Polymeric matrix compatibilized naphthopyrans

A naphthopyran compound represented by the following graphic formulae:

• wherein,
• (a) R1 is the group R which is represented by one of the following formulae:
• —A;
• (1)
• —D—A;
• (2)
• —D—E—U;
• (3)
• —D—U;
• (4)
• —E—U;
• (5)
• or
• —U;
• (6)
• wherein —A is represented by the following formula:
• —[(OC2H4)x(OC3H6)y(OC4H8)z]—J
• wherein —J is selected from:
• —OCH2COOH;
• —OCH(CH3)COOH;
• —OC(O)(CH2)wCOOH;
• —OC6H4SO3H;
• —OC5H10SO3H;
• —OC4H8SO3H;
• —OC3H6SO3H;
• —OC2H4SO3H;
• or —OSO3H;
• w is an integer from 1 to 18;
• x, y and z are each a number between 0 and 50, and the sum of x, y and z is between 1 and 50;
• —D— is —C(O)— or —CH2—;
• —E— is represented by the following formula:
• —[(OC2H4)x(OC3H6)y(OC4H8)z]—
• wherein x, y and z are the same as defined for —A;
• —U is a residue of an organic polyol having at least one hydroxyl group, or a derivative of said residue wherein one or more of said hydroxyls have been reacted to form the carboxyl, sulfo or sulfono group containing substituents —J, the group selected from (meth)acryloxy, 2-(methacryloxy)ethylcarbamyl or epoxy, or a mixture thereof provided that —U is not the same as —E—OH;
• or R1 is hydrogen, C1-C3 alkyl or the group, —C(O)W, W being —OR7, —N(R8)R9, piperidino or morpholino, wherein R7 is allyl, C1-C6 alkyl, phenyl, mono(C1-C6)alkyl substituted phenyl, mono(C1-C6)alkoxy substituted phenyl, phenyl(C1-C3)alkyl, mono(C1-C6)alkyl substituted phenyl(C1-C3)alkyl, mono(C1-C6)alkoxy substituted phenyl(C1-C3)alkyl, C1-C6 alkoxy(C2-C4)alkyl or C1-C6 haloalkyl;
• R8 and R9 are each selected from the group consisting of C1-C6 alkyl, C5-C7 cycloalkyl, phenyl, mono-substituted phenyl and di-substituted phenyl, said phenyl substituents being C1-C6 alkyl or C1-C6 alkoxy, and said halo substituent being chloro or fluoro;
• (b) R1′ is the group R, C1-C3 alkyl or the group, —C(O)W, W being —OR7, —N(R8)R9, piperidino or morpholino, wherein R7 is allyl, C1-C6 alkyl, phenyl, mono(C1-C6)alkyl substituted phenyl, mono(C1-C6)alkoxy substituted phenyl, phenyl(C1-C3)alkyl, mono(C1-C6)alkyl substituted phenyl(C1-C3)alkyl, mono(C1-C6)alkoxy substituted phenyl(C1-C3)alkyl, C1-C6 alkoxy(C2-C4)alkyl or C1-C6 haloalkyl;
• R8 and R9 are each selected from the group consisting of C1-C6 alkyl, C5-C7 cycloalkyl, phenyl, mono-substituted phenyl and di-substituted phenyl, said phenyl substituents being C1-C6 alkyl or C1-C6 alkoxy, and said halo substituent being chloro or fluoro;
• (c) R2 is selected from the group consisting of the group R, mono-R-substituted phenyl, hydrogen, C1-C6 alkyl, C3-C7 cycloalkyl, phenyl, mono-substituted phenyl, di-substituted phenyl and the groups —OR10 and —OC(O)R10, wherein R10 is C1-C6 alkyl, phenyl(C1-C3)alkyl, mono(C1-C6)alkyl substituted phenyl(C1-C3)alkyl, mono(C1-C6)alkoxy substituted phenyl(C1-C3)alkyl, C1-C6 alkoxy(C2-C4)alkyl, C3-C7 cycloalkyl or mono(C1-C4)alkyl substituted C3-C7 cycloalkyl, and said phenyl substituent being C1-C6 alkyl or C1-C6 alkoxy;
• (d) each R3 and R4 are selected from the group consisting of the group R, hydrogen, C1-C6 alkyl, C3-C7 cycloalkyl, phenyl, mono-substituted phenyl, di-substituted phenyl and the groups —OR10 and —OC(O)R10, wherein R10 is C1-C6 alkyl, phenyl(C1-C3)-alkyl, mono(C1-C6)alkyl substituted phenyl(C1-C3)alkyl, mono(C1-C6)alkoxy substituted phenyl(C1-C3)alkyl, C1-C6 alkoxy(C2-C4)alkyl, C3-C7 cycloalkyl or mono(C1-C4)alkyl substituted C3-C7 cycloalkyl, and n is selected from the integers 0, 1 and 2 and said phenyl substituent being C1-C6 alkyl or C1-C6 alkoxy;
• (e) R5 and R6 together form an oxo group, a spiro-carbocyclic ring containing 3 to 6 carbon atoms or a spiro-heterocyclic group containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms including the spirocarbon atom, said spiro-carbocyclic and spiro-heterocyclic groups being annellated with 0, 1 or 2 benzene rings;
• or R5 and R6 are each the group R, hydrogen, hydroxy, C1-C6 alkyl, C3-C7 cycloalkyl, allyl, phenyl, mono-substituted phenyl, benzyl, mono-substituted benzyl, chloro, fluoro, the group, —C(O)X, wherein X is hydroxy, C1-C6 alkyl, C1-C6 alkoxy, phenyl, mono-substituted phenyl, amino, mono(C1-C6)alkylamino, or di(C1-C6)alkylamino;
