US 10,532,997 B2 · Photochromic compounds

Abstract

A photochromic compound is provided, which may be a pyran, an oxazine, or a fulgide. The photochromic compound has at least one substituent Q attached thereto, each Q independently being —N3, —CN, —COOR′, —CCR′, —C(R′)C(R′)R′, —OCOR′, —OCOOR′, —SR′, —OSO2R′″, and/or CON(R′)R′, wherein each R′ is hydrogen, an unsubstituted or substituted alkyl group having from 1 to 18 carbon atoms; an unsubstituted or substituted aryl group, an unsubstituted or substituted alkene or alkyne group having from 2 to 18 carbon atoms, wherein the substituents are halo or hydroxyl and R′″ is —CF3 or a perfluorinated alkyl group having from 2 to 18 carbon atoms The number, locations and nature of the constituents Q are dependent upon the structure of the photochromic compound.

A naphthol represented by the following graphic formula:

wherein:
(A) substituent Q comprises —N3, —CN, —COOR′, —CCR′, —C(R′)C(R′)R′, —OCOR′, —OCOOR′, —SR′, —OSO2Rm′″, and/or CON(R′)R′, wherein each R′ independently comprises hydrogen, an unsubstituted or substituted alkyl group having from 1 to 18 carbon atoms, an unsubstituted or substituted aryl group, an unsubstituted or substituted alkene or alkyne group having from 2 to 18 carbon atoms, wherein said substituents are chosen from halo and hydroxyl and R′″ comprises —CF3 or a perfluorinated alkyl group having from 2 to 18 carbon atoms;
and
(B) each i is an integer chosen from 0 to the total number of available positions and each R is independently chosen for each occurrence from:
(a) hydrogen, C1-C18 alkyl, C2-C18 alkylidene, C2-C18 alkylidyne, vinyl, C3-C10 cycloalkyl, C1-C18 haloalkyl, allyl, halogen, and benzyl that is unsubstituted or mono-substituted with at least one of C1-C18 alkyl and C1-C18 alkoxy;
(b) phenyl that is mono-substituted at the para position with at least one substituent chosen from:
C1-C18 alkoxy, linear or branched chain C1-C20 alkylene, linear or branched chain C1-C4 polyoxyalkylene, cyclic C3-C20 alkylene, phenylene, naphthylene, C1-C18 alkyl substituted phenylene, mono- or poly-urethane(C1-C20)alkylene, mono- or poly-ester(C1-C20)alkylene, mono- or poly-carbonate(C1-C20)alkylene, polysilanylene, polysiloxanylene and mixtures thereof wherein the at least one substituent is connected to an aryl group of a photochromic material;
(c) —CH(CN)2 and —CH(COOX1)2, wherein X1 is chosen from at least one of a lengthening agent L, hydrogen, C1-C18 alkyl that is unsubstituted or mono-substituted with phenyl, phenyl(C1-C18)alkyl that is mono-substituted with C1-C18 alkyl, C1-C18 haloalkyl, or C1-C18 alkoxy, and an aryl group that is unsubstituted, mono- or di-substituted, wherein each aryl substituent is independently chosen from C1-C18 alkyl, C1-C18 haloalkyl, lengthening agent L and C1-C18 alkoxy;
(d) —CH(X2)(X3), wherein:
(i) X2 is chosen from at least one of a lengthening agent L, hydrogen, C1-C18 alkyl, and an aryl group that is unsubstituted, mono- or di-substituted, wherein each aryl substituent is independently chosen from C1-C18 alkyl and C1-C18 alkoxy;
and
(ii) X3 is chosen from at least one of —COOX1, —COX1, —COX4, and —CH2OX5, wherein:
(A) X4 is chosen from at least one of morpholino, piperidino, amino that is unsubstituted, mono- or di-substituted with C1-C18 alkyl, and an unsubstituted, mono or di-substituted group chosen from phenylamino and diphenylamino, wherein each substituent is independently chosen from C1-C18 alkyl or C1-C18 alkoxy;
and
(B) X5 is chosen from a lengthening agent L, hydrogen, —C(O)X2, C1-C18 alkyl that is unsubstituted or mono-substituted with (C1-C18)alkoxy or phenyl, phenyl(C1-C18)alkyl that is mono-substituted with (C1-C18)alkoxy, and an aryl group that is unsubstituted, mono- or di-substituted, wherein each aryl substituent is independently chosen from C1-C18 alkyl and C1-C18 alkoxy;
