U.S. patent application number 09/738175 was filed with the patent office on 2002-01-17 for novel substituted naphthopyrans.
Invention is credited to Lin, Jibin.
Application Number | 20020007078 09/738175 |
Document ID | / |
Family ID | 26871421 |
Filed Date | 2002-01-17 |
United States Patent
Application |
20020007078 |
Kind Code |
A1 |
Lin, Jibin |
January 17, 2002 |
Novel substituted naphthopyrans
Abstract
Described are novel reversible photochromic naphthopyran
compounds, examples of which are compounds having a cycloalkyl
ester substituent at the number 5 carbon atom and optionally
certain substituents at the number 6 carbon atom of the naphtho
portion of the naphthopyran and certain 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 naphtho portion of the
naphthopyran. These compounds may be represented by the following
graphic formulae: 1 Also described are various substrates, e.g.,
paper, glass, organic polymeric materials, etc., that contain or
that are coated with such compounds. Optically clear articles such
as ophthalmic lenses or other plastic transparencies that
incorporate the novel naphthopyran compounds or combinations
thereof with complementary photochromic compounds, e.g., certain
other naphthopyrans, indenonaphthopyrans, benzopyrans, oxazine-type
compounds, etc., are also described.
Inventors: |
Lin, Jibin; (Fremont,
CA) |
Correspondence
Address: |
PPG INDUSTRIES INC
INTELLECTUAL PROPERTY DEPT
ONE PPG PLACE
PITTSBURGH
PA
15272
US
|
Family ID: |
26871421 |
Appl. No.: |
09/738175 |
Filed: |
December 15, 2000 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60175640 |
Jan 12, 2000 |
|
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Current U.S.
Class: |
549/389 |
Current CPC
Class: |
G02B 5/23 20130101; Y10T
428/31855 20150401; C07D 311/92 20130101 |
Class at
Publication: |
549/389 |
International
Class: |
C07D 311/92 |
Claims
I claim:
1. A naphthopyran compound of 2H-naphtho[1,2-b]pyran structure,
characterized by having in the 5 position, a group, C(O)OR.sub.1,
wherein R.sub.1 is (C.sub.3-C.sub.12) cycloalkyl,
mono(C.sub.1-C.sub.6)alkyl substituted C.sub.3-C.sub.12 cycloalkyl,
mono(C.sub.1-C.sub.6)alkoxy substituted C.sub.3-C.sub.12
cycloalkyl, halo(C.sub.3-C.sub.12)cycloalkyl- , C.sub.4-C.sub.12
bicyloalkyl or C.sub.7-C.sub.12 tricycloalkyl, said halo being
bromo, chloro, fluoro or iodo.
2. The naphthopyran compound of claim 1 wherein said naphthopyran
is represented by the following graphic formula: 11wherein, (a)
R.sub.1 is C.sub.3-C.sub.12 cycloalkyl, mono(C.sub.1-C.sub.6)alkyl
substituted C.sub.3-C.sub.12 cycloalkyl,
mono(C.sub.1-C.sub.6)alkoxy substituted C.sub.3-C.sub.12
cycloalkyl, halo(C.sub.3-C.sub.12)cycloalkyl, C.sub.4-C.sub.12
bicycloalkyl or C.sub.7-C.sub.12 tricycloalkyl; (b) R.sub.2 is
hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.7 cycloalkyl,
phenyl, mono-, di-, or tri-substituted phenyl, the group
--OR.sub.4, wherein R.sub.4 is hydrogen, C.sub.1-C.sub.6 alkyl,
phenyl(C.sub.1-C.sub.3)alkyl, mono(C.sub.1-C.sub.6)alkyl
substituted phenyl(C.sub.1-C.sub.3)alkyl,
mono(C.sub.1-C.sub.6)alkoxy substituted
phenyl(C.sub.1-C.sub.3)alkyl,
(C.sub.1-C.sub.6)alkoxy(C.sub.2-C.sub.4)alk- yl, C.sub.3-C.sub.7
cycloalkyl, mono(C.sub.1-C.sub.4)alkyl substituted C.sub.3-C.sub.7
cycloalkyl, C.sub.1-C.sub.6 haloalkyl, allyl, the group,
--CH(R.sub.5)X, wherein X is CN, CF.sub.3, halogen or --C(O)W
wherein W is --OR.sub.9 or --N(R.sub.10)R.sub.11, R.sub.5 is
hydrogen or C.sub.1-C.sub.6 alkyl, R.sub.9 is hydrogen, allyl,
C.sub.1-C.sub.6 alkyl, phenyl, mono(C.sub.1-C.sub.6)alkyl
substituted phenyl, mono(C.sub.1-C.sub.6)alkoxy substituted phenyl,
phenyl(C.sub.1-C.sub.3)al- kyl, mono(C.sub.1-C.sub.6)alkyl
substituted phenyl(C.sub.1-C.sub.3)alkyl,
mono(C.sub.1-C.sub.6)alkoxy substituted
phenyl(C.sub.1-C.sub.3)alkyl, C.sub.1-C.sub.6
alkoxy(C.sub.2-C.sub.4)alkyl, C.sub.1-C.sub.6 haloalkyl or R.sub.1,
and R.sub.10 and R.sub.11 are each selected from the group
consisting of hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.7
cycloalkyl, phenyl, mono-substituted phenyl and di-substituted
phenyl, or R.sub.4 is the group, --C(O)Y, wherein Y is hydrogen,
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, mono- or
di-substituted or unsubstituted aryl groups phenyl or naphthyl,
phenoxy, C.sub.1-C.sub.6 mono- or di-alkyl substituted phenoxy,
C.sub.1-C.sub.6 mono- or di-alkoxy substituted phenoxy,
C.sub.1-C.sub.6 alkylamino, phenylamino, C.sub.1-C.sub.6 mono- or
di-alkyl substituted phenylamino, or C.sub.1-C.sub.6 mono- or
di-alkoxy substituted phenylamino, said aryl substituents being
selected from C.sub.1-C.sub.6 alkyl or C.sub.1-C.sub.6 alkoxy, said
halogen or halo substituents being bromo, chloro, fluoro or iodo;
(c) each R.sub.3 is R.sub.2 and n is an integer selected from 0, 1,
2 or 3; and (d) B and B' are each selected from the group
consisting of: (i) the unsubstituted, mono-, di- and
tri-substituted aryl groups, phenyl and naphthyl; (ii)
9-julolidinyl and the unsubstituted, mono- and di-substituted
heteroaromatic groups 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 (d)(i) and (ii) being
selected from the group consisting of hydroxy, aryl,
mono(C.sub.1-C.sub.6)alkoxyar- yl, 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.s- ub.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 aryl being phenyl or
naphthyl and said halo and halogen being bromo, chloro, fluoro or
iodo; (iii) the unsubstituted or mono-substituted groups,