• or R5 and R6 are each the group, —OR11, wherein R11 is C1-C6 alkyl, phenyl(C1-C3)alkyl, mono(C1-C6)alkyl substituted phenyl(C1-C3)alkyl, mono(C1-C6)alkoxy substituted phenyl(C1-C3)alkyl, C1-C6 alkoxy(C2-C4)alkyl, C3-C7 cycloalkyl, mono(C1-C4)alkyl substituted C3-C7 cycloalkyl, C1-C6 chloroalkyl, C1-C6 fluoroalkyl, allyl, the group, —CH(R12)Y, wherein R12 is hydrogen or C1-C3 alkyl and Y is CN, CF3, or COOR13 and R13 is hydrogen or C1-C3 alkyl;
• or R11 is the group, —C(O)Z, wherein Z is hydrogen, C1-C6 alkyl, C1-C6 alkoxy, the unsubstituted, mono- or di-substituted aryl groups phenyl or naphthyl, phenoxy, mono- or di-(C1-C6)alkyl substituted phenoxy, mono- or di-(C1-C6)alkoxy substituted phenoxy, amino, mono(C1-C6)alkylamino, di(C1-C6)alkylamino, phenylamino, mono- or di-(C1-C6)alkyl substituted phenylamino, or mono- or di-(C1-C6)alkoxy substituted phenylamino, each of said phenyl, benzyl and aryl group substituents being C1-C6 alkyl or C1-C6 alkoxy;
• (f) B and B′ are each selected from the group consisting of:
• (i) mono-R-substituted phenyl;
• (ii) the unsubstituted, mono-, di- and tri-substituted aryl groups, phenyl and naphthyl;
• (iii) 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 (f)(ii) and (iii) being selected from the group consisting of hydroxy, aryl, mono(C1-C6)alkoxyaryl, di(C1-C6)alkoxyaryl, mono(C1-C6)alkylaryl, di(C1-C6)alkylaryl, chloroaryl, fluoroaryl, C3-C7 cycloalkylaryl, C3-C7 cycloalkyl, C3-C7 cycloalkyloxy, C3-C7 cycloalkyloxy(C1-C6)alkyl, C3-C7 cycloalkyloxy(C1-C6)alkoxy, aryl(C1-C6)alkyl, aryl(C1-C6)alkoxy, aryloxy, aryloxy(C1-C6)alkyl, aryloxy(C1-C6)alkoxy, mono- and di-(C1-C6)alkylaryl(C1-C6)alkyl, mono- and di-(C1-C6)alkoxyaryl(C1-C6)alkyl, mono- and di-(C1-C6)alkylaryl(C1-C6)alkoxy, mono- and di-(C1-C6)alkoxyaryl(C1-C6)alkoxy, amino, mono(C1-C6)alkylamino, di(C1-C6)alkylamino, diarylamino, N-(C1-C6)alkylpiperazino, N-arylpiperazino, aziridino, indolino, piperidino, arylpiperidino, morpholino, thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino, pyrryl, C1-C6 alkyl, C1-C6 chloroalkyl, C1-C6 fluoroalkyl, C1-C6 alkoxy, mono(C1-C6)alkoxy(C1-C4)alkyl, acryloxy, methacryloxy, bromo, chloro and fluoro, said aryl being phenyl or naphthyl;
• (iv) 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 C1-C6 alkyl, C1-C4 alkoxy, phenyl, fluoro, chloro and bromo;
• (v) monosubstituted phenyl, having a substituent at the para position that is a linking group, —(CH2)t— or —O—(CH2)t—, wherein t is the integer 1, 2, 3, 4, 5 or 6, connected to an aryl group, which is a member of another photochromic naphthopyran;
• (vi) the groups represented by the following graphic formulae:
• wherein L is carbon or oxygen and M is oxygen or substituted nitrogen, provided that when M is substituted nitrogen, L is carbon, said nitrogen substituents being selected from the group consisting of hydrogen, C1-C6 alkyl and C2-C6 acyl;
• each R14 is C1-C6 alkyl, C1-C6 alkoxy, hydroxy, chloro or fluoro;
• R15 and R16 are each hydrogen or C1-C6 alkyl;
• and q is the integer 0, 1 or 2;
• (vii) C1-C6 alkyl, C1-C6 chloroalkyl, C1-C6 fluoroalkyl, C1-C6 alkoxy(C1-C4)alkyl, C3-C6 cycloalkyl, mono(C1-C6)alkoxy(C3-C6)cycloalkyl, mono(C1-C6)alkyl(C3-C6)-cycloalkyl, chloro(C3-C6)cycloalkyl, fluoro(C3-C6)cycloalkyl and C4-C12 bicycloalkyl;
• and
• (viii) the group represented by the following graphic formula:
• wherein P is hydrogen or C1-C4 alkyl and Q 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 C1-C4 alkyl, C1-C4 alkoxy, fluoro or chloro;
• or
• (g) 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 C3-C12 spiro-monocyclic hydrocarbon rings, saturated C7-C12 spiro-bicyclic hydrocarbon rings, and saturated C7-C12 spiro-tricyclic hydrocarbon rings, each of said fluoren-9-ylidene substituents being selected from the group consisting of C1-C4 alkyl, C1-C4 alkoxy, fluoro and chloro, provided that there is at least one R group or mono-R-substituted phenyl on said naphthopyran.