(e) an unsubstituted, mono-, di-, or tri-substituted aryl group;
9-julolidinyl;
or an 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, benzopyridyl, indolinyl, and fluorenyl;
wherein each aryl and heteroaromatic substituent is independently chosen for each occurrence from:
(i) a lengthening agent L;
(ii) —COOX1 or —C(O)X6, wherein X6 is chosen from at least one of:
a lengthening agent L, hydrogen, C1-C18 alkoxy, phenoxy that is unsubstituted, mono- or di-substituted with C1-C18 alkyl or C1-C18 alkoxy, an aryl group that is unsubstituted, mono- or di-substituted with C1-C18 alkyl or C1-C18 alkoxy, an amino group that is unsubstituted, mono- or di-substituted with C1-C18 alkyl, and a phenylamino group that is unsubstituted, mono- or di-substituted with C1-C18 alkyl or C1-C18 alkoxy;
(iii) aryl, haloaryl, C3-C10 cycloalkylaryl, and an aryl group that is mono- or di-substituted with C1-C18 alkyl or C1-C18 alkoxy;
(iv) C1-C18 alkyl, C3 - C10 cycloalkyl, C3-C10cycloalkyloxy(C1-C18)alkyl, aryl(C1-C18)alkyl, aryloxy(C1-C18)alkyl, mono- or di-(C1-C18)alkylaryl (C1-C18)alkyl, mono- or di-(C1-C18)alkoxyaryl(C1-C18)alkyl, C1-C18 haloalkyl, and mono(C1-C18)alkoxy(C1-C18)alkyl;
(v) C1-C18 alkoxy, C3-C10 cycloalkoxy;
cycloalkyloxy(C1-C18)alkoxy, aryl(C1-C18)alkoxy, aryloxy(C1-C18)alkoxy, mono- or di-(C1-C18)alkylaryl(C1-C18)alkoxy, and mono- or di-(C1-C18)alkoxyaryl(C1-C18)alkoxy;
(vi) aminocarbonyl, aminocarbonyl(C1-C18)alkylene, amino, mono- or di-(C1-C18)alkylamino, diarylamino, piperazino, N-(C1-C18)alkylpiperazino, N-arylpiperazino, aziridino, indolino, piperidino, morpholino, thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino, pyrrolidyl, hydroxy, acryloxy, methacryloxy, and halogen;
(vii) —OX7 or —N(X7)2, wherein X7 is chosen from:
(A) a lengthening agent L, hydrogen, C1-C18 alkyl, C1-C18 acyl, phenyl(C1-C18)alkyl, mono (C1-C18)alkyl substituted phenyl(C1-C18) alkyl, mono (C1-C18)alkoxy substituted phenyl(C1-C18)alkyl;
C1-C18alkoxy(C1-C18)alkyl;
C3-C10 cycloalkyl;
mono(C1-C18)alkyl substituted C3-C10 cycloalkyl, C1-C18 haloalkyl, allyl, benzoyl, mono-subsituted benzoyl, naphthoyl or mono-substituted naphthoyl, wherein each of said benzoyl and naphthoyl substituents are independently chosen from C1-C18 alkyl, and C1-C18 alkoxy;
(B) —CH(X8)X9, wherein X8 is chosen from a lengthening agent L, hydrogen or C1-C18 alkyl;
and X9 is chosen from a lengthening agent L, —CN, —CF3, or —COOX10, wherein X10 is chosen from a lengthening agent L, hydrogen or C1-C18 alkyl;
(C) —C(O)X6;
or
(D) tri(C1-C18)alkylsilyl, tri(C1-C18)alkylsilyloxy, tri(C1-C18)alkoxysilyl, tri(C1-C18)alkoxysilyloxy, di(C1-C18)alkyl(C1-C18alkoxy)silyl, di(C1-C18)alkyl(C1-C18 alkoxy)silyloxy, di(C1-C18)alkoxy(C1-C18 alkyl)silyl or di(C1-C18)alkoxy(C1-C18 alkyl)silyloxy;
(viii) SX11, wherein X11 is chosen from a lengthening agent L, hydrogen, C1-C18alkyl, C1-C18haloalkyl, an aryl group that is unsubstituted, or mono- or di-substituted with C1-C18alkyl, C1-C18alkoxy, or halogen;
(ix) a nitrogen containing ring represented by Formula i:
wherein
(A) n is an integer chosen from 0, 1, 2, and 3, and each U is independently chosen for each occurrence from —CH2—, —CH(X12)—, —C(X12)2—, —CH(X13)—, —C(X13)2—, and —C(X12)(X13)—, wherein X12 is chosen from a lengthening agent L and C1-C18 alkyl, and X13 is chosen from a lengthening agent L, phenyl and naphthyl, and
(B) U′ is chosen from U, —O—, —S—, —S(O)—, —NH—, —N(X12)— or —N(X13)—, and m is an integer chosen from 1, 2, and 3, and
