalkyloxy(C.sub.1-C.sub.6)alkyl, C.sub.3-C.sub.7
cycloalkyloxy(C.sub.1-C.sub.6)alkoxy, aryl(C.sub.1-C.sub.6)alkyl,
aryl(C.sub.1-C.sub.6)alkoxy, aryloxy,
aryloxy(C.sub.1-C.sub.6)alkyl, aryloxy(C.sub.1-C.sub.6)alkoxy,
mono- and di(C.sub.1-C.sub.6)alkylaryl(C.- sub.1-C.sub.6)alkyl,
mono- and di(C.sub.1-C.sub.6)alkoxyaryl(C.sub.1-C.sub- .6)alkyl,
mono- and di(C.sub.1-C.sub.6)alkylaryl(C.sub.1-C.sub.6)alkoxy,
mono- and di(C.sub.1-C.sub.6)alkoxyaryl(C.sub.1-C.sub.6)alkoxy,
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 bromoalkyl, C.sub.1-C.sub.6
chloroalkyl, C.sub.1-C.sub.6 fluoroalkyl, C.sub.1-C.sub.6 alkoxy,
mono(C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.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.sub.2
is selected from the group consisting of aryl, aryloxy,
aryl(C.sub.1-C.sub.3)alkyl, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3
chloroalkyl, C.sub.1-C.sub.3 fluoroalkyl, C.sub.1-C.sub.3 alkoxy,
mono(C.sub.1-C.sub.3)alkoxy(C.sub.1-- C.sub.3)alkyl, fluoro and
chloro and n is the integer 0, 1 or 2. In another contemplated
embodiment, each R.sub.2 is selected from the group consisting of
C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 alkoxy, aryl, fluoro and
chloro and n is the integer 0 or 1.
[0018] R.sub.3 in graphic formula I may be C.sub.1-C.sub.4 alkyl,
phenyl, mono(C.sub.1-C.sub.4)alkyl substituted phenyl,
mono(C.sub.1-C.sub.4)alkox- y substituted phenyl,
phenyl(C.sub.1-C.sub.2)alkyl, mono(C.sub.1-C.sub.4)alkyl
substituted phenyl(C.sub.1-C.sub.2)alkyl,
mono(C.sub.1-C.sub.4)alkoxy substituted
phenyl(C.sub.1-C.sub.2)alkyl,
mono(C.sub.1-C.sub.4)alkoxy(C.sub.2-C.sub.3)alkyl, or
C.sub.1-C.sub.4 haloalkyl, and p is the integer 0, 1 or 2, provided
that the sum of n and p is less than or equal to 3 and when p is 2,
n is 0. In one contemplated embodiment, R.sub.3 is C.sub.1-C.sub.3
alkyl and p is the integer 0 or 1. In another contemplated
embodiment,, the ester group containing R.sub.3 is ortho to the
atom of the Ar group linked to the number 5 carbon atom of the
naphtho portion of the naphthopyran.
[0019] B and B' in graphic formula I may each be selected from the
group consisting of:
[0020] (i) an unsubstituted, mono-, di- and tri-substituted aryl
group consisting of phenyl and naphthyl;
[0021] (ii) an unsubstituted, mono- and di-substituted
heteroaromatic group consisting of pyridyl, furanyl,
benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl,
benzothien-3-yl, dibenzofuran-4-yl, dibenzothien-4-yl, and
carbazol-4-yl, each of said aryl and heteroaromatic substituents in
parts (i) and (ii) being selected from the group consisting of
hydroxy, aryl, mono(C.sub.1-C.sub.6)alkoxyaryl,
di(C.sub.1-C.sub.6)alkoxyaryl, mono(C.sub.1-C.sub.6)alkylaryl,
di(C.sub.1-C.sub.6)alkylaryl, haloaryl, C.sub.3-C.sub.7
cycloalkylaryl, C.sub.3-C.sub.7 cycloalkyl, C.sub.3-C.sub.7
cycloalkyloxy, C.sub.3-C.sub.7 cycloalkyloxy(C.sub.1-C.sub.6)alkyl,
C.sub.3-C.sub.7 cycloalkyloxy(C.sub.1-C.sub.6)alkoxy,
aryl(C.sub.1-C.sub.6)alkyl, aryl(C.sub.1-C.sub.6)alkoxy, aryloxy,
aryloxy(C.sub.1-C.sub.6)alkyl, aryloxy(C.sub.1-C.sub.6)alkoxy,
mono- and di(C.sub.1-C.sub.6)alkylaryl(C.- sub.1-C.sub.6)alkyl,
mono- and di(C.sub.1-C.sub.6)alkoxyaryl(C.sub.1-C.sub- .6)alkyl,
mono- and di(C.sub.1-C.sub.6)alkylaryl(C.sub.1-C.sub.6)alkoxy,
mono- and di(C.sub.1-C.sub.6)alkoxyaryl(C.sub.1-C.sub.6)alkoxy,
amino, mono(C.sub.1-C.sub.6)alkylamino,
di(C.sub.1-C.sub.6)alkylamino, diarylamino,
N-(C.sub.1-C.sub.6)alkylpiperazino, N-arylpiperazino, aziridino,
indolino, piperidino, arylpiperidino, morpholino, thiomorpholino,
tetrahydroquinolino, tetrahydroisoquinolino, pyrryl,
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6
alkoxy, mono(C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.4)alkyl,
acryloxy, methacryloxy and halogen, said halogen and halo being
bromo, chloro, fluoro or iodo;
[0022] (iii) the group represented by graphic formula IIA or IIB:
3
[0023] wherein E may be methylene or oxygen and D may be oxygen or
substituted nitrogen, provided that when D is substituted nitrogen,
E is methylene, said nitrogen substituents being selected from the
group consisting of hydrogen, C.sub.1-C.sub.6 alkyl and
C.sub.2-C.sub.6 acyl; each R.sub.4 is C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 alkoxy, hydroxy, or halogen, said halogen being
bromo, chloro, fluoro or iodo; R.sub.5 and R.sub.6 are each
hydrogen or C.sub.1-C.sub.6 alkyl; and q is the integer 0, 1 or
2;
[0024] (iv) C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl,
C.sub.1-C.sub.6 alkoxy(C.sub.1-C.sub.4)alkyl; and
[0025] (v) the group represented by the following graphic formula:
4
[0026] wherein X in graphic formula IIC may be hydrogen or
C.sub.1-C.sub.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.sub.1-C.sub.4
alkyl, C.sub.1-C.sub.4 alkoxy, or halogen.
