Photochromic oxazine compounds and methods for their...

Details Photochromic oxazine compounds and methods for their... Photochromic oxazine compounds and methods for their...

2001-12-21

2004-04-13

Owens, Amelia (Department: 1625)

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

Organic compounds

Chalcogen in the nitrogen containing substituent

C544S070000, C544S071000, C546S064000

Reexamination Certificate

active

06720420

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to oxazine compounds. In particular, the invention provides oxazine compounds and methods for their manufacture, which compounds are useful as photochromic compounds.
BACKGROUND OF THE INVENTION
Various classes of photochromic compounds have been synthesized and suggested for use in applications in which reversible color changes or darkening is induced by sunlight. For example, spirooxazine and chromene compounds are known for excellent fatigue resistance. Additionally, photochromic 2,2-disubstituted [2H-1,4]-naphthoxazine compounds, such as those are disclosed in U.S. Pat. No. 5,801,243, are known. These compounds have better fatigue resistance than chromene compounds, but are disadvantageous in that methods for their preparation are extremely limited. Thus, a need exists for additional photochromic oxazine compounds that overcome the disadvantages of the known compounds.
DESCRIPTION OF THE INVENTION AND ITS PREFERRED EMBODIMENTS
The present invention provides oxazine compounds having aromatic, heteroaromatic, or aliphatic substituents at the 2 position of the oxazine moiety. Additionally, a one pot method with excellent yields is provided for producing the compounds.
In one embodiment, the invention provides a compound comprising the formula:
wherein X is nitrogen or carbon;
R
1
and R
2
are each independently hydrogen, hydroxy, nitro, cyano, allyl, a 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, a halogen, a halo(C
1
-C
20
)alkyl, halo(C
3
-C
20
)cycloalkyl, halo(C
1
-C
20
)alkoxy, substituted with at least one halogen atom wherein the halogen is fluoro, chloro, bromo, or iodo, unsubstituted aryl, aryl substituted with (C
1
-C
6
)alkyl or (C
1
-C
6
)alkoxy or aryloxy, and preferably phenyl or naphthyl, unsubstituted heteroaryl or heteroaryl substituted with (C
1
-C
6
)alkyl or (C
1
-C
6
)alkoxy and preferably furyl, thienyl, pyrryl, indolyl, or pyridyl, arylalkyl or unsubtsituted heteroarylalkyl or heteroarylalkyl substituted with (C
1
-C
6
)alkyl or (C
1
-C
6
)alkoxy, substituted or unsubstituted nitrogen-containing heterocyclic ring, —N(R
1
)R
2
or CON(R
1
)R
2
wherein R
1
and R
2
are each independently hydrogen, (C
1
-C
20
)alkyl, (C
3
-C
20
)cycloalkyl, unsubstituted phenyl or phenyl substituted with (C
1
-C
6
)alkyl or (C
1
-C
6
)alkoxy, or a —OCOR or —COOR or —COR group wherein R is hydrogen, (C
1
-C
20
)alkyl, (C
3
-C
20
)cycloalkyl, or substituted or unsubstituted aryl or heteroaryl;
n is an integer from 0 to 4; and
A and A′ are each independently:
(a) a linear or branched (C
1
-C
12
)alkyl, (C
3
-C
12
)cycloalkyl, aryl(C
1
-C
6
)alkyl, 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, or (C
1
-C
12
)alkylthio wherein each of the aryl preferably are phenyl or naphthyl and each of the heteroaryl may be furyl, thienyl, pyrryl, indolyl, benzofuryl, benzothienyl, pyridyl, dibenzofuryl, dibenzothienyl, or carbazolyl;
(b) unsubstituted or mono- di- or tri-substituted aryl groups, such as phenyl and naphthyl;
(c) unsubstituted or mono-, or di-substituted heteroaromatic groups, such as furyl, thienyl, pyrryl, indolyl, benzofuryl, benzothienyl, pyridyl, dibenzofuryl, dibenzothienyl, carbazolyl;
