US 7,094,368 B2 · Pyrano-quinolines, pyrano-quinolinones, combinations thereof, photochromic compositions and articles

wherein:

(a) each R1 is independently chosen from:

(i) hydrogen, hydroxy, C1–C12 alkyl, C2–C12 alkylidence, C2–C12 alkylidyne, vinyl, C3–C7 cycloalkyl, C1–C12 haloalkyl, allyl, benzyl, mono-substituted benzyl, halogen or the group, —C(O)W, wherein W being hydroxy, C1–C12 alkyl, C1–C12 alkoxy, phenyl, mono-substituted phenyl, amino, mono(C1–C12)alkylamino, di(C1–C12)alkylamino;

said amino substituents being C1–C12 alkyl, phenyl, benzyl or naphthyl;

each of said benzyl and phenyl substituents being C1–C12 alkyl or C1–C12 alkoxy:

(ii) an unsubstituted, mono- di- or tri-substituted group chosen from phenyl, naphthyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl, benzofuranyl, thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl or indolyl;

each of said group substituents in (ii) being chosen independently for each occurrence from halogen, C1–C12 alkyl or C1–C12 alkoxy;

(iii) a mono-substituted phenyl, said phenyl having a substituent located at the para position being —(CH2)t— or —O—(CH2)t—, wherein t is an integer chosen from 1, 2, 3, 4, 5 or 6;

said substituent being connected to an aryl group on another photochromic material;

(iv) —OR2, R2 being chosen from

(a′) hydrogen, C1–C12 alkyl, C1–C12 acyl, phenyl(C1–C12)alkyl, mono(C1–C12)alkyl substituted phenyl(C1–C1 2)alkyl, mono(C1–C12)alkoxy substituted phenyl(C1–C12)alkyl, C1–C12 alkoxy(C1–C12)alkyl, C3–C7 cycloalkyl, mono(C1–C12)alkyl substituted C3–C7 cycloalkyl, C1–C12 haloalkyl, allyl, benzoyl, mono-substituted benzoyl, naphthoyl or mono-substituted naphthoyl;

each of said benzoyl and naphthoyl substituents being independently chosen from C1–C12 alkyl or C1–C12 alkoxy;

(b′) —CH(R3)Q, wherein R3 being chosen from hydrogen or C1–C12 alkyl and Q being chosen from —CN, —CF3, or —COOR4 and R4 being chosen from hydrogen or C1–C12 alkyl;

(c′) —C(O)V, wherein V being chosen from hydrogen, C1–C12 alkoxy, phenoxy, mono- or di-(C1–C12)alkyl substituted phenoxy, mono- or di-(C1–C12)alkoxy substituted phenoxy, an unsubstituted, mono- or di-substituted aryl group, amino, mono(C1–C12)alkylamino, di(C1–C12)alkylamino, phenylamino, mono- or di-(C1–C12)alkyl substituted phenylamino, or mono- or di-(C1–C12)alkoxy substituted phenylamino;

each of said aryl group substituents being independently chosen from C1–C12 alkyl or C1–C12 alkoxy;

or

(d′) tri(C1–C12)alkylsilyl, tri(C1–C12)alkoxysilyl, di(C1–C12)alkyl (C1–C12 alkoxy)silyl or di(C1–C12)alkoxy(C1–C12 alkyl)silyl;

(v) —CH(Q′)2, Q′ being chosen from —CN or COOR6 and R6 being chosen from hydrogen, C1–C12 alkyl, phenyl(C1–C12)alkyl, mono(C1–C12)alkyl substituted phenyl(C1–C12)alkyl, mono(C1–C12)alkoxy substituted phenyl(C1–C12)alkyl or an unsubstituted, mono- or di-substituted aryl group;

each of said aryl group substituents being independently chosen from C1–C12 alkyl or C1–C12 alkoxy;