[0027] In one contemplated embodiment, B and B' are each selected
from the group consisting of: (i) phenyl, mono-substituted phenyl
and di-substituted phenyl, preferably substituted in the meta
and/or para positions; (ii) the unsubstituted, mono- and
di-substituted heteroaromatic groups furanyl, benzofuran-2-yl,
thienyl, benzothien-2-yl, dibenzofuran-2-yl and dibenzothien-2-yl,
each of said phenyl and heteroaromatic substituents in (i) and (ii)
being selected from the group consisting of hydroxy, aryl, aryloxy,
aryl(C.sub.1-C.sub.3)alkyl, amino, mono(C.sub.1-C.sub.3)alkylamino,
di(C.sub.1-C.sub.3)alkylamino, N--(C.sub.1-C.sub.3)alkylpiperazino,
indolino, piperidino, morpholino, pyrryl, C.sub.1-C.sub.3 alkyl,
C.sub.1-C.sub.3 chloroalkyl, C.sub.1-C.sub.3 fluoroalkyl,
C.sub.1-C.sub.3 alkoxy,
mono(C.sub.1-C.sub.3)alkoxy(C.sub.1-C.sub.3)alkyl, fluoro and
chloro; (iii) the groups represented by the graphic formulae IIA
and IIB, wherein E is methylene and D is oxygen, R.sub.4 is
C.sub.1-C.sub.3 alkyl or C.sub.1-C.sub.3 alkoxy, R.sub.5 and
R.sub.6 are each hydrogen or C.sub.1-C.sub.4 alkyl; and q is the
integer 0 or 1; (iv) C.sub.1-C.sub.4 alkyl; and (v) the group
represented by the graphic formula IIC wherein X is hydrogen or
methyl and Z is phenyl or mono-substituted phenyl, said phenyl
substituent being selected from the group consisting of
C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 alkoxy and fluoro.
[0028] In another contemplated embodiment, B and B' are each
selected from the group consisting of (i) phenyl, mono- and
di-substituted phenyl; (ii) the unsubstituted, mono- and
di-substituted heteroaromatic groups furanyl, benzofuran-2-yl,
thienyl and benzothien-2-yl, each of said phenyl and heteroaromatic
substituents in (i) and (ii) being selected from the group
consisting of hydroxy, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3
alkoxy, aryl, indolino, fluoro and chloro; and (iii) the group
represented by graphic formula IIA, wherein E is carbon and D is
oxygen, R.sub.4 is C.sub.1-C.sub.3 alkyl or C.sub.1-C.sub.3 alkoxy,
R.sub.5 and R.sub.6 are each hydrogen or C.sub.1-C.sub.3 alkyl, and
q is the integer 0 or 1.
[0029] Compounds represented by graphic formula I may be prepared
by the following described Reactions A through D. Compounds
represented by graphic formula V or VA are either purchased or
prepared by Friedel-Crafts methods shown in Reaction A using an
appropriately substituted or unsubstituted benzoyl chloride of
graphic formula IV with a commercially available substituted or
unsubstituted benzene compound of graphic formula III. See the
publication Friedel-Crafts and Related Reactions, George A. Olah,
Interscience Publishers, 1964, Vol. 3, Chapter XXXI (Aromatic
Ketone Synthesis), and "Regioselective Friedel-Crafts Acylation of
1,2,3,4-Tetrahydroquinoline and Related Nitrogen Heterocycles:
Effect on NH Protective Groups and Ring Size" by Ishihara, Yugi et
al, J. Chem. Soc., Perkin Trans. 1, pages 3401 to 3406, 1992.
