Photochromic bis-naphthopyran compounds and methods for...

Details Photochromic bis-naphthopyran compounds and methods for... Photochromic bis-naphthopyran compounds and methods for...

2001-09-04

2004-06-08

McKane, Joseph K. (Department: 1626)

Organic compounds -- part of the class 532-570 series

Organic compounds

Chalcogen in the nitrogen containing substituent

C544S150000, C546S209000, C546S280400, C546S282700, C548S527000, C549S013000, C549S389000, C365S119000

Reexamination Certificate

active

06747145

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to photochromic naphthopyran compounds. More particularly, this invention provides photochromic bis-naphthopyran compounds as well as methods for their manufacture and their use.
BACKGROUND OF THE INVENTION
Several types of photochromic compounds are known for use in applications in which reversible color change, or darkening, induced by sunlight is desirable. These applications include for example, ophthalmic lenses, solar protection lenses, filters, camera optical systems, decorative objects, windows and the like.
However, the known compounds are disadvantageous in that they do not exhibit both high optical density and the ability to return to their original color quickly once the activating light source is removed. Thus, there is a need for new compounds with fast response to ultraviolet (“UV”) irradiation, high colorability and long lifetime.
DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS
The present invention provides bis-naphthopyran compounds that exhibit a wide range of color, i.e., from pink to purple to blue gray, upon activation by a source of UV light and that, when the irradiation is discontinued, the original color is recovered. The bis-naphthopyran compounds of the present invention exhibit broad coloration ability, fast coloration response, and good fatigue-resistance.
In one embodiment, the present invention provides a compound comprising:
wherein X is sulfur or oxygen;
R′, R″ may be the same or different and are each independently hydrogen, hydroxy, halogen, nitro, cyano, allyl, linear or branched (C
1
-C
20
)alkyl, (C
3
-C
20
)cycloalkyl, (C
1
-C
20
)alkoxy, (C
1
-C
20
)alkylacetylenyl, phenylacetylenyl, (C
1
-C
20
)alkenyl, phenylvinyl, halo(C
1
-C
20
)alkyl, halo(C
3
-C
20
)cycloalkyl, halo(C
1
-C
20
)alkoxy, aryl, aryloxy or heteroaryl optionally substituted with (C
1
-C
6
)alkyl or (C
1
-C
6
)alkoxy; arylalkyl or heteroarylalkyl; nitrogen-containing heterocyclic ring having 5 or 6 atoms optionally substituted with (C
1
-C
6
)alkyl or (C
1
-C
6
)alkoxy, —N(R
1
)R
2
, CON(R
1
)R
2
, wherein R
1
and R
2
may be the same or different and are each independently hydrogen, (C
1
-C
20
)alkyl, (C
3
-C
20
)cycloalkyl, and optionally substituted phenyl; —OCOR, —COOR or —COR, wherein R represents hydrogen, (C
1
-C
20
)alkyl, (C
3
-C
20
)cycloalkyl, or aryl or heteroaryl optionally substituted with (C
1
-C
6
)alkyl or (C
1
-C
6
)alkoxy;
A′, A″ may be same or different and are each independently:
(a) linear or branched (C
1
-C
12
)alkyl, (C
3
-C
12
)cycloalkyl, aryl(C
1
-C
6
)alkyl or heteroaryl(C
1
-C
6
)alkyl, (C
1
-C
6
)alkoxy(C
1
-C
6
)alkyl, (C
1
-C
12
)alkoxy, halo(C
1
-C
12
)alkyl, (C
1
-C
12
)haloalkoxy, (C
1
-C
12
)alkylthio;
(b) substituted or unsubstituted aryl groups;
(c) substituted or unsubstituted heteroaryl groups;
(d) a group of the following formulae:
wherein B is hydrogen, (C
1
-C
12
)alkyl or substituted or unsubstituted aryl;
(e) unsubstituted or mono-substituted pyrazolyl, pyridyl, imidazolyl, pyrazolinyl, imidazolinyl, or acridinyl, each of the said substituents being (C
1
-C
6
)alkyl, (C
1
-C
6
)alkoxy, fluoro, chloro, or phenyl.
(f) a group of the following formulae:
 wherein C and D may be the same or different and are each independently carbon, oxygen, (C
1
-C
12
)alkyl nitrogen, or (C
1
-C
12
)acyl nitrogen;
 R
3
and R
4
are each hydrogen or (C
1
-C
12
)alkyl; and
 wherein the phenyl moiety is optionally substituted with (C
1
-C
12
)alkyl, (C
1
-C
12
)alkoxy, (C
2
-C
12
)acyl, fluoro, or chloro;
n is an integer from 1 to 8; and
m is an integer from 0 to 3.