(vi) —CH(R7)G, R7 being chosen from hydrogen, C1–C12 alkyl or an unsubstituted, mono- or di-substituted aryl group and G being chosen from —COOR5, —COR8 or —CH2OR9;

wherein R8 being chosen from hydrogen, C1–C12 alkyl, an unsubstituted, mono- or di-substituted aryl group, amino, mono(C1–C12)alkylamino, di(C1–C12)alkylamino, phenylamino, mono- or di-(C1–C12)alkyl substituted phenylamino, mono- or di-(C1–C12)alkoxy substituted phenylamino, diphenylamino, mono- or di(C1–C12)alkyl substituted diphenylamino, mono- or di(C1–C12)alkoxy substituted diphenylamino, morpholino or piperidino R9 being chosen from hydrogen, —C(O)R6, C1–C12 alkyl, C1–C12 alkoxy(C1–C12)alkyl, phenyl(C1–C12)alkyl, mono(C1–C12)alkoxy substituted phenyl(C1–C12)alkyl or an unsubstituted, mono- or di-substituted aryl group, each of said aryl group substituents being independently chosen from C1–C12 alkyl or C1–C12 alkoxy;

(vii) the group T represented by the formula:

-Z[(OC2H4)x(OC3H6)y(OC4H8)z]Z′ or

—[(OC2H4)x(OC3H6)y(OC4H8)z]Z′

wherein -Z is chosen from —C(O)— or —CH2—, Z′ being chosen from C1–C12 alkoxy or a polymerizable group, x, y and z are each an number between 0 and 50, and the sum of x, y and z is between 2 and 50;

(viii) —SR10, R10 being chosen from C1–C12 alkyl, aryl, mono- or di-substituted aryl, and each of said aryl substituents being chosen independently from C1–C12 alkyl, C1–C12 alkoxy or halogen;

(ix) —N(R11)R12, wherein R11 and R12 are the same as R2 described hereinbefore at (a)(iv)(a′), (a)(iv)(b′) and (a)(iv)(c′);

(x) a nitrogen containing ring represented by the following graphic formula IIA:

wherein each Y being independently chosen for each occurrence from —CH2—, —CH(R13)—, —C(R13)(R13)—, —CH(aryl)—, —CH(aryl)2— or —C(R13)(aryl)—;

X being —Y—, —O—, —S—, —S(O)—, —S(O2)—, —NH—, —NR13— or —N—aryl;

R13 being C1–C12 alkyl;

said aryl group being phenyl or naphthyl, m is an integer chosen from 1, 2 or 3 and p is an integer chosen from 0, 1, 2 or 3;

provided that when p is 0, X is Y;

(xi) a group represented by one of the following graphic formulae IIB or IIC:

wherein R15, R16 and R17 are each chosen independently for each occurrence in each formula from hydrogen, C1–C12 alkyl, phenyl or naphthyl;

or the groups R15 and R16 together form a ring of 5 to 8 carbon atoms, R14 being chosen independently for each occurrence from C1–C12 alkyl, C1–C12 alkoxy, or halogen and v is an integer chosen from 0, 1 or 2;

(xii) unsubstituted, mono- or di- substituted C4–C18 spirobicyclic amine;

(xiii) unsubstituted, mono- or di-substituted C4–C18 spirotricyclic amine;

said substituents for (xii) and (xiii) being independently chosen for each occurrence from aryl, C1–C12 alkyl, C1–C12 alkoxy or phenyl (C1–C12) alkyl;

or

(xiv) adjacent R1 substituents come together to form one of the following graphic formulae IID, IIE, or IIF;

wherein J and K being independently chosen for each occurrence in each formula from oxygen or —NR11—, R11, R14, R15 and R16 each being the same as described herein before, and n is an integer chosen from 0, 1, 2, 3 or 4;

and

(b) B and B′ are each independently chosen from:

(i) mono-T-substituted phenyl wherein the group T is represented by the formula:

-Z[(OC2H4)x(OC3H6)y(OC4H8)z]Z′ or

—[(OC2H4)x(OC3H6)y(OC4H8)z]′

wherein -Z is —C(O)— or —CH2, Z′ is C1–C12 alkoxy or a polymerizable group, x, y and z are each an number between 0 and 50, and the sum of x, y and z is between 2 and 50;

(ii) an unsubstituted, mono-, di-, or tri-substituted aryl group;