[0030] In Reaction A, the compounds represented by graphic formulae
III and IV are dissolved in a solvent, such as carbon disulfide or
methylene chloride, and reacted in the presence of a Lewis acid,
such as aluminum chloride or tin tetrachloride, to form the
corresponding substituted benzophenone represented by graphic
formula V (or VA in Reaction B). R and R' represent possible
substituents, as described hereinbefore with respect to graphic
formula I. 5
[0031] In Reaction B, the substituted or unsubstituted ketone
represented by graphic formula VA, in which B and B' may represent
groups other than substituted or unsubstituted phenyl, as shown in
graphic formula V, is reacted with sodium acetylide in a suitable
solvent, such as anhydrous tetrahydrofuran (THF), to form the
corresponding propargyl alcohol represented by graphic formula VI
Propargyl alcohols having B or B' groups other than substituted and
unsubstituted phenyl may be prepared from commercially available
ketones or ketones prepared via reaction of an acyl halide with a
substituted or unsubstituted benzene, naphthalene or heteroaromatic
compound. Propargyl alcohols having a B or B' group represented by
graphic formula IIC may be prepared by the methods described in
U.S. Pat. No. 5,274,132, column 2, lines 40 to 68. 6
[0032] In Reaction C, the compounds represented by graphic formulae
VII and VIII are first reacted at elevated temperatures and then
further reacted in the presence of a base such as potassium
hydroxide to form the corresponding substituted naphthol
represented by graphic formula IX. Compounds VII and VIII may each
be purchased. Alternatively, compound VIII may be prepared by the
method described by T. Sakamoto et al., Synthesis, pages 312-314
(1983) and by S. Takahashi et al., Synthesis, pages 627-630 (1980).
Synthesis of phenyl naphthols are further described in C. Kipping
et al., J. Pralet. Chem., Vol. 315, pages 887-894 (1973) and J. Bao
et al., J. Amer. Chem. Soc., Vol. 118, pages 3392-3405 (1996).
7
[0033] In Reaction D, the propargyl alcohol represented by graphic
formula VI is coupled with the naphthol represented by graphic
formula IX in the presence of an acid such as p-toluene sulfonic
acid (PTSA) and in a suitable solvent such as toluene to form
compounds represented by graphic formula I. 8
[0034] Compounds represented by graphic formula I may be used in
those applications in which organic photochromic substances may be
employed, such as optical lenses, e.g., vision correcting
ophthalmic lenses, contact lenses and plano lenses, face shields,
goggles, visors, camera lenses, windows, automotive windshields,
aircraft and automotive transparencies, e.g., T-roofs, sidelights
and backlights, plastic films and sheets, textiles and coatings,
e.g., coating compositions. As used herein, coating compositions
are defined herein to include polymeric coating compositions
prepared from materials such as polyurethanes, epoxy resins and
other resins used to produce synthetic polymers; paints, i.e., a
pigmented liquid or paste used for the decoration, protection
and/or the identification of a substrate; and inks, i.e., a
pigmented liquid or paste used for writing and printing on
substrates. Potential substrates for coating compositions
containing the compounds of the present invention include paper,
glass, ceramics, wood, masonry, textiles, metals and polymeric
organic materials.
[0035] Coating compositions may be used to produce polymeric
coatings on optical elements, verification marks on security
documents, e.g., documents such as banknotes, passport and drivers'
licenses, for which authentication or verification of authenticity
may be desired. The 5-aromatic substituted naphthopyrans
represented by graphic formula I exhibit color changes from
colorless to colors ranging from yellow to orange.
[0036] Examples of naphthopyrans and contemplated naphthopyran
compounds that have or are expected to have desirable photochromic
properties and are within the scope of the invention include the
following:
[0037] (a)
2,2-diphenyl-5-(2-methoxycarbonylphenyl)-2H-naphtho[1,2-b]pyran-
;
[0038] (b)
2,2-diphenyl-5-(4-methoxycarbonylphenyl)-2H-naphtho[1,2-b]pyran-
;
[0039] (c) 2,2-diphenyl-5-(thien-2-yl)-2H-naphtho[1,2-b]pyran;
[0040] (d) 2,2-diphenyl-5-(phenyl)-2H-naphtho[1,2-b]pyran;
[0041] (e) 2-phenyl,
2-(4-methoxyphenyl)-5-phenyl-2H-naphtho[1,2-b]pyran;
[0042] (f)
2,2-di(4-methoxyphenyl)-5-phenyl-2H-naphtho[1,2-b]pyran;
[0043] (g) 2-phenyl,
2-(4-morpholinophenyl)-5-phenyl-2H-naphtho[1,2-b]pyra- n;
[0044] (h)
2,2-di(4-methoxyphenyl)-9-methoxy-5-phenyl-2H-naphtho[1,2-b]pyr-
an;
[0045] (i) 2-phenyl,
2-(4-morpholinophenyl)-9-methoxy-5-phenyl-2H-naphtho[-
1,2-b]pyran;
[0046] (j)
2,2-di(4-methoxyphenyl)-5-(4-methylphenyl)-2H-naphtho[1,2-b]pyr-
an;
[0047] (k) 2-phenyl,
2-(4-methoxyphenyl)-5-(4-methylphenyl)-2H-naphtho[1,2- -b]pyran;
and
[0048] (l)
2,2-di(4-methoxyphenyl)-9-methoxy-5-(4-methylphenyl)-2H-naphtho-
[1,2-b]pyran.