pyrazolyl, imidazolyl, pyridyl, pyrazolinyl, imidazolinyl,
pyrrolinyl, phenothiazinyl, phenoxazinyl, phenazinyl or acridinyl,
each of said substituents being selected from the group consisting
of C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.4 alkoxy, phenyl, and
halogen; (iv) monosubstituted phenyl, having a substituent at the
para position that is a linking group, --(CH.sub.2).sub.t-- or
--O--(CH.sub.2).sub.t--, wherein t is the integer 1, 2, 3, 4, 5 or
6, connected to an aryl group, e.g. phenyl or naphthyl, which is a
member of another photochromic naphthopyran, such as
naphtho[2,1-b]pyran or naphtho[1,2-b]pyran; (v) the group
represented by the following graphic formula: 12wherein E is
methylene or oxygen and G is oxygen or substituted nitrogen,
provided that when G 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.6 is C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, hydroxy,
or halogen; R.sub.7 and R.sub.8 are each hydrogen or
C.sub.1-C.sub.6 alkyl; and q is the integer 0, 1 or 2; (vi)
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, C.sub.3-C.sub.12 cycloalkyl,
mono(C.sub.1-C.sub.6)alkoxy(C.sub.3-C.sub.12- )cycloalkyl,
mono(C.sub.1-C.sub.6)alkyl(C.sub.3-C.sub.12)-cycloalkyl,
halo(C.sub.3-C.sub.12)cycloalkyl and C.sub.4-C.sub.12 bicycloalkyl;
and (vii) the group represented by the following graphic formula:
13wherein L is hydrogen or C.sub.1-C.sub.4 alkyl and M is selected
from the 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 or halogen; or (e) B and B' taken together
form fluoren-9-ylidene, mono-, or di-substituted fluoren-9-ylidene
or a member selected from the group consisting of saturated
C.sub.3-C.sub.12 spiro-monocyclic hydrocarbon rings, saturated
C.sub.4-C.sub.12 spiro-bicylic hydrocarbon rings, and saturated
C.sub.7-C.sub.12 spiro-tricyclic hydrocarbon rings, each of said
fluoren-9-ylidene substituents being selected from the group
consisting of C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy and
halogen.
3. The naphthopyran of claim 2 wherein: (a) R.sub.1 is
C.sub.3-C.sub.10 cycloalkyl, mono(C.sub.1-C.sub.3)alkyl substituted
C.sub.3-C.sub.10 cycloalkyl, mono(C.sub.1-C.sub.3)alkoxy
substituted C.sub.3-C.sub.10 cycloalkyl,
chloro(C.sub.3-C.sub.10)cycloalkyl, fluoro(C.sub.1-C.sub.3)cy-
cloalkyl, C.sub.4-C.sub.10 bicycloalkyl or C.sub.7-C.sub.10
tricycloalkyl; (b) R.sub.2 is hydrogen, C.sub.1-C.sub.3 alkyl,
C.sub.3-C.sub.5 cycloalkyl, phenyl, mono- or di-substituted phenyl
or --OR.sub.4, wherein R.sub.4 is hydrogen, C.sub.1-C.sub.3 alkyl,
or the group, --CH(R.sub.5)X, wherein X is CN or --C(O)W wherein W
is --OR.sub.9 or --N(R.sub.10)R.sub.11, R.sub.5 is hydrogen or
methyl, R.sub.9 is hydrogen, 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(C.sub.2-C.sub.3- )alkyl,
C.sub.1-C.sub.4 haloalkyl or R.sub.1, and R.sub.10 nd R.sub.11 are
each selected from the group consisting of hydrogen,
C.sub.1-C.sub.4 alkyl, C.sub.5-C.sub.7 cycloalkyl, phenyl,
mono-substituted phenyl and di-substituted phenyl; or R.sub.4 is
the group --C(O)Y wherein Y is C.sub.1-C.sub.3 alkyl or
C.sub.1-C.sub.3 alkoxy, said phenyl substituents being
C.sub.1-C.sub.3 alkyl or C.sub.1-C.sub.3 alkoxy and said halo being
chloro or fluoro; (c) each R.sub.3 is hydrogen, C.sub.1-C.sub.4
alkyl, C.sub.3-C.sub.10 cycloalkyl, phenyl, mono- or di-
substituted phenyl, said phenyl substituents being C.sub.1-C.sub.3
alkyl or C.sub.1-C.sub.3 alkoxy, and n is the integer 0, 1 or 2;
(d) B and B' are each selected from the group consisting of: (i)
phenyl, mono-substituted and di-substituted phenyl; (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 (d) (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, chloro and
fluoro; (iii) the group represented by the following graphic
formula: 14wherein E is methylene and G is oxygen, R.sub.6 is
C.sub.1-C.sub.3 alkyl or C.sub.1-C.sub.3 alkoxy; R.sub.7 and
R.sub.8 are each hydrogen or C.sub.1-C.sub.4 alkyl; and q is 0 or
1; (iv) C.sub.1-C.sub.4 alkyl; and (v) the group represented by the
following graphic formula: 15wherein L is hydrogen or methyl, M is
phenyl or mono-substituted phenyl, said phenyl substituent being
C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 alkoxy or fluoro; or (e) B
and B' taken together form fluoren-9-ylidene, mono-substituted
fluoren-9-ylidene or a member selected from the group consisting of
saturated C.sub.3-C.sub.8 spiro-monocyclic hydrocarbon rings,
saturated C.sub.7-C.sub.10 spiro-bicyclic hydrocarbon rings, and
saturated C.sub.7-C.sub.10 spiro-tricyclic hydrocarbon rings, said
fluoren-9-ylidene substituent being selected from the group
consisting of C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 alkoxy, fluoro
and chloro.
4. The naphthopyran of claim 3 wherein: (a) R.sub.1 is
C.sub.3-C.sub.7 cycloalkyl; (b) R.sub.2 is hydrogen or
C.sub.1-C.sub.3 alkyl (c) R.sub.3 is hydrogen or C.sub.1-C.sub.3
alkyl, and n is the integer 0 or 1; (d) 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 (d)(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, phenyl, indolino, fluoro and chloro; (iii) the group
represented by the following graphic formula: 16wherein E is
methylene and G is oxygen, R.sub.6 is C.sub.1-C.sub.3 alkyl or
C.sub.1-C.sub.3 alkoxy; R.sub.7 and R.sub.8 are each hydrogen or
C.sub.1-C.sub.3 alkyl; and q is 0 or 1; or (e) B and B' taken
together form fluoren-9-ylidene, adamantylidene, bornylidene,
norbornylidene, or bicyclo[3.3.1]nonan-9-ylidene.