(iii) 9-julolidinyl or the unsubstituted, mono- or di-substituted heteroaromatic group chosen from pyridyl furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazoyl, benzopynidyl, indolinyl or fluorenyl, each of said aryl and heteroaromatic substituents in (ii) and (iii) being independently chosen from hydroxy, the group, —C(O)W, defined hereinbefore, aryl, mono(C1–C12)alkoxyaryl, di(C1–C12)alkoxyaryl, mono(C1–C12)alkylaryl, di(C1–C12)alkylaryl, haloaryl, C3–C7 cycloalkylaryl, C3–C7 cycloalkyl, C3–C7 cycloalkyloxy, C3–C7 cycloalkyloxy(C1–C12)alkyl, C3–C7 cycloalkyloxy(C1–C12)alkoxy, aryl(C1–C12)alkyl, aryl(C1–C12)alkoxy, aryloxy, aryloxy(C1–C12)alkyl, aryloxy(C1–C12)alkoxy, mono- or di-(C1–C12)alkylaryl(C1–C12)alkyl, mono- or di-(C1–C12)alkoxyaryl(C1–C12)alkyl, mono- or di-(C1–C12)alkylaryl(C1–C12)alkoxy, mono- or di-(C1–C12)alkoxyaryl(C1–C12)alkoxy, amino, mono(C1–C12)alkylamino, di(C1–C12)alkylamino, diarylamino, piperazino, N-(C1–C12)alkylpiperazino, N-arylpiperazino, aziridino, indolino, piperidino, morpholino, thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino, pyrrolidyl, C1–C12 alkyl, C1–C12 haloalkyl, C1–C12 alkoxy, mono(C1–C12)alkoxy(C1–C12)alkyl, acryloxy, methacryloxy, or halogen;

(iv) an unsubstituted or mono-substituted group chosen from pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolinyl, phenothiazinyl, phenoxazinyl, phenazinyl or acridinyl, each of said substituents being independently chosen from C1–C12 alkyl, C1–C12 alkoxy, phenyl, or halogen;

(v) a monosubstituted phenyl, said phenyl having a substituent located at the para position being —(CH2)t— or —O—(CH2)t—, wherein t is chosen from the integer 1, 2, 3, 4, 5 or 6, said substituent being connected to an aryl group on another photochromic material;

(vi) a group represented by one of the following graphic formulae IIG or IIH:

wherein A being independently chosen in each formula from methylene or oxygen and D being independently chosen in each formula from oxygen or substituted nitrogen, provided that when D is substituted nitrogen, A is methylene;

said nitrogen substituents being chosen from hydrogen, C1–C12 alkyl, or C2–C12 acyl;

each R19 being independently chosen for each occurrence in each formula from C1–C12 alkyl, C1–C12 alkoxy, hydroxy, or halogen;

R17 and R18 each being independently chosen in each formula from hydrogen or C1–C12 alkyl;

and q being chosen from the integer 0, 1 or 2;

(vii) C1–C12 alkyl, C1–C12 haloalkyl, C1–C12 alkoxy(C1–C12)alkyl, C3–C7 cycloalkyl, mono(C1–C12)alkoxy (C3–C7)cycloalkyl, mono(C1–C12)alkyl(C3–C7)-cycloalkyl, halo(C3–C7)cycloalkyl, or C4–C12 bicycloalkyl, provided that both B and B′ are not chosen from (vii):

(viii) a group represented by the following graphic formula IIJ:

wherein L being chosen from hydrogen or C1–C12 alkyl and M being chosen from an unsubstituted, mono-, or di-substituted group chosen from naphthyl, phenyl, furanyl, or thienyl;

each of said group substituents being independently chosen from C1–C12 alkyl, C1–C12 alkoxy, or halogen;

or

(ix) B and B′ taken together form a fluoren-9-ylidene, mono-, or di- substituted fluoren-9-ylidene or a spirocyclic group chosen from saturated C3–C12 spiro-monocyclic hydrocarbon rings, saturated C7–C12 spiro-bicyclic hydrocarbon rings, or saturated C7–C12 spiro-tricyclic hydrocarbon rings, provided that said spirocyclic group is not norbornylidene or bicyclor[3.3.1]9-nonylidene, each of said fluoren-9-ylidene substituents being independently chosen from C1–C12 alkyl, C1–C12 alkoxy or halogen.

Pyrano-quinolines, pyrano-quinolinones, combinations thereof, photochromic compositions and articles

Life of this patent

Pyrano-quinolines, pyrano-quinolinones, combinations thereof, photochromic compositions and articles

Life of this patent

Abstract

Claims5