(x) a group represented by Formula ii or iii:
wherein X14, X15, and X16 are independently chosen for each occurrence from a lengthening agent L, hydrogen, C1-C18 alkyl, phenyl or naphthyl, or X14 and X15 together form a ring of 5 to 8 carbon atoms;
p is an integer chosen from 0, 1, or 2, and X17 is independently chosen for each occurrence from a lengthening agent L, C1-C18 alkyl, C1-C18 alkoxy, or halogen;
(f) an unsubstituted or mono-substituted group chosen from pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolidinyl, phenothiazinyl, phenoxazinyl, phenazinyl, or acridinyl, wherein each substituent is independently chosen from a lengthening agent L, C1-C18 alkyl, C1-C18 alkoxy, phenyl, hydroxy, amino or halogen;
(g) a group represented by Formula iv or v:
wherein
(i) V′ is independently chosen in each formula from —O—, —CH—, C1-C6 alkylene, and C3-C10 cycloalkylene,
(ii) V is independently chosen in each formula from —O— or —N(X21)—, wherein X21 is from a lengthening agent L represented by Formula I above, hydrogen, C1-C18 alkyl, and C2-C18 acyl, provided that if V is —N(X21)—, V′ is —CH2—,
(iii) X18 and X19 are each independently chosen from a lengthening agent L, hydrogen and C1-C18 alkyl, and
(iv) k is chosen from 0, 1, and 2, and each X20 is independently chosen for each occurrence from a lengthening agent L, C1-C18 alkyl, C1-C18 alkoxy, hydroxy and halogen;
(h) a group represented by Formula vi:
(i) X22 is chosen from a lengthening agent L, hydrogen and C1-C18 alkyl, and
(ii) X23 is chosen from a lengthening agent L and an unsubstituted, mono-, or di-substituted group chosen from aryl, furanyl and thienyl, wherein each substituent is independently chosen for each occurrence from C1-C18 alkyl, C1-C18 alkoxy, and halogen;
—C(O)X24, wherein X24 is chosen from a lengthening agent L, hydroxy, C1-C18 alkyl, C1-C18 haloalkyl, C1-C18 alkoxy, phenyl that is unsubstituted or mono-substituted with C1-C18 alkyl or C1-C18 alkoxy, amino that is unsubstituted, mono- or di-substituted with at least one of C1-C18 alkyl, aryl and benzyl;
(j) —COOX1;
(k) —OX7 and —N(X7)2;
(l) —SX11;
(m) the nitrogen containing ring represented by Formula i;
(n) the group represented by one of Formula ii or iii;
(o) a lengthening agent L represented by:
—[S1]c-[Q1-[S2]d]d′-[Q2-[S3]e]e′-[Q3-[S4]f]f′—S5—P
wherein:
(i) each Q1, Q2, and Q3 is independently chosen for each occurrence from:
a divalent group chosen from:
an unsubstituted or a substituted aromatic group, an unsubstituted or a substituted alicyclic group, an unsubstituted or a substituted heterocyclic group, and mixtures thereof, wherein substituents are chosen from:
a group represented by P, liquid crystal mesogens, halogen, poly(C1-C18 alkoxy), C18 alkoxycarbonyl, C1-C18 alkylcarbonyl, C1-C18 alkoxycarbonyloxy, aryloxycarbonyloxy, perfluoro(C1-C18)alkoxy, perfluoro(C1-C18)alkoxycarbonyl, perfluoro(C1-C8)alkylcarbonyl, perfluoro(C1-C18)alkylamino, di-(perfluoro(C1-C18)alkyl)amino, perfluoro(C1-C18)alkylthio, C1-C18 alkylthio, C1-C18 acetyl, C3-C10 cycloalkyl, C3-C10cycloalkoxy, a straight-chain or branched C1-C18 alkyl group that is mono-substituted with cyano, halo, or C1-C18 alkoxy, or poly-substituted with halo, and a group comprising one of the following formulae:
-M(T)(t−1) and -M(OT)(t−1), wherein M is chosen from aluminum, antimony, tantalum, titanium, zirconium and silicon, T is chosen from organofunctional radicals, organofunctional hydrocarbon radicals, aliphatic hydrocarbon radicals and aromatic hydrocarbon radicals, and t is the valence of M;
(ii) c, d, e, and f are each independently chosen from an integer ranging from 0 to 20, inclusive;