5. A naphthopyran compound selected from the group consisting of:
(a)
2,2-Diphenyl-5-cyclohexyloxycarbonyl-8-methyl-[2H]-naphtho[1,2-b]pyran;
(b)
2,2-Bis(4-methoxyphenyl)-5-cyclopropyloxycarbonyl-6-methoxy-[2H]-naph-
tho[1,2-b]pyran; (c)
2,2-Bis(4-methoxyphenyl)-5-cyclooctyloxycarbonyl-6-(e-
thoxycarbonyl)methoxy-[2H]-naphtho[1,2-b]pyran; (d)
2,2-Bis(4-methylphenyl)-5-cyclohexyloxycarbonyl-6-(methoxycarbonyloxy)-[2-
H]-naphtho[1,2-b]pyran; (e)
2,2-Diphenyl-5-cyclopropyloxycarbonyl-6-acetox-
y-[2H]-naphtho[1,2-b]pyran; (f)
2,2-Bis(4-methoxyphenyl)-5-cyclooctyloxyca-
rbonyl-6-methyl-[2H]-naphtho[1,2-b]pyran; (g)
2,2-Bis(4-methoxyphenyl)-5-c-
ycloheptyloxycarbonyl-6-methyl-9-methoxy-[2H]-naphtho[1,2-b]pyran;
(h)
2-(4-Methoxyphenyl)-2-(2-methyl,2,3-dihydrobenzofuran-5-yl)-5-cyclobutylo-
xycarbonyl-6-(ethoxycarbonyl)methoxy-[2H]-naphtho[1,2-b]pyran; (i)
2-phenyl-2-(2-dibenzofuryl)-5-cyclohexyloxycarbonyl-8-methyl-[2H]-naphtho-
[1,2-b]pyran; (j)
2,2-diphenyl-5-cyclohexyloxycarbonyl-8-methoxy-[2H]-naph-
tho[1,2-b]pyran; (k)
2-phenyl-2-(4-methoxyphenyl)-5-cyclohexyloxycarbonyl--
8-methoxy-[2H]-naphtho[1,2-b]pyran; and (1)
2-phenyl-2-(4-methylphenyl)-5--
cyclohexyloxycarbonyl-8-methoxy-[2H]-naphtho[1,2-b]pyran.
6. A photochromic article comprising in combination, 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 claims priority to provisional application
60/175,640, filed on Jan. 12, 2000.
DESCRIPTION OF THE INVENTION
[0002] The present invention relates to substituted
2H-naphtho[1,2-b]pyran compounds and to compositions and articles
containing such naphthopyran compounds. When exposed to light
radiation involving 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. Nos. 5,458,814, 5,573,712, 5,650,098, 5,656,206
and 5,658,500 disclose 2H-naphtho[1,2-b]pyrans substituted in the
5- and 6-positions that possess a reasonable rate of fade as well
as high colorability. The compounds exhibit activated colors
ranging from yellow to red/purple. International Patent Application
Publication No. WO 98/04937 describes 2H-naphtho[1,2-b]pyrans
having alkoxy groups as substituents at the 7- or 9- positions of
the naphthopyran ring.
[0007] Photochromic compounds may be incorporated into plastic
substrates, such as ophthalmic lenses, by various methods described
in the art. Such methods include dissolving or dispersing the
compound within the surface of a substrate, e.g., imbibition of the
photochromic compound into the substrate by immersion of the
substrate in a hot solution of the photochromic compound or by
depositing the photochromic compound on the surface of the
substrate and thermally transferring the photochromic compound from
a carrier into the substrate. The term "imbibition" or "imbibe" is
intended to mean and include permeation of the photochromic
compound into the substrate, solvent assisted transfer absorption
of the photochromic compound into the substrate, vapor phase
transfer and other such transfer mechanisms.
[0008] The extent to which the photochromic compounds penetrate the
polymeric substrate generally increases with increasing
temperature, increasing concentration of photochromic compounds at
the surface of the polymeric substrate and increasing period of
contact with the polymeric substrate. The ease with which the
photochromic compounds are incorporated is also dependent upon the
characteristics of the photochromic compounds and of the polymeric
substrate. The molecular size, melting point, and carrier matrix
solubility of the photochromic compounds as well as the receptivity
of the polymeric substrate all affect the ease of incorporation of
the photochromic compounds.
[0009] In some cases, due to the numerous variables affecting
production of photochromic articles, photochromic compounds may not
be incorporated into the plastic substrate with sufficient
uniformity and to a sufficient depth. This can result in poor
performance of the photochromic compound, e.g., inadequate
reversible color change of the photochromic article and non-neutral
color formation. Depending on the solubility of the photochromic
compound in the inbibition composition, crystals may form and cause
cosmetic defects on the surface of the photochromic article.
[0010] Methods for incorporating photochromic compounds into
polymeric substrates have been disclosed in U.S. Pat. Nos.
4,286,957, 4,880,667, 5,789,015 and 5,975,696. Various photochromic
compositions used in the process of incorporating photochromic
compounds into polymeric substrates have been disclosed in U.S.
Pat. Nos. 5,185,390, 5,391,327 and 5,770,115. As disclosed in U.S.
Pat. No. 5,753,146, in order to achieve activated neutral colors,
it is necessary to select and combine photochromic naphthopyran
compounds on the basis of their lambda max value, sensitivity,
optical density and fade rate under solar simulated conditions.
[0011] It has been unexpectedly discovered that
2H-naphtho[1,2-b]pyran compounds having a cycloalkyl
ester-substituent in the 5-position are more soluble in polymeric
matrices used in imbibition processes than 2H-naphtho[1,2-b]pyrans
having similar photochromic properties that are substituted with a
non-cycloalkyl ester. The cycloalkyl ester-substituted
2H-naphtho[1,2-b]pyran compounds may be used individually or in
combination with other complementary photochromic compounds to
produce photochromic articles. When used in place of non-cycloalkyl
ester-substituted 2H-naphtho[1,2-b]pyran compounds in imbibition
processes with polymeric carriers, e.g., hydroxypropyl cellulose,
use of the compounds of the present invention enables the
successful preparation of photochromic imbibed lenses of neutral
activated colors having a reduced occurrence of cosmetic
defects.
DETAILED DESCRIPTION OF THE INVENTION
[0012] 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.
[0013] In accordance with the present invention, it has now been
discovered that 2H-naphtho[1,2-b]pyrans having a cycloalkyl ester
substituent at the 5-position may be prepared. These naphthopyran
compounds demonstrate improved solubility in polymeric matrices
used as carriers in imbibition processes. Use of the compounds of
the present invention in place of non-cycloalkyl ester-substituted
2H-naphtho[1,2-b]pyrans in imbibition processes makes possible the
preparation of photochromic articles of neutral color having a
reduced occurrence of cosmetic defects.