“Nitrogen-containing heterocyclic ring having 5 or 6 atoms” includes, without limitation, pyrrolidino, piperidino, morpholino, and the like. “Halogen” or “halo” means fluoro, chloro, bromo, or iodo. Preferably fluoro, chloro, or bromo is used. “Aryl” includes, without limitation, phenyl or naphthyl. “Heteroaryl” includes, without limitation, furyl, thienyl, pyrryl, indolyl, benzofuryl, benzothienyl, pyridyl, dibenzofuryl, dibenzothienyl, and carbazolyl.
“Substituted aryl or heteroaryl groups” includes, without limitation aryl or heteroaryl groups that are mono-, di-, or tri-substituted by a substituent that is: halogen nitro, amino, cyano, hydroxy, epoxy, vinyl, allyl, hydroxyethoxy, methoxyethoxy, hydroxyethoxyethoxy, methoxyethoxyethoxy; (C
1
-C
12
)alkyl, (C
1
-C
12
)alkoxy, (C
1
-C
12
)alkylaryl, aryl, aryloxy, aryl(C
1
-C
12
)alkyl, aryl(C
1
-C
12
)alkoxy, (C
1
-C
12
)alkoxyaryl, halo(C
1
-C
12
)alkyl, haloaryl, cyclo(C
3
-C
12
)alkyl, cyclo(C
1
-C
12
)alkoxy, aryloxyaryl, aryloxy(C
1
-C
12
)alkyl, aryloxy(C
1
-C
12
)alkoxy, acryloxy, methacryloxy; a heterocyclic nitrogen-containing substituent, such as N-(C
1
-C
12
)alkylpiperazino, N-aryl-piperizino, aziridino, indolino, pyrrolidino, pyrrolino, piperidino, (C
1
-C
4
)alkylpiperidino, di(C
1
-C
4
)alkylpiperidino, 4-piperidinopiperidino, morpholino, 2,6-di(C
1
-C
4
)alkylmorpholino, thiomorpholino, thioazolidino, tetrahydroquinolino, pyrryl; —N(R
1
)R
2
, CON(R
1
)R
2
, wherein R
1
and R
2
are the same or different and are independently hydrogen, (C
1
-C
12
)alkyl, (C
3
-C
12
)cycloalkyl, phenyl, mono- or di-substituted phenyl; or —COR, —OCOR or —COOR, wherein R is hydrogen, (C
1
-C
12
)alkyl, (C
3
-C
12
)cycloalkyl, halo(C
1
-C
6
)alkyl, unsubstituted, mono- or di-substituted phenyl, unsubstituted, mono- or di-substituted naphthyl, unsubstituted, mono- or di- substituted furyl, or thienyl, and combination thereof.
In a preferred embodiment, the present invention provides a compound of Formula I wherein:
X is sulfur or oxygen;
R′, R″ are the same or different and are each independently hydrogen, nitro, cyano, allyl, fluoro, chloro, bromo, trifluoromethyl, trichloromethyl, pyrrolidino, piperidino, morpholino, phenyl, benzyl; linear or branched (C
1
-C
6
)alkyl, (C
1
-C
6
)alkoxy, or —OCOR or —COOR wherein R is hydrogen, (C
1
-C
6
)alkyl, (C
3
-C
6
)cycloalkyl;
A′, A″ are the same or different and are each independently:
(a) linear or branched (C
1
-C
6
)alkyl, (C
3
-C
6
)cycloalkyl, aryl(C
1
-C
4
)alkyl or heteroaryl(C
1
-C
4
)alkyl, (C
1
-C
6
)alkoxy(C
1
-C
6
)alkyl;
(b) unsubstituted, mono-, di-substituted aryl selected from phenyl or naphthyl, preferably substituted in the meta position, the para position, or both;
(c) unsubstituted or mono-substituted heteroaryl groups that are furyl, thienyl, pyrryl, indolyl, benzofuryl, benzothienyl, pyridyl, dibenzofuryl, dibenzothienyl, or carbazolyl the substituents being nitro, amino, cyano, hydroxy, epoxy, hydroxyethoxy, methoxyethoxy, hydroxyethoxyethoxy, methoxyethoxyethoxy, fluoro, chloro, bromo, iodo, vinyl, allyl, trifluoromethyl, phenyl, (C
1
-C
6
)alkyl, (C
1
-C
6
)alkoxy, cyclo(C
3
-C
6
)alkyl, cyclo(C
1
-C
6
)alkoxy, (C
1
-C
6
))alkylamino, di(C
1
-C
6
)alkylamino, diarylamino, phenylacetylenyl, or phenylvinyl;
a heterocyclic nitrogen-containing substituent, such as N(C
1
-C
6
)alkylpiperazino, N-aryl-piperizino, aziridino, indolino, pyrrolidino, pyrrolino, piperidino, (C
1
-C
4
)alkylpiperidino, di(C
1
-C
4
)alkylpiperidino, 4-piperidinopiperidino, morpholino, 2,6-di(C
1
-C
4
)alkylmorpholino, thiomorpholino, thioazolidino, tetrahydroquinolino, or pyrryl;
N(R
1
)R
2
, CON(R
1
)R
2
, wherein R
1
and R
2
are the same or different and are each independently hydrogen, (C
1
-C
6
)alkyl, (C
3
-C
6
)cycloalkyl, phenyl or —COR, —OCOR or —COOR wherein R is hydrogen, (C
1
-C
6
)alkyl, (C
3
-C
6
)cycloalkyl, or phenyl;
n is an integer from 1 to 6; and
m is an integer from 0 to 2.
In a still more preferred embodiment, the invention provides a compound of Formula I wherein:
X is sulfur;
R′, R″ are the same or different and are each independently hydrogen, nitro, cyano, fluoro, chloro, bromo, pyrrolidino, piperidino, morpholino, phenyl, benzyl, (C
1
-C
4
)alkyl, or (C
1
-C
4
)alkoxy;
A′, A″ are the same or different and are each independently:
a linear or branched (C
1
-C
4
)alkyl, (C
3
-C
6
)cycloalkyl;
unsubstituted, mono-, or

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