and each S1, S2, S3, S4, and S5 is independently chosen for each occurrence from a spacer unit chosen from:
(1) —(CH2)g—, —(CF2)h—, —Si(CH2)g—, —(Si[(CH3)2]O)h—, wherein g is independently chosen for each occurrence from 1 to 20;
h is a whole number from 1 to 16 inclusive;
(2) —N(Z)—, —C(Z)═C(Z)—, —C(Z)═N—, —C(Z′)—C(Z′)— or a single bond, wherein Z is independently chosen for each occurrence from hydrogen, C1-C18 alkyl, C3-C10 cycloalkyl and aryl, and Z′ is independently chosen for each occurrence from C1-C18 alkyl, C3-C10 cycloalkyl and aryl;
and
(3) —O—, —C(O)—, —C≡C—, —N═N—, —S—, —S(O)—, —S(O)(O)—, —(O)S(O)—, —(O)S(O)O—, —O(O)S(O)O—, or straight-chain or branched C1-C24 alklene residue, said C1-C24 alkylene residue being unsubstituted, mono-substituted by cyano or halo, or poly-substituted by halo;
provided that when two spacer units comprising heteroatoms are linked together the spacer units are linked so that heteroatoms are not directly linked to each other and when S1 and S5 are linked to PC and P, respectively, they are linked so that two heteroatoms are not directly linked to each other;
(iii) P is chosen from:
hydroxy, amino, C2-C18 alkenyl, C2-C18 alkynyl, azido, silyl, siloxy, silylhydride, (tetrahydro-2H-pyran-2-yl)oxy, thio, isocyanato, thioisocyanato, acryloyloxy, methacryloyloxy, 2-(acryloyloxy)ethylcarbamyl, 2-(methacryloyloxy)ethylcarbamyl, aziridinyl, allyloxycarbonyloxy, epoxy, carboxylic acid, carboxylic ester, acryloylamino, methacryloylamino, aminocarbonyl, C1-C18 alkyl aminocarbonyl, aminocarbonyl(C1-C18)alkyl, C1-C18 alkyloxycarbonyloxy, halocarbonyl, hydrogen, aryl, hydroxy(C1-C18)alkyl, C1-C18 alkyl, C1-C18 alkoxy, amino (C1-C18)alkyl, C1-C18 alkylamino, di-(C1C18) alkyl amino, C1-C18 alkyl(C1-C18)alkoxy, C1-C18 alkoxy(C1-C18)alkoxy, nitro, poly(C1-C18)alkyl ether, (C1-C18)alkyl(C1-C18)alkoxy(C1-C18)alkyl, polyethyleneoxy, polypropyleneoxy, ethylenyl, acryloyl, acryloyloxy(C1-C18)alkyl, methacryloyl, methacryloyloxy(C1-C18)alkyl, 2-chloroacryloyl, 2-phenylacryloyl, acryloyloxyphenyl, 2-chloroacryloylamino, 2-phenylacryloylaminocarbonyl, oxetanyl, glycidyl, cyano, isocyanato(C1-C18)alkyl, itaconic acid ester, vinyl ether, vinyl ester, a styrene derivative, main-chain and side-chain liquid crystal polymers, siloxane derivatives, ethyleneimine derivatives, maleic acid derivatives, fumaric acid derivatives, unsubstituted cinnamic acid derivatives, cinnamic acid derivatives that are substituted with at least one of methyl, methoxy, cyano and halogen, or substituted or unsubstituted chiral or non-chiral monovalent or divalent groups chosen from steroid radicals, terpenoid radicals, alkaloid radicals and mixtures thereof, wherein the substituents are independently chosen from C1-C18 alkyl, C1-C18 alkoxy, amino, C3-C10 cycloalkyl, C1-C18 alkyl(C1-C18)alkoxy, fluoro(C1C18)alkyl, cyano, cyano(C1-C18)alkyl, cyano(C1-C18)alkoxy or mixtures thereof, or P is a structure having from 2 to 4 reactive groups or P is an unsubstituted or substituted ring opening metathesis polymerization precursor;
and
(iv) d′, e′ and f′ are each independently chosen from 0, 1, 2, 3, and 4, provided that a sum of d′+e′+f′ is at least 1;
(p) immediately adjacent R groups together form a group represented by Formula vii, viii, or ix:
wherein
(i) W and W′ are independently chosen for each occurrence from —O—, —N(X7)—, —C(X14)—, —C(X17)—,
(ii) X14, X15 and X17 are as set forth above, and
(iii) q is an integer chosen from 0, 1, 2, 3, and 4.

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Photochromic compounds

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Photochromic compounds

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Abstract

Claims3