[0014] The types of cosmetic defects that can occur on the polymer
surface during the imbibition process from the use of a
photochromic compound that is not compatible, e.g., soluble, in the
imbibition composition include pits, dimples, spots, orange peel,
uneven patterns and distortions of reflected light. The terms used
to describe these cosmetic defects are also used to describe
defects in coatings. Definitions of these and other such surface
defect terms are found in the Paint/Coating Dictionary by the
Federation of Societies for Coating Technology, Philadelphia.
[0015] In one contemplated embodiment, photochromic articles
prepared by the imbibition of photochromic compounds of the present
invention into polymeric organic substrates have a negligible
occurrence of cosmetic defects. By the term negligible, it is meant
that the number of cosmetic defects is so small and of so little
consequence as to warrant little or no attention.
[0016] The compounds of the present invention may be described as
naphthopyrans having substituents at the 2 position of the pyran
ring, at the number 5 position and optionally at the 6 carbon atoms
of the naphtho-portion of the naphthopyran ring. Substituents may
also be present at the 7, 8, 9 or 10 carbon atoms of the naphtho
portion of the naphthopyran ring. These compounds may be
represented by the following graphic formula I in which the
internal numbers 1 through 10 identify the ring atoms of the
naphthopyran: 2
[0017] In graphic formula I, R.sub.1 is C.sub.3-C.sub.12
cycloalkyl, e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and
cyclododecyl; mono(C.sub.1-C.sub.6)alkyl substituted
C.sub.3-C.sub.12 cycloalkyl, e.g., methylcyclopropyl,
ethylcyclopentyl, propylcyclohexyl, etc.;
mono(C.sub.1-C.sub.6)alkoxy substituted C.sub.3-C.sub.12
cycloalkyl, halo(C.sub.3-C.sub.12)cycloalkyl; C.sub.4-C.sub.12
bicycloalkyl, e.g., bicyclo[2.2.1]heptyl (norbornyl),
1,7,7-trimethyl bicyclo[2.2.1]heptyl (bornyl), bicyclo[3.2.1]octyl,
bicyclo[3.3.1]nonan-9-yl and bicyclo[4.3.2]undecyl; or
C.sub.7-C.sub.12 tricycloalkyl, e.g.,
tricyclo[2.2.1.0.sup.2,6]heptyl, tricyclo[3.3.1.1.sup.3,7]decyl
(adamantyl), and tricyclo[5.3.1.1.sup.2,6]dodecyl. The halo
substituents are bromo, chloro, fluoro or iodo.
[0018] In one contemplated embodiment, R.sub.1 is C.sub.3-C.sub.10
cycloalkyl, mono(C.sub.1-C.sub.3)alkyl substituted C.sub.3-C.sub.10
cycloalkyl, mono(C.sub.1-C.sub.3)alkoxy substituted
C.sub.3-C.sub.10 cycloalkyl, halo(C.sub.3-C.sub.10) cycloalkyl,
C.sub.7-C.sub.10 bicycloalkyl or C.sub.7-C.sub.10 tricycloalkyl,
wherein the halo substituents are chloro or fluoro. In another
contemplated embodiment, R.sub.1 is C.sub.3-C.sub.7 cycloalkyl.
[0019] R.sub.2 in graphic formula I may be hydrogen,
C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.7 cycloalkyl, phenyl, mono-,
di- or tri-substituted phenyl, the group --OR.sub.4, wherein
R.sub.4 is hydrogen, C.sub.1-C.sub.6 alkyl,
phenyl(C.sub.1-C.sub.3)alkyl, mono(C.sub.1-C.sub.6)alkyl
substituted phenyl(C.sub.1-C.sub.3)alkyl,
mono(C.sub.1-C.sub.6)alkoxy substituted
phenyl(C.sub.1-C.sub.3)alkyl,
(C.sub.1-C.sub.6)alkoxy(C.sub.2-C.sub.4)alkyl, C.sub.3-C.sub.7
cycloalkyl, mono(C.sub.1-C.sub.4)alkyl substituted C.sub.3-C.sub.7
cycloalkyl, C.sub.1-C.sub.6 haloalkyl, allyl or the group,
--CH(R.sub.5)X, wherein X is CN, CF.sub.3, halogen or --C(O)W
wherein W is --OR.sub.9 or --N(R.sub.10)R.sub.11, R.sub.5 is
hydrogen or C.sub.1-C.sub.6 alkyl, R.sub.9 is hydrogen, allyl,
C.sub.1-C.sub.6 alkyl, phenyl, mono(C.sub.1-C.sub.6)alkyl
substituted phenyl, mono(C.sub.1-C.sub.6)alkoxy substituted phenyl,
phenyl(C.sub.1-C.sub.3)al- kyl, mono(C.sub.1-C.sub.6)alkyl
substituted phenyl(C.sub.1-C.sub.3)alkyl,
mono(C.sub.1-C.sub.6)alkoxy substituted
phenyl(C.sub.1-C.sub.3)alkyl, C.sub.1-C.sub.6
alkoxy(C.sub.2-C.sub.4)alkyl, C.sub.1-C.sub.6 haloalkyl or R.sub.1,
and R.sub.10 and R.sub.11 are each selected from the group
consisting of hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.7
cycloalkyl, phenyl, mono-substituted phenyl and di-substituted
phenyl; or R.sub.4 is the group, --C(O)Y, wherein Y is hydrogen,
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, the mono- or
di-substituted or unsubstituted aryl groups phenyl or naphthyl,
phenoxy, C.sub.1-C.sub.6 mono- or di-alkyl substituted phenoxy,
C.sub.1-C.sub.6 mono- or di-alkoxy substituted phenoxy,
C.sub.1-C.sub.6 alkylamino, phenylamino, C.sub.1-C.sub.6 mono- or
di-alkyl substituted phenylamino, or C.sub.1-C.sub.6 mono- or
di-alkoxy substituted phenylamino, each of said aryl, i.e., phenyl
or naphthyl, substituents being selected from C.sub.1-C.sub.6 alkyl
or C.sub.1-C.sub.6 alkoxy, each of said halogen or halo
substituents are bromo, chloro, fluoro or iodo.
[0020] In one contemplated embodiment, R.sub.2 is hydrogen,
C.sub.1-C.sub.3 alkyl, C.sub.3-C.sub.5 cycloalkyl, phenyl, mono- or
di-substituted phenyl or --OR.sub.4, wherein R.sub.4 is hydrogen,
C.sub.1-C.sub.3 alkyl, or the group, --CH(R.sub.5)X, wherein X is
CN or --C(O)W wherein W is --OR.sub.9 or --N(R.sub.10)R.sub.11,
R.sub.5 is hydrogen or methyl, R.sub.9 is hydrogen, 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(C.sub.2-C.sub.3)alkyl, C.sub.1-C.sub.4
haloalkyl or R.sub.1, and R.sub.10 and R.sub.11 are each selected
from the group consisting of hydrogen, C.sub.1-C.sub.4 alkyl,
C.sub.5-C.sub.7 cycloalkyl, phenyl, mono-substituted phenyl and
di-substituted phenyl; or R.sub.4 is the group --C(O)Y wherein Y is
C.sub.1-C.sub.3 alkyl or C.sub.1-C.sub.3 alkoxy, each of said
phenyl substituents being C.sub.1-C.sub.3 alkyl or C.sub.1-C.sub.3
alkoxy, and each of said halo substituents are chloro or fluoro. In
another contemplated embodiment, R.sub.2 is hydrogen or
C.sub.1-C.sub.3 alkyl.