[0049] Other than where otherwise indicated, all numbers expressing
wavelengths, quantities of ingredients or reaction conditions used
herein are to be understood as modified in all instances by the
term "about".
[0050] The disclosures of the patents and articles cited herein
describing procedures for making the 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.
[0051] It is contemplated that the organic photochromic
naphthopyrans of the present invention may be used alone, in
combination with other naphthopyrans of the present invention, or
in combination with one or more other appropriate complementary
organic photochromic materials, i.e., organic photochromic
compounds having at least one activated absorption maxima within
the range of between about 400 and 700 nanometers, or substances
containing same, and may be incorporated, e.g., dissolved or
dispersed, in a polymeric organic host material used to prepare
photochromic articles and which color when activated to an
appropriate hue.
[0052] The complementary organic photochromic compounds may include
other naphthopyrans, benzopyrans, indenonaphthopyrans, oxazines,
phenanthropyrans, spiro(benzindoline)naphthopyrans,
spiro(indoline)benzopyrans, spiro(indoline)naphthopyrans,
spiro(indoline)quinopyrans, spiro(indoline)pyrans,
spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines,
spiro(benzindoline)pyridobenzoxazines,
spiro(benzindoline)naphthoxazines, spiro(indoline)benzoxazines,
mercury dithizonates, fulgides, fulgimides and mixtures of such
photochromic compounds. Many of such photochromic compounds are
described in the open literature, e.g., U.S. Pat. Nos. 5,645,767
and 6,153,126.
[0053] Each of the photochromic substances described herein may be
used in amounts (or in a ratio) such that an organic host material
to which the photochromic compounds or mixture of compounds is
applied or in which they are incorporated exhibits a desired
resultant color, e.g., a substantially neutral color when activated
with unfiltered sunlight, i.e., as near a neutral color as possible
given the colors of the activated photochromic compounds. Neutral
gray and neutral brown colors are preferred. Further discussion of
neutral colors and ways to describe colors may be found in U.S.
Pat. No. 5,645,767 column 12, line 66 to column 13, line 19.
[0054] The amount of photochromic substance or composition
containing same applied to or incorporated into a coating
composition or a host material is not critical provided that a
sufficient amount is used to produce a photochromic effect
discernible to the naked eye upon activation. Generally such amount
can be described as a photochromic amount. The particular amount
used depends often upon the intensity of color desired upon
irradiation thereof and upon the method used to incorporate or
apply the photochromic substances. Typically, the more photochromic
substance applied or incorporated, the greater is the color
intensity up to a certain limit.
[0055] The relative amounts of the aforesaid photochromic compounds
used will vary and depend in part upon the relative intensities of
the color of the activated species of such compounds, and the
ultimate color desired. Generally, the amount of total photochromic
substance incorporated into or applied to a photochromic optical
host material may range from 0.05 to 2.0, e.g., from 0.2 to 1.0,
milligrams per square centimeter of surface to which the
photochromic substance(s) is incorporated or applied. The amount of
photochromic material incorporated into a coating composition may
range from 0.1 to 40 weight percent based on the weight of the
liquid coating composition.
[0056] The photochromic naphthopyrans of the present invention may
be associated with the host material by various methods described
in the art. See, for example, column 13, lines 40 to 58 of U.S.
Pat. No. 5,645,767. Aqueous or organic solutions or dispersions of
the photochromic compounds may be used to incorporate the
photochromic compounds into a polymeric organic host material or
other materials such as textiles and coating compositions. Coating
compositions may be applied to the substrate using a coating
process such as that described in U.S. Pat. No. 3,971,872.
[0057] Application of the polymeric coating may be by any of the
methods used in coating technology such as, for example, spray
coating, spin coating, spread coating, curtain coating, dip
coating, casting or roll-coating and methods used in preparing
overlays, such as the method of the type described in U.S. Pat. No.
4,873,029. The application method selected also depends on the
thickness of the cured coating. Coatings having a thickness ranging
from 1 to 50 microns may be applied by conventional methods used in
coating technology. coatings of a thickness greater than 50 microns
may require molding methods typically used for overlays.
[0058] The polymeric coating composition includes compositions
resulting in thermoplastic or thermosetting coatings, which are
described in the Kirk-Othmer Encyclopedia of Chemical Technology,
Fourth Edition, Volume 6, pages 669 to 760. The coating may
comprise at least one polymer selected from the group consisting of
polyurethanes, melamine resins, polyvinyl alcohol, polyacrylates,
polymethacrylates, polyamide resins and epoxy resins. Such
polymer-forming coating compositions are described in U.S. Pat. No.
4,425,403.
[0059] The host material will usually be transparent, but may be
translucent or even opaque. The host material need only be pervious
to that portion of the electromagnetic spectrum, which activates
the photochromic substance, i.e., that wavelength of ultraviolet
(UV) light that produces the open or colored form of the substance
and that portion of the visible spectrum that includes the
absorption maximum wavelength of the substance in its UV activated
form, i.e., the open form. Preferably, the host color should not be
such that it masks the color of the activated form of the
photochromic compounds, i.e., so the change in color is readily
apparent to the observer. Compatible tints may be applied to the
host material as described in U.S. Pat. No. 5,645,767 in column 13,
line 59 to column 14, line 3.