(d) a group of either of the formulae:
 wherein B is hydrogen, (C
1
-C
12
)alkyl, unsubstituted or mono- or di-substituted aryl, such as phenyl and naphthyl
 wherein each of said aryl and heteroaromatic substituents in (b), (c) and (d) are nitro, amino, cyano, hydroxy, epoxy, vinyl, allyl, hydroxyethoxy, methoxyethoxy, hydroxyethoxyethoxy, methoxyethoxyethoxy
 fluoro, chloro, bromo, or iodo, (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, or
 a heterocyclic nitrogen-containing substituent, including, without limitation, 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, or —N(R
1
)R
2
or CON(R
1
)R
2
wherein R
1
and R
2
are each independently hydrogen, (C
1
-C
12
)alkyl, (C
3
-C
12
)cycloalkyl, phenyl, mono- or di-substituted phenyl, a —COR, —OCOR or —COOR group 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, or unsubstituted, mono- or di-substituted naphthyl, unsubstituted, mono- or di-substituted furyl or thienyl;
(e) unsubstituted or mono-substituted pyrazolyl, pyridyl, imidazolyl, pyrazolinyl, imidazolinyl, or acridinyl, wherein the substituents are each independently (C
1
-C
6
)alkyl, (C
1
-C
6
)alkoxy, fluoro, chloro, phenyl; or
(f) a group represented by either of the formulae:
wherein C and D are each independently carbon, oxygen, (C
1
-C
12
)alkyl nitrogen, or (C
1
-C
12
)acyl nitrogen and R
3
and R
4
are each independently hydrogen or (C
1
-C
12
)alkyl.
In embodiments in which halogen is selected, preferably it is fluoro, chloro or bromo.
In a preferred embodiment, X is carbon or nitrogen, R
1
and R
2
are each independently hydrogen, nitro, cyano, allyl, fluoro, chloro, bromo, trifluoromethyl, trichloromethyl, pyrrolidino, piperidino, morpholino, phenyl, benzyl, a linear or branched (C
1
-C
6
)alkyl, (C
1
-C
6
)alkoxy, or a —OCOR or —COOR group wherein R is hydrogen, (C
1
-C
6
)alkyl, or (C
3
-C
6
)cycloalkyl;
n is an integer from 0 to 2; and
A and A′ are each independently:
(a) a linear or branched (C
1
-C
6
)alkyl, (C
3
-C
6
)cycloalkyl; aryl(C
1
-C
4
)alkyl heteroaryl(C
1
-C
4
)alkyl, or (C
1
-C
6
)alkoxy(C
1
-C
6
)alkyl;
(b) unsubstituted or mono- or di-substituted aryl, such as phenyl or naphthyl, preferably substituted in either or both the meta or para positions;
(c) unsubstituted or mono-substituted heteroaromatic groups, such as furyl, thienyl, pyrryl, indolyl, benzofuryl, benzothienyl, pyridyl, dibenzofuryl, dibenzothienyl, or carbazolyl;
wherein each of the aryl and heteroaromatic substituents in (b) and (c) are independently nitro, amino, cyano, hydroxy, epoxy, hydroxyethoxy, methoxyethoxy, hydroxyethoxyethoxy, methoxyethoxyethoxy, fluoro, chloro, bromo, or 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, phenylvinyl, a heterocyclic nitrogen-containing substituent, including, without limitation, 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, pyrryl, or a —N(R
1
)R
2
, CON(R
1
)R
2
wherein R
1
and R
2
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.
More preferably, X carbon or nitrogen; R
1
, R
2
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;
n is an integer from 0 to 2; and
A and A′ are each independently a linear or branched (C
1
-C
4
)alkyl, (C
3
-C
6
)cycloalkyl, unsubstituted or mono-, or di-substituted phenyl, preferably substituted in either or both the meta and para positions with a substituent selected from the group consisting of nitro, amino, acyl, cyano, methoxy, ethoxy, methoxyethoxy, fluoro, chloro, vinyl, allyl

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