[0021] Each R.sub.3 in graphic formula I may be independently
selected from the aforementioned substituents assigned to R.sub.2,
and n is selected from the integers 0, 1, 2, and 3. In one
contemplated embodiment, each R.sub.3 is hydrogen, C.sub.1-C.sub.4
alkyl, C.sub.3-C.sub.10 cycloalkyl, phenyl, mono- or di-
substituted phenyl, said phenyl substituents being C.sub.1-C.sub.3
alkyl or C.sub.1-C.sub.3 alkoxy, and n is the integer 0, 1 or 2. In
another contemplated embodiment, R.sub.3 is hydrogen or
C.sub.1-C.sub.3 alkyl and n is 0 or 1.
[0022] In the definitions of R.sub.1, R.sub.2 and R.sub.3 in
graphic formula I, like letters have the same meaning unless stated
otherwise. The carbon ranges disclosed for the substituents herein
were selected on the basis of commercial availability. Compounds of
the present invention may have substituents having carbon ranges
outside of those listed as such materials become available.
[0023] B and B' may each be selected from the group consisting
of:
[0024] (a) the unsubstituted, mono-, di- and tri-substituted aryl
groups, phenyl and naphthyl;
[0025] (b) 9-julolidinyl and the unsubstituted, mono- and
di-substituted heteroaromatic groups 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 (a)
and (b) 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.s- ub.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 halo and halogen being
bromo, chloro, fluoro or iodo; each aryl, either alone or as a
component of a substituent, e.g., haloaryl, aryloxy, etc.,
described for the aryl and heteroaromatic substituents in parts (a)
and (b) is phenyl or naphthyl;
[0026] (c) the unsubstituted or mono-substituted groups, pyrazolyl,
imidazolyl, pyridyl, pyrazolinyl, imidazolinyl, pyrrolinyl,
phenothiazinyl, phenoxazinyl, phenazinyl or acridinyl, each of said
substituents for said groups in part (c) being selected from the
group consisting of C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy,
phenyl, and halogen, as defined in part (b);
[0027] (d) monosubstituted phenyl, having a substituent at the para
position that is the linking group, --(CH.sub.2).sub.t-- or
--O--(CH.sub.2).sub.t--, wherein t is the integer 1, 2, 3, 4, 5 or
6, connected to an aryl group, e.g. phenyl or naphthyl, which is a
member of another photochromic naphthopyran, such as
naphtho[2,1-b]pyran or naphtho[1,2-b]pyran;
[0028] (e) the group represented by the following graphic formula
IIA or IIB: 3
[0029] wherein E is methylene or oxygen and G is oxygen or
substituted nitrogen, provided that when G 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.6 is C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 alkoxy, hydroxy, halogen; R.sub.7 and R.sub.8 are
each hydrogen or C.sub.1-C.sub.6 alkyl; and q is the integer 0, 1
or 2;
[0030] (f) 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, C.sub.3-C.sub.12
cycloalkyl,
mono(C.sub.1-C.sub.6)alkoxy(C.sub.3-C.sub.12)cycloalkyl,
mono(C.sub.1-C.sub.6)alkyl(C.sub.3-C.sub.12)-cycloalkyl,
halo(C.sub.3-C.sub.12)cycloalkyl and C.sub.4-C.sub.12 bicycloalkyl,
said halo being bromo, chloro, fluoro or iodo; and
[0031] (g) the group represented by the following graphic formula
IIC: 4
[0032] wherein L is hydrogen or C.sub.1-C.sub.4 alkyl and M is
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 (g) being C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 alkoxy or halogen.
[0033] Alternatively, B and B' taken together may form
fluoren-9-ylidene, mono-, or di-substituted fluoren-9-ylidene or
form a member selected from the group consisting of saturated
C.sub.3-C.sub.12 spiro-monocyclic hydrocarbon rings, e.g.,
cyclopropylidene, cyclobutylidene, cyclopentylidene,
cyclohexylidene, cycloheptylidene, cyclooctylidene,
cyclononylidene, cyclodecylidene cycloundecylidene, and
cyclododecylidene; saturated C.sub.4-C.sub.12 spiro-bicyclic
hydrocarbon rings, e.g., bicyclo[2.2.1]heptylidene
(norbornylidene), 1,7,7-trimethyl bicyclo[2.2.1]heptylidene
(bornylidene), bicyclo[3.2.1]octylidene,
bicyclo[3.3.1]nonan-9-ylidene, bicyclo[4.3.2]undecane, and
saturated C.sub.7-C.sub.12 spiro-tricyclic hydrocarbon rings, e.g.,
tricyclo[2.2.1.0.sup.2,6]heptylidene, tricyclo[3.3.1.1.sup.3,7
]decylidene (adamantylidene), and tricyclo[5.3.1.1.sup.2,6
]dodecylidene, each of said fluoren-9-ylidene substituents being
selected from the group consisting of C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 alkoxy and halogen.
[0034] In one contemplated embodiment, B and B' are each selected
from the group consisting of:
[0035] (a) phenyl, mono-substituted and di-substituted phenyl;
[0036] (b) 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 parts (a) and (b)
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, chloro and
fluoro;
[0037] (c) the groups represented by graphic formulae IIA and IIB
wherein E is methylene and G is oxygen, R.sub.6 is C.sub.1-C.sub.3
alkyl or C.sub.1-C.sub.3 alkoxy; R.sub.7 and R.sub.8 are each
hydrogen or C.sub.1-C.sub.4 alkyl; and q is 0 or 1;
[0038] (d) C.sub.1-C.sub.4 alkyl; and
[0039] (e) the group represented by graphic formula IIC, wherein L
is hydrogen or methyl and M is phenyl or mono-substituted phenyl,
said phenyl substituent being C.sub.1-C.sub.3 alkyl,
C.sub.1-C.sub.3 alkoxy or fluoro; or B and B' taken together form
fluoren-9-ylidene, mono-substituted fluoren-9-ylidene or a member
selected from the group consisting of saturated C.sub.3-C.sub.10
spiro-monocyclic hydrocarbon rings, saturated C.sub.7-C.sub.10
spiro-bicyclic hydrocarbon rings, and saturated C.sub.7-C.sub.10
spiro-tricyclic hydrocarbon rings, said fluoren-9-ylidene
substituent being selected from the group consisting of
C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 alkoxy, fluoro and
chloro.