[0060] Most preferably, the polymeric organic host material is a
solid transparent or optically clear material, e.g., materials
suitable for optical applications, such as piano, ophthalmic and
contact lenses, windows, automotive transparencies, e.g.,
windshields, aircraft transparencies, plastic sheeting, polymeric
films, etc.
[0061] Examples of polymeric organic host materials which may be
used with the photochromic compounds described herein include:
polymers, i.e., homopolymers and copolymers, of the bis(allyl
carbonate) monomers, diethylene glycol dimethacrylate monomers,
diisopropenyl benzene monomers, ethoxylated bisphenol A
dimethacrylate monomers, ethylene glycol bismethacrylate monomers,
poly(ethylene glycol) bismethacrylate monomers, ethoxylated phenol
bismethacrylate monomers, alkoxylated polyhydric alcohol acrylate
monomers, such as ethoxylated trimethylol propane triacrylate
monomers, urethane acrylate monomers, such as those described in
U.S. Pat. No. 5,373,033, and vinylbenzene monomers, such as those
described in U.S. Pat. No. 5,475,074 and styrene; polymers, i.e.,
homopolymers and copolymers, mono- or polyfunctional, e.g., di- or
multi-functional, acrylate and/or methacrylate monomers,
poly(C.sub.1-C.sub.12 alkyl methacrylates), such as poly(methyl
methacrylate), poly(oxyalkylene)dimethacrylate, poly(alkoxylated
phenol methacrylates), cellulose acetate, cellulose triacetate,
cellulose acetate propionate, cellulose acetate butyrate,
poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride),
poly(vinylidene chloride), polyurethanes, polythiourethanes,
thermoplastic polycarbonates, polyesters, poly(ethylene
terephthalate), polystyrene, poly(alpha methylstyrene),
copoly(styrene-methyl methacrylate), copoly(styrene-acrylonitrile),
polyvinylbutyral and polymers, i.e., homopolymers and copolymers,
of diallylidene pentaerythritol, particularly copolymers with
polyol (allyl carbonate) monomers, e.g., diethylene glycol
bis(allyl carbonate), and acrylate monomers, e.g., ethyl acrylate,
butyl acrylate. Further examples of polymeric organic host
materials are disclosed in the U.S. Pat. No. 5,753,146, column 8,
line 62 to column 10, line 34.
[0062] Transparent copolymers and blends of transparent polymers
are also suitable as host materials. Preferably, the host material
or substrate for the photochromic polymeric coating composition is
an optically clear polymerized organic material prepared from a
thermoplastic polycarbonate resin, such as the carbonate-linked
resin derived from bisphenol A and phosgene, which is sold under
the trademark, LEXAN; a polyester, such as the material sold under
the trademark, MYLAR; a poly(methyl methacrylate), such as the
material sold under the trademark, PLEXIGLAS; polymerizates of a
polyol(allyl carbonate) monomer, especially diethylene glycol
bis(allyl carbonate), which monomer is sold under the trademark
CR-39, and polymerizates of copolymers of a polyol (allyl
carbonate), e.g., diethylene glycol bis(allyl carbonate), with
other copolymerizable monomeric materials, such as copolymers with
vinyl acetate, e.g., copolymers of from 80-90 percent diethylene
glycol bis(allyl carbonate) and 10-20 percent vinyl acetate,
particularly 80-85 percent of the bis(allyl carbonate) and 15-20
percent vinyl acetate, and copolymers with a polyurethane having
terminal diacrylate functionality, as described in U.S. Pat. Nos.
4,360,653 and 4,994,208; and copolymers with aliphatic urethanes,
the terminal portion of which contain allyl or acrylyl functional
groups, as described in U.S. Pat. No. 5,200,483; poly(vinyl
acetate), polyvinylbutyral, polyurethane, polythiourethanes,
polymers of members of the group consisting of diethylene glycol
dimethacrylate monomers, diisopropenyl benzene monomers,
ethoxylated bisphenol A dimethacrylate monomers, ethylene glycol
bismethacrylate monomers, poly(ethylene glycol) bismethacrylate
monomers, ethoxylated phenol bismethacrylate monomers and
ethoxylated trimethylol propane triacrylate monomers; cellulose
acetate, cellulose propionate, cellulose butyrate, cellulose
acetate butyrate, polystyrene and copolymers of styrene with methyl
methacrylate, vinyl acetate and acrylonitrile.
[0063] More particularly contemplated is use of the photochromic
naphthopyrans of the present invention with optical organic resin
monomers used to produce optically clear coatings and
polymerizates, i.e., materials suitable for optical applications,
such as for example plano and ophthalmic lenses, windows, and
automotive transparencies. Such optically clear polymerizates may
have a refractive index that may range from 1.48 to 1.75, e.g.,
from 1.495 to 1.66.