[0040] In another contemplated embodiment, B and B' are each
selected from the group consisting of:
[0041] (a) phenyl, mono- and di-substituted phenyl, preferably
substituted in the meta and/or para positions;
[0042] (b) 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 (a) and (b) being selected from the group
consisting of hydroxy, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3
alkoxy, phenyl, indolino, fluoro and chloro;
[0043] (c) the group represented by graphic formulae IIA wherein E
is methylene and G is oxygen, R.sub.6 is C.sub.1-C.sub.3 alkyl or
C.sub.1-C.sub.3 alkoxy; R.sub.7 and R.sub.8 are each hydrogen or
C.sub.1-C.sub.3 alkyl; and q is 0 or 1; or B and B' taken together
form fluoren-9-ylidene, adamantylidene, bornylidene,
norbornylidene, or bicyclo[3.3.1]nonan-9-ylidene.
[0044] Compounds represented by graphic formula I may be prepared
by the following steps. In Reaction A, compounds represented by
graphic formula V or VA are either purchased or prepared by
Friedel-Crafts methods 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.
[0045] 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 potential
phenyl substituents. 5
[0046] In Reaction B, the substituted or unsubstituted ketone is
represented by graphic formula VA, in which B and B' may represent
groups other than substituted or unsubstituted phenyl, 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
[0047] In Reaction C, a method for making the compounds represented
by graphic formula XI that may not be commercially available is
disclosed. A substituted or unsubstituted acetophenone,
benzophenone, or benzaldehyde represented by graphic formula VII is
reacted with dimethyl succinate (graphic formula VIII) in the
presence of a base such as sodium hydride or a potassium t-butoxide
in a suitable solvent such as toluene to form the appropriate
substituted monoester of an .alpha.-arylidene succinic acid,
represented by graphic formula IX. Other substituents on the
compound represented by graphic formula IX may be prepared by using
different succinate esters, such as diethyl succinate. Compound IX
is heated with acetic anhydride and anhydrous sodium acetate to
form the corresponding acetate derivative represented by the
graphic formula X. Compound X is reacted with potassium hydroxide
in an aqueous alcohol mixture such as ethanol in water to form the
corresponding substituted naphthoic acid, represented by graphic
formula XI. Reaction C is further described in the text Organic
Reactions, Vol. VI, Chapter 1, pages 1-73, John Wiley & Sons,
Inc., New York. 7
[0048] In Reaction D, 4-hydroxy-2-naphthoic acid substituted with
(R.sub.3)n and R.sub.2 at the 1-position, represented by graphic
formula XI, is reacted with R.sub.1-halide, e.g., cyclohexyl
iodide, in the presence of potassium carbonate in a suitable
solvent such as anhydrous dimethylformamide (DMF), to form the
corresponding 4-hydroxy-2-naphthoate substituted with (R.sub.3)n
and R.sub.2 at the 1-position, which is represented by graphic
formula XII. This reaction is further described in The Journal of
Organic Chemistry, 46(17), 1981, page 3477. The compound
represented by graphic formula XI may be prepared by following the
scheme of Reaction c disclosed in U.S. Pat. No. 6,106,744. 8
[0049] In Reaction E, the propargyl alcohol represented by graphic
formula VI is coupled with the naphthol represented by graphic
formula XIA (which represents the same compounds as graphic formula
VIII except that the bonding of the substituent at the 2-position
is shown) to form compounds represented by graphic formula I. 9
[0050] As shown in Reaction F, when R.sub.2 in graphic formula I is
-OH, this substituent can be converted to a variety of different
groups by reacting such compounds, as represented by graphic
formula IA, with acylating or alkylating agents. For example,
Compound IA may be reacted with methyl iodide (or other alkylating
agent) in the presence of anhydrous potassium carbonate in a
suitable solvent such as anhydrous acetone to form compounds
represented by graphic formula IB, in which R.sub.2 is a methoxy
substitutent. Alkylating reactions are further described in
"Organic Synthesis," Vol. 31, pages 90-93, John Wiley & Sons,
Inc., New York, NY. Alternatively, Compound IA may be reacted with
acetyl chloride (or other acylating agent) in the presence of
triethylamine in an appropriate solvent, such as methylene
chloride, to form compounds represented by the graphic formula IC,
in which R.sub.2 is an acetoxy substitutent. Acylating reactions
are further described in "Organic Synthesis," Vol. 32, pages 72-77,
John Wiley & Sons, Inc., New York, NY. 10
[0051] 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.
[0052] Coating compositions may be used to produce 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 2H-naphtho-[1,2-b]pyrans represented by graphic
formula I exhibit color changes from colorless to colors ranging
from yellow to red/purple.
[0053] Examples of naphthopyrans and contemplated naphthopyrans
that have or are expected to have desirable photochromic properties
and that are within the scope of the invention are the
following:
[0054] (a)
2,2-Diphenyl-5-cyclohexyloxycarbonyl-8-methyl-[2H]-naphtho[1,2--
b]pyran;
[0055] (b)
2,2-Bis(4-methoxyphenyl)-5-cyclopropyloxycarbonyl-6-methoxy-[2H-
]-naphtho[1,2-b]pyran;
[0056] (c)
2,2-Bis(4-methoxyphenyl)-5-cyclooctyloxycarbonyl-6-(ethoxycarbo-
nyl)methoxy-[2H]-naphtho[1,2-b]pyran;
[0057] (d)
2,2-Bis(4-methylphenyl)-5-cyclohexyloxycarbonyl-6-(methoxycarbo-
nyloxy)-[2H]-naphtho[1,2-b]pyran;
[0058] (e)
2,2-Diphenyl-5-cyclopropyloxycarbonyl-6-acetoxy-[2H]-naphtho[1,-
2-b]pyran;
[0059] (f)
2,2-Bis(4-methoxyphenyl)-5-cyclooctyloxycarbonyl-6-methyl-[2H]--
naphtho[1,2-b]pyran;
[0060] (g)
2,2-Bis(4-methoxyphenyl)-5-cycloheptyloxycarbonyl-6-methyl-9-me-
thoxy-[2H]-naphtho[1,2-b]pyran;
[0061] (h)
2-(4-Methoxyphenyl)-2-(2-methyl,2,3-dihydrobenzofuran-5-yl)-5-c-
yclobutyloxycarbonyl-6-(ethoxycarbonyl)methoxy-[2H]-naphtho[1,2-b]pyran;
[0062] (i)
2-phenyl-2-(2-dibenzofuryl)-5-cyclohexyloxycarbonyl-8-methyl-[2-
H]-naphtho[1,2-b]pyran;
[0063] (j)
2,2-diphenyl-5-cyclohexyloxycarbonyl-8-methoxy-[2H]-naphtho[1,2-
-b]pyran;
[0064] (k)
2-phenyl-2-(4-methoxyphenyl)-5-cyclohexyloxycarbonyl-8-methoxy--
[2H]-naphtho[1,2-b]pyran; and
[0065] (l)
2-phenyl-2-(4-methylphenyl)-5-cyclohexyloxycarbonyl-8-methoxy-[-
2H]-naphtho[1,2-b]pyran.
[0066] Other than in the operating examples, or 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".
[0067] The disclosures of the patents and articles cited herein
describing photochromic imbibition processes and compositions,
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.
[0068] It is contemplated that the photochromic naphthopyrans of
the present invention may each be used alone or in combination with
other naphthopyrans of the present invention. Alternatively, the
photochromic naphthopyrans of the present invention may be used 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 400 and 700 nanometers, or substances
containing the same. The photochromic compounds may be
incorporated, e.g., dissolved or dispersed, in a polymeric organic
host material used to prepare photochromic articles which color
when activated to an appropriate hue.
[0069] The complementary organic photochromic materials may include
other naphthopyrans, benzopyrans, indenonaphthopyrans,
phenanthorpyrans, 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. Such photochromic compounds are described
in U.S. Pat. Nos. 5,645,767 and 6,153,126.
[0070] The photochromic compounds of the present invention may be
associated with a polymeric organic host material or other
substrate by various means. They may be incorporated, i.e.,
dissolved and/or dispersed, into the host material, polymerized
with other components of the host material, and/or incorporated
into a coating applied to a substrate, e.g., a polymeric coating
applied to one surface of the polymeric organic host material.
[0071] Each of the photochromic substances described herein may be
used in amounts (or in a ratio) such that an organic host material
or substrate to which the photochromic compounds or mixture of
compounds is associated, 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.
[0072] The amount of the photochromic naphthopyrans to be applied
to or incorporated into a coating composition or 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 compounds. Typically, the
more photochromic compound applied or incorporated, the greater is
the color intensity up to a certain limit.
[0073] 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, the ultimate
color desired and the method of application to the host material or
substrate. Generally, the amount of total photochromic compound
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 compound 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.
[0074] 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.
[0075] 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.
[0076] 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.
[0077] 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.
[0078] Most preferably, the polymeric organic host material is a
solid transparent or optically clear material, e.g., materials
suitable for optical applications, such as plano, ophthalmic and
contact lenses, windows, automotive transparencies, e.g.,
windshields, aircraft transparencies, plastic sheeting, polymeric
films, etc.
[0079] 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.
[0080] 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.
[0081] 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.
[0082] 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.
[0083] 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
[0084] 7-Methyl-4-hydroxy-2-naphthoic acid (25 grams), cyclohexyl
iodide (27.3 grams) and potassium carbonate (50 grams) were added
to a reaction flask containing 200 milliliters (mL) of
dimethylformamide and heated to reflux. After maintaining the
reflux temperature for 18 hours, the contents of the reaction flask
was added to a beaker containing 500 mL of a mixture of ice and
water. The resulting mixture was extracted three times with diethyl
ether (100 mL) each time. The recovered product, 3 grams, had a
nuclear magnetic resonance (NMR) spectrum which showed the product
to have a structure consistent with 7-methyl-4-hydroxy-2-cyclohex-
yloxycarbonyl naphthalene.
Step 2
[0085] 7-Methyl-4-hydroxy-2-cyclohexyloxycarbonyl naphthalene (3
grams) from Step 1 and 1,1-diphenyl-2-propyn-1-ol (2.5 grams) were
added to a reaction flask (equipped with a magnetic stirrer, Stark
trap and condenser) containing 100 mL of chloroform and stirred. A
catalytic amount of p-toluenesulfonic acid (about 100 milligrams)
was added, and the mixture was heated to reflux and stirred for 2
hours. Afterwards, the reaction mixture was washed with water and
the remaining solvent was removed under vacuum. The resulting
residue was purified using a silica gel column and 15 weight
percent ethylacetate in hexane as the eluant. The photochromic
fractions were combined and the solvent was removed under vacuum.
The resulting product was induced to crystallize from a 1:1
toluene/ether mixture to yield 1.5 grams of bright yellow crystals.
The recovered product had a melting point of 188-189.degree. C. A
nuclear magnetic resonance (NMR) spectrum showed the product to
have a structure consistent with
2,2-diphenyl-5-cyclohexyloxycarbonyl-8-methyl-[2H]-naphth-
o[1,2-b]pyran.
EXAMPLE 2
[0086] The procedure of Example 1 was followed except that in Step
2, 1-phenyl-1-(2-dibenzofuryl)-2-propyn-1-ol was used in place of
1,1-diphenyl-2-propyn-1-ol. The NMR spectrum showed the structure
to be consistent with
2-phenyl-2-(2-dibenzofuryl)-5-cyclohexyloxycarbonyl-8-met-
hyl-[2H]-naphtho[1,2-b]pyran.
EXAMPLE 3
[0087] The procedure of Example 1 was followed except that in Step
2, 7-methoxy-4-hydroxy-2-cyclohexyloxycarbonyl naphthalene was used
in place of 7-methyl-4-hydroxy-2-cyclohexyloxycarbonyl naphthalene.
The NMR spectrum showed the structure to be consistent with
2,2-diphenyl-5-cyclohexyloxycarbonyl-8-methoxy-[2H]-naphtho[1,2-b]pyran.
EXAMPLE 4
[0088] The procedure of Example 1 was followed except that in Step
2, 7-methoxy-4-hydroxy-2-cyclohexyloxycarbonyl naphthalene was used
in place of 7-methyl-4-hydroxy-2-cyclohexyloxycarbonyl naphthalene
and 1-phenyl-1-(4-methoxyphenyl)-2-propyn-1-ol was used in place of
1,1-diphenyl-2-propyn-1-ol. The NMR spectrum showed the structure
to be consistent with
2-phenyl-2-(4-methoxyphenyl)-5-cyclohexyloxycarbonyl-8-me-
thoxy-[2H]-naphtho[1,2-b]pyran.
EXAMPLE 5
[0089] The procedure of Example 1 was followed except that in Step
2, 7-methoxy-4-hydroxy-2-cyclohexyloxycarbonyl naphthalene was used
in place of 7-methyl-4-hydroxy-2-cyclohexyloxycarbonyl naphthalene
and 1-phenyl -1-(4-methylphenyl)-2-propyn-1-ol was used in place of
1,1-diphenyl-2-propyn-1-ol. The NMR spectrum showed the structure
to be consistent with
2-phenyl-2-(4-methylphenyl)-5-cyclohexyloxycarbonyl-8-met- hoxy-
[2H]-naphtho[1,2-b]pyran.