[0064] Specifically contemplated are polymerizates of optical
resins sold by PPG Industries, Inc. under the CR-designation, e.g.,
CR-307, CR-407 and CR-607, and polymerizates prepared for use as
hard or soft contact lenses. Methods for producing both types of
contact lenses are disclosed in U.S. Pat. No. 5,166,345, column 11,
line 52, to column 12, line 52. Additional polymerizates
contemplated for use with the photochromic naphthopyrans of the
present invention are polymerizates used to form soft contact
lenses with high moisture content described in U.S. Pat. No.
5,965,630 and extended wear contact lenses described in U.S. Pat.
No. 5,965,631.
[0065] The present invention is more particularly described in the
following examples, which are intended as illustrative only, since
numerous modifications and variations therein will be apparent to
those skilled in the art.
EXAMPLE 1
Step 1
[0066] Phenyl acetyl chloride (20 milliliters (mL)) and phenyl
acetylene (10 mL) were mixed in a reaction flask equipped with a
magnetic stirrer, oil bath and a condenser. The mixture was
maintained at a temperature of 180.degree. C. and stirred
overnight. After cooling to room temperature, potassium hydroxide
(5 grams), water (10 mL) and methanol (200 mL) were added to the
reaction flask and the reaction mixture was stirred overnight at
room temperature. The methanol was removed under vacuum and the
remaining black residue was dissolved in a 10 weight percent
solution of potassium hydroxide (150 mL). The resulting solution
was extracted with ether three times. The remaining aqueous portion
was acidified and extracted with ether three times. The ether
extracts were combined, washed with sodium bicarbonate solution
three times and dried over anhydrous sodium sulfate. The solvent,
methanol, was removed on a rotary evaporator to yield 11.0 grams of
product which crystallized at room temperature. A nuclear magnetic
resonance (NMR) spectrum showed the product to have a structure
consistent with 3-phenyl-1-naphthol.
Step 2
[0067] 3-Phenyl-1-naphthol (4.4 grams) from Step 1,
1,1-diphenylpropargyl alcohol (4.6 grams), p-toluene sulfonic acid
(0.2 gram) and toluene (100 mL) were mixed in a reaction flask and
stirred for one hour at room temperature. The reaction mixture was
heated to 50-60.degree. C. and stirred for another two hours. The
resulting mixture was washed with water twice and dried over
anhydrous sodium sulfate. The solvent, toluene, was removed using a
rotary evaporator. The resulting product was purified on a silica
gel column (using hexane as the eluant) to yield 3.7 grams of a
crystalline product having a melting point of 150-151.degree. C. An
NMR spectrum showed the product to have a structure consistent with
2,2-diphenyl-5-phenyl-2H-naphtho[1,2-b]pyran.
EXAMPLE 2
[0068] The procedure of Example 1 was followed except that in Step
2, 1-phenyl, 1-(4-methoxyphenyl)-propargyl alcohol was used instead
of 1,1-diphenyl-propargyl alcohol. NMR analysis showed the product
to have a structure consistent with 2-phenyl,
2-(4-methoxyphenyl)-5-phenyl-2H-napht- ho[1,2-b]pyran.
EXAMPLE 3
[0069] The procedure of Example 1 was followed except that in Step
2, 1,1-di(4-methoxyphenyl)-propargyl alcohol was used instead of
1,1-diphenyl-propargyl alcohol. NMR analysis showed the product to
have a structure consistent with
2,2-di(4-methoxyphenyl)-5-phenyl-2H-naphtho[1,2- -b]pyran.
EXAMPLE 4
[0070] The procedure of Example 1 was followed except that in Step
2, 1-phenyl, 1-(4-morpholinophenyl)-propargyl alcohol was used
instead of 1,1-diphenyl-propargyl alcohol. NMR analysis showed the
product to have a structure consistent with 2-phenyl,
2-(4-morpholinophenyl)-5-phenyl-2H-na- phtho[1,2-b]pyran.
EXAMPLE 5
Step 1
[0071] The procedure of Step 1 of Example 1 was followed except
that: 4-methoxy phenyl acetyl chloride was used in place of phenyl
acetyl chloride. The resulting mixture containing
7-methoxy-3-phenyl-1-naphthol was used in the next step without
further purification.
Step 2
[0072] The procedure of Step 2 of Example 1 was followed except
that: 7-methoxy-3-phenyl-1-naphthol and
1,1-di(4-methoxyphenyl)-propargyl alcohol were used in place of
1,1-di phenyl-propargyl alcohol. NMR analysis showed the product to
have a structure consistent with
2,2-di(4-methoxyphenyl)-9-methoxy-5-phenyl-2H-naphtho[1,2-b]pyran.
EXAMPLE 6
[0073] The procedure Example 5 was followed except that in Step 2,
1-phenyl, 1-(4-morpholinophenyl)-propargyl alcohol was used in
place of 1,1-di(4-methoxyphenyl)-propargyl alcohol. NMR analysis
showed the product to have a structure consistent with 2-phenyl,
2-(4-morpholinophenyl)-9-methoxy-5-phenyl-2H-naphtho[1,2-b]pyran.
EXAMPLE 7
Step 1
[0074] The procedure of Step 1 of Example 1 was followed except
that 4-ethynyl toluene was used in place of phenyl acetylene. The
resulting mixture containing 3-(4-methylphenyl)-1-naphthol was used
in the next step without further purification.