COMPARATIVE EXAMPLES 1-2
[0090] Two 2H-naphthopyrans having non-cycloalkyl ester
substituents at the 5 position were prepared following the
procedures of U.S. Pat. No. 5,458,814. The compounds of the
Comparative Examples were determined to be:
[0091] (CE1) 2, 2-diphenyl-5-methoxycarbonyl-8-methyl-
[2H]-naphtho[1,2-b]pyran; and
[0092] (CE2)
2,2-diphenyl-5-isopropoxycarbonyl-8-methyl-[2H]-naphtho[1,2-b-
]pyran.
EXAMPLE 6
Part A
[0093] Testing was done with the photochromic compounds described
in Examples 1-5 and Comparative Examples (CE) 1 and 2 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
[0094] 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/cm.sup.2). 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.
[0095] A monitoring, collimated beam of light from a tungsten lamp
was passed through the square at a small angle (approximately 300)
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.
[0096] 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.
[0097] The optical properties of the photochromic compound 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.RTM. Saturation) was taken under
identical conditions as the .DELTA.OD/Min, except UV exposure was
continued for 15 minutes. The lambda max (Vis) is the wavelength in
nanometers (nm) 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) wavelength
was 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 reach one half the
highest absorbance at room temperature (72.degree. F., 22.2.degree.
C.) after removal of the source of activating light.
1TABLE 1 Example (.lambda.) max .DELTA.OD/MIN .DELTA.OD @ Bleach
Rate Number (VIS) Sensitivity Saturation (T 1/2) 1 467 0.32 0.38 72
2 493 0.22 0.19 44 3 460 0.40 0.52 79 4 480 0.39 0.35 45 5 460 0.37
0.45 64 CE1 467 0.27 0.37 71
[0098] The results of Table 1 show that the compounds of the
present invention demonstrate a range of photochromic properties,
e.g., lambda max values from 460 to 493 nanometers, sensitivity
levels from 0.22 to 0.40, values for .DELTA.OD @ Saturation from
0.19 to 0.52 and Bleach Rates from 44 to 79 seconds. Comparative
Examples 1 and 2, having a methyl ester substituent and an
isopropyl ester substituent, respectively, at the 5-position of the
naphtho portion of the naphthopyran, demonstrate photochromic
properties similar to Example 1.
Part C
[0099] The following materials were added in the order and the
manner described to a container suitable for use with a BRINKMAN
PT-3000 homogenizer and mixed by the homogenizer at a speed of 5000
rpm for 2 minutes or until the materials were dissolved.
2 Material Weight (grams) 2-Ethoxy ethyl ether 30.0
Tetrahydrofurfuryl alcohol 35.0 n-Methyl pyrrolidone 20.0
Hydroxypropyl cellulose 12.0 Silica 0.9
[0100] The photochromic compounds of Example 1, Comparative
Examples 1 and 2 were individually added with TINUVIN.RTM. 144 UV
stabilizer, reported to be a hindered amine available from
Ciba-Geigy, to 10 ml aliquots of the homogenate to make the
imbibition compositions. The weight percent, based on the total
weight of the imbibition composition, of the photochromic compound
and stabilizer for the two different concentrations tested (A and
B) is listed in the following table.
3 Conc. A Conc. B Material Weight % Weight % Photochromic Compound
2.4 4.7 TINUVIN .RTM. 144 UV stabilizer 1.2 2.3
Part D
[0101] The solutions of Part C for Example 1, Comparative Examples
1 and 2 and stabilizer were imbibed into duplicate sample lenses
cast from an optical resin sold by PPG Industries, Inc. under the
designation CR-307. This was done by applying the imbibition
formulation onto the surface of the test lenses by spin coating.
The applied coatings had a clear appearance when wet and became
hazy when dry. The average wet weight of the resin film that formed
on the lens ranged from 0.35 to 0.40 grams per lens. The resin film
was dried beneath an infrared lamp (Fostoria Sun-mite Model FFH-912
900 Watts) held about 13 inches above the lenses for 10 to 15
minutes.
[0102] The lenses were then heated in a hot-air oven at
135-140.degree. C. for 3 hours and one of each pair of duplicate
lenses was examined visually. The visual examination was done by
moving the coated lens surface from a position parallel to a
fluorescent light to a position that is perpendicular while
observing any defects in the coating. The fluorescent light was a
34 Watt 4 feet (122 centimeters) long light positioned at a
distance of about 6 feet (183 centimeters) above the lens. The
appearance of each lens coated with the solutions of concentration
A or B samples is described in Table 2. After cooling, the resin
film was removed from the other duplicate test samples by rinsing
with water and wiping with an acetone soaked tissue. The lenses
were examined visually in the same manner as described above. The
results of the second visual examination are listed in Table 3.
4TABLE 2 Appearance of Appearance of Imbibition Film of Imbibition
Film of Concentration A Concentration B Sample sample on surface
sample on surface Example 1 and No defects A few scattered,
stabilizer* small, raised crystals Comparative Example Numerous
scattered, Numerous scattered, 1 and stabilizer* small, raised
small, raised crystals crystals and an unevenly coated surface
pattern Comparative Example Numerous scattered, Numerous scattered,
2 and stabilizer* small, raised small, raised crystals crystals and
an unevenly coated surface pattern Stabilizer* is TINUVIN .RTM. 144
UV stabilizer.
[0103]
5TABLE 3 Appearance of Appearance of surface after surface after
removal of removal of Imbibition Film of Imbibition Film of
Concentration A Concentration B Sample sample sample Example 1 and
No defects Rare dimples stabilizer* No distortion of reflected
light Comparative Example Scattered dimples, Orange peel 1 and
stabilizer* Some distortion of Severe distortion reflected light of
reflected light around dimples Comparative Example Few dimples
present Fine orange peel 2 and stabilizer* Slight distortion Severe
distortion around dimples of reflected light Stabilizer* is TINUVIN
.RTM. 144 UV stabilizer.
[0104] The results of Table 2 show the improved compatibility,
i.e., solubility, of the Example 1 compound in the imbibition resin
film as compared to the compounds of Comparative Examples 1 and 2.
The imbibition resin film containing the compound of Example 1
demonstrates no observable defects when used at 2.4 weight percent
and a few observable defects when used at 4.7 weight percent of the
imbibition composition. The imbibition resin films containing
Comparative Examples 1 and 2 demonstrate numerous defects at the
lower concentration and additionally had unevenly coated surface
patterns at the higher concentration.
[0105] The results of Table 3 show the effects of the imbibition
compositions containing photochromic compounds of Example 1 and
Comparative Examples 1 and 2 on the surface of the polymeric host.
The lens imbibed with the composition containing Example 1 at 2.4
weight percent demonstrate no defects and only rare defects are
observed with the composition containing 4.7 weight percent. The
lenses imbibed with Comparative Examples 1 and 2 show dimple
defects and some distortion of reflected light at the lower
concentration and orange peel and severe distortion of reflected
light at the higher concentrations.
[0106] 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.
* * * * *