Step 2
[0075] The procedure of Step 2 of Example 1 was followed except
that 3-(4-methylphenyl)-1-naphthol and
1,1-di(4-methoxyphenyl)-propargyl alcohol were used. NMR analysis
showed the product to have a structure consistent with
2,2-di(4-methoxyphenyl)-5-(4-methylphenyl)-2H-naphtho[1,2-
-b]pyran.
EXAMPLE 8
[0076] The procedure of Example 7 was followed except that in Step
2, 1-phenyl, 1-(4-methoxyphenyl)-propargyl alcohol was used in
place of 1,1-di(4-methoxyphenyl)-propargyl alcohol. NMR analysis
showed the product to have a structure consistent with 2-phenyl,
2-(4-methoxyphenyl)-5-(4-methylphenyl)-2H-naphtho[1,2-b]pyran.
EXAMPLE 9
Step 1
[0077] The procedure of Step 1 of Example 1 was followed except
that 4-methoxy phenyl acetyl chloride was used in place of phenyl
acetyl chloride and 4-ethynyl toluene was used in place of phenyl
acetylene. The resulting mixture containing
3-(4-methylphenyl)-7-methoxy-1-naphthol was used in the next step
without further purification.
Step 2
[0078] The procedure of Step 2 of Example 1 was followed except
that 3-(4-methylphenyl)-7-methoxy-3-phenyl-1-naphthol and
1,1-di(4-methoxyphenyl)-propargyl alcohol were used. NMR analysis
showed the product to have a structure consistent with
2,2-di(4-methoxyphenyl)-9-
-methoxy-5-(4-methylphenyl)-2H-naphtho[1,2-b]pyran.
COMPARATIVE EXAMPLES 1-3
[0079] Comparative Example 1 was prepared according to the
procedures for preparing Comparative Example 1 in U.S. Pat. No.
5,458,814, column 18, lines 1-8. The compound was determined to be
2,2-diphenyl-[2H]naphtho[1,2- -b]pyran.
[0080] Comparative Example 2 was produced following the procedures
of Step 2 of Example 1 of U.S. Pat. No. 5,458,814, except that
1-hydroxynaphthylene was used in place of
methyl-1,4-dihydroxy-2-naphthoa- te to produce
2,2-di(4-methoxyphenyl)-[2H]naphtho[1,2-b]pyran.
[0081] Comparative Example 3 was prepared according to the
procedures for preparing Example 2 in U.S. Pat. No. 5,658,501. The
compound was determined to be
2,2-di(4-methoxyphenyl)-5-(2,4-dimethoxyphenyl)-6-acetox-
y-[2H]naphtho[1,2-b]pyran.
EXAMPLE 10
Part A
[0082] Testing was done with the photochromic compounds described
in Examples 1 through 9 and Comparative Examples 1 through 3 in the
following manner. A quantity of photochromic compound calculated to
yield a 1.5.times.10.sup.-3 molal solution was added to a flask
containing 50 grams of a monomer blend of 4 parts ethoxylated
bisphenol A dimethacrylate (BPA 2EO DMA), 1 part poly(ethylene
glycol) 600 dimethacrylate, and 0.033 weight percent
2,2'-azobis(2-methyl propionitrile) (AIBN). The photochromic
compound was dissolved into the monomer blend by stirring and
gentle heating, if necessary. After a clear solution was obtained,
it was poured into a flat sheet mold having the interior dimensions
of 2.2 mm.times.6 inches (15.24 cm) .times.6 inches (15.24 cm). The
mold was sealed and placed in a horizontal air flow, programmable
oven programmed to increase the temperature from 40.degree. C. to
95.degree. C. over a 5 hour interval, hold the temperature at
95.degree. C. for 3 hours, lower it to 60.degree. C. over a 2 hour
interval and then hold it at 60.degree. C. for 16 hours. After the
mold was opened, the polymer sheet was cut using a diamond blade
saw into 2 inch (5.1 centimeters) test squares.
Part B
[0083] The photochromic test squares prepared in Part A were tested
for photochromic response on an optical bench. Prior to testing on
the optical bench, the photochromic test squares were conditioned,
i.e., exposed to 365 nanometer ultraviolet light for about 15
minutes to activate the photochromic compounds and then placed in a
76.degree. C. oven for about 15 minutes to bleach or inactivate the
photochromic compounds. The test squares were then cooled to room
temperature, exposed to fluorescent room lighting for at least 2
hours and then kept covered for at least 2 hours prior to testing
on an optical bench maintained at 72.degree. F. (22.2.degree. C.).
The bench was fitted with a 250 watt Xenon arc lamp, a remote
controlled shutter, a copper sulfate bath acting as a heat sink for
the arc lamp, a Schott WG-320 nm cut-off filter which removes short
wavelength radiation; neutral density filter(s) and a sample holder
in which the square to be tested was inserted. The power output of
the optical bench, i.e., the dosage of light that the sample lens
would be exposed to, was calibrated with a photochromic test square
used as a reference standard. This resulted in a power output
ranging from 0.15 to 0.20 milliwatts per square centimeter
(mW/cm2). Measurement of the power output was made using a GRASEBY
Optronics Model S-371 portable photometer (Serial #21536) with a
UV-A detector (Serial #22411) or comparable equipment. The UV-A
detector was placed into the sample holder and the light output was
measured. Adjustments to the power output were made by increasing
or decreasing the lamp wattage or by adding or removing neutral
density filters in the light path.
[0084] A monitoring, collimated beam of light from a tungsten lamp
was passed through the square at a small angle (approximately
30.degree.) normal to the square. After passing through the square,
the light from the tungsten lamp was directed to a detector through
Spectral Energy Corp. GM-200 monochromator set at the previously
determined visible lambda max of the photochromic compound being
measured. The output signals from the detector were processed by a
radiometer.
[0085] Change in optical density (.DELTA.OD) was determined by
inserting a test square in the bleached state into the sample
holder, adjusting the transmittance scale to 100%, opening the
shutter from the Xenon lamp to provide ultraviolet radiation to
change the test square from the bleached state to an activated
(i.e., darkened) state, measuring the transmittance in the
activated state, and calculating the change in optical density
according to the formula: .DELTA.OD=log(100/%Ta), where %Ta is the
percent transmittance in the activated state and the logarithm is
to the base 10.
[0086] The optical properties of the photochromic compounds in the
test squares are reported in Table 1. The .DELTA.OD/Min, which
represents the sensitivity of the photochromic compound's response
to UV light, was measured over the first five (5) seconds of UV
exposure, then expressed on a per minute basis. The saturation
optical density (.DELTA.OD@ Saturation) was taken under identical
conditions as the .DELTA.OD/Min, except UV exposure was continued
for 15 minutes.
[0087] The lambda max (Vis) is the wavelength in the visible
spectrum at which the maximum absorption of the activated (colored)
form of the photochromic compound in a test square occurs. The
lambda max (Vis) wavelengths reported in Table 1 were determined by
testing the photochromic test square polymerizates of Part A in a
Varian Cary 3 uv-visible spectrophotometer. The bleach rate (T 1/2)
is the time interval in seconds for the absorbance of the activated
form of the photochromic compound in the test squares to read one
half the highest absorbance at room temperature (72.degree. F.,
22.2.degree. C.) after removal of the source of activating
light.
[0088] Each of the compounds of the Examples and the Comparative
Examples exhibited dual peak absorptions in the visible spectrum
(lambda max visible) in distinct color regions. For the highest
lambda max visible (Band B), the corresponding optical density
(.DELTA. OD/Min, and .DELTA. OD at saturation), for the compounds
of the Examples and Comparative Examples are tabulated in Table 1.
Table 1 also includes the bleach rate (T 1/2) for each of the
compounds as measured at Band B.
1TABLE 1 Bleach Compound Sensitivity .DELTA.OD @ Rate .lambda. MAX
Example .DELTA.OD/MIN Saturation T 1/2 sec (nm) Vis 1 (Band A) 406
1 (Band B) 0.12 0.27 120 489 Comp. Ex. 1 403 (Band A) Comp. Ex. 1
0.11 0.85 >1200 480 (Band B) 2 (Band A) 419 2 (Band B) 0.12 0.18
71 500 3 (Band A) 424 3 (Band B) 0.13 0.11 50 510 4 (Band A) 448 4
(Band B) 0.13 0.15 72 538 5 (Band A) 436 5 (Band B) 0.10 0.10 56
538 6 (Band A) 482 6 (Band B) 0.12 0.17 78 553 7 (Band A) 425 7
(Band B) 0.10 0.11 52 511 8 (Band B) 419 8 (Band B) 0.16 0.18 73
501 9 (Band B) 436 9 (Band B) 0.09 0.12 56 539 Comp. Ex. 2 417
(Band A) Comp. Ex. 2 0.14 0.59 377 507 (Band B) Comp. Ex. 3 422
(Band A) Comp. Ex. 3 0.15 0.55 248 511 (Band B)
[0089] The results of Table 1 show that the compounds of the
present invention demonstrate a range of photochromic properties,
e.g., lambda max values for Band A from 406 to 482 nanometers and
for Band B from 489 to 553 nanometers, sensitivity levels from 0.09
to 0.16, values for .DELTA.OD@ Saturation from 0.10 to 0.27 and
Bleach Rates from 50 to 120 seconds. Comparative Example 1 is an
unsubstituted naphthopyran that has comparable lambda max values
and sensitivities to Example 1, except that the bleach rate of
Example 1 is ten times faster. Comparative Examples 2 and 3 have
methoxy substituents on the phenyl at the 2 position. Comparative
Example 3 also has a dimethoxy substituent at position 5 and an
acetoxy substituent at position 6. A comparison between Comparative
Examples 2 and 3 and Example 3, 5 and 7 show that in each case, the
compounds of the present invention fade faster than the comparative
examples.
[0090] The present invention has been described with reference to
specific details of particular embodiments thereof. It is not
intended that such details be regarded as limitations upon the
scope of the invention except insofar as to the extent that they
are included in the accompanying claims.
* * * * *