# US 10,501,477 B2 · Photochromic thienochromene compounds

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- Number: US 10,501,477 B2
- Document ID: US10501477B2
- Status: Granted
- Kind: B2
- Application number: 15/556,672
- Filed: 2015-03-10
- Published: 2018-02-22
- Granted: 2019-12-10
- Earliest claimed: 2015-03-10
- Assignees: Transitions Optical, Inc.
- Applicants: Transitions Optical, Inc.
- Inventors: Jun Deng; Brian R. Stepp; Eric Spitler; Wenjing Xiao; Massimiliano Tomasulo; Robert W. Walters
- Web page: https://patentgrep.com/patent/US10501477B2

## CPC

- C07D 495/14: Ortho-condensed systems
- C07D 493/14: Ortho-condensed systems
- C09B 57/00: Other synthetic dyes of known constitution
- C09K 9/02: Organic tenebrescent materials
- G02B 5/23: Photochromic filters
- G03C 1/73: containing organic compounds
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C09B: ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES {, e.g. PIGMENTS}; MORDANTS; LAKES (fermentation or enzyme using processes to synthesise a desired chemical compound C12P)
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G03C: PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES (for photomechanical purposes G03F); PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY (photographic processes characterised by the use or manipulation of apparatus classifiable per se in subclass G03B, see G03B; photomechanical production of textured or patterned surfaces G03F; electrophotography, magnetography G03G)

## Abstract

The present invention relates to photochromic compounds, such as thienochromene compounds represented by the following Formulas (1a) and/or (1b). The present invention also relates to photochromic compositions and articles containing one or more such photochromic thienochromene compounds.

## Claims

### Claim 1

A photochromic compound represented by at least one of the following Formulas (Ia) and (Ib),
wherein independently for each of Formulas (Ia) and (Ib),
R3, and R4 are in each case independently selected from, hydrogen; hydrocarbyl;
substituted hydrocarbyl; interrupted hydrocarbyl; substituted interrupted hydrocarbyl, wherein each interrupted hydrocarbyl and each substituted interrupted hydrocarbyl, are in each case independently interrupted with at least one interrupting group selected from the group consisting of —O—, —S—, —C(O)—, —C(O)O—, —OC(O)O—, —B(R11′)—, —P(R11′)—, —P(O)(R11′)—, —S(O)—, —SO2—, —N═N—, —C(O)N(R11′)—, —OC(O)N(R11′)—, —N(R11′)C(O)N(R11′)—, —N(R11′)— where R11′ in each case is independently selected from hydrogen, hydrocarbyl or substituted hydrocarbyl, —Si(OR8′)w(R8′)t—, where w and t are each independently selected from 0 to 2, provided that the sum of w and t is 2, and each R8′ is independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations of two or more interrupting groups thereof; halogen; cyano; and —N(R11″)R12′, wherein R11″ and R12′ are each independently selected from hydrogen, hydrocarbyl or substituted hydrocarbyl, or R11″ and R12′ together forma ring structure or a ring structure including at least one heteroatom; or
R3 and R4 together form a ring structure;
R1 and R2 together form a ring structure, and said ring structure is selected from the following Formulas (IIa), (IIb), (IIc), and (IId),
wherein each ring structure represented by Formulas (IIa), (IIb), (IIc), and (IId), is fused to said photochromic compound at carbons a and b,
n, independently for Formulas (IIa), (IIb), (IIc), and (IId), is 1 to 4,
p, independently for Formulas (IIb) and (IIc), is 1 or 2,
R5 independently for each n, and independently for Formulas (IIa), (IIb), (IIc), and (IId), and
R6 independently for each p, and independently for Formulas (IIb) and (IIc), are in each case independently selected from, hydrogen; hydrocarbyl; substituted hydrocarbyl; interrupted hydrocarbyl; substituted interrupted hydrocarbyl, wherein each interrupted hydrocarbyl and each substituted interrupted hydrocarbyl, are in each case independently interrupted with at least one interrupting group selected from the group consisting of —O—, —S—, —C(O)—, —C(O)O—, —OC(O)O—, —B(R11′)—, —P(R11′)—, —P(O)(R11′)—, —S(O)—, —SO2—, —N═N—, —C(O)N(R11′)—, —OC(O)N(R11′)—, —N(R11′)C(O)N(R11′)—, —N(R11′)— where R11′ in each case is independently selected from hydrogen, hydrocarbyl or substituted hydrocarbyl, —Si(OR8′)w(R8′)t—, where w and t are each independently selected from 0 to 2, provided that the sum of w and t is 2, and each R8′ is independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations of two or more interrupting groups thereof; halogen; cyano; and —N(R11″)R12′, wherein R11″ and R12′ are each independently selected from hydrogen, hydrocarbyl or substituted hydrocarbyl, or R11″ and R12′ together forma ring structure or a ring structure including at least one heteroatom; and
R7 and R8 independently for Formula (IId) are each independently selected from hydrogen; hydrocarbyl; substituted hydrocarbyl; interrupted hydrocarbyl; and substituted interrupted hydrocarbyl, wherein each interrupted hydrocarbyl and each substituted interrupted hydrocarbyl, are each independently interrupted with at least one interrupting group selected from the group consisting of —O—, —S—, —N(R11′)—, where R11′ is selected from hydrogen, hydrocarbyl or substituted hydrocarbyl, and combinations of two or more interrupting groups thereof; or R7 and R8 together forma ring structure; and
B and B′ are each independently selected from unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, alkenyl, and alkynyl, or B and B′ taken together forma ring structure.

### Claim 2 (depends on 1)

The photochromic compound of claim 1, wherein
independently for Formulas (Ia) and (Ib), one of, R3 is, R4 is, R5 is, R6 is, B is substituted with, and B′ is substituted with,
in each case independently, a group L represented by the following Formula (III),
[S1]c-[Q1-[S2]d]d′-[Q2-[S3]e]e′-[Q3-[S4]f]f′—S5—P Formula (III)
wherein:
(a) Q1, Q2, and Q3 for each occurrence, are independently selected from a divalent group selected from unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, unsubstituted cycloalkyl, substituted cycloalkyl, unsubstituted heterocycloalky, and substituted heterocycloalkyl;
wherein the aryl substituents, heteroaryl substituents, cycloalkyl substituents, and heterocycloalkyl substituents are each independently selected from P, liquid crystal mesogens, halogen, poly(C1-C18 alkoxy), C1-C18 alkoxycarbonyl, C1-C18 alkylcarbonyl, C1-C18 alkoxycarbonyloxy, aryloxycarbonyloxy, perfluoro(C1-C18)alkoxy, perfluoro(C1-C18)alkoxycarbonyl, perfluoro(C1-C18)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-C10 cycloalkoxy, straight-chain C1-C18 alkyl, and branched C1-C18 alkyl;
wherein said straight-chain C1-C18 alkyl and branched C1-C18 alkyl are mono-substituted with a group selected from cyano, halogen, and C1-C18 alkoxy; or
wherein said straight-chain C1-C18 alkyl and branched C1-C18 alkyl are poly-substituted with at least two groups independently selected from halogen, -M(T)(v-1) and -M(OT)(v-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 v is the valence of M;
(b) c, d, e, and f are each independently chosen from an integer of 1 to 20; and each S1, S2, S3, S4, and S5 is independently chosen for each occurrence from a spacer unit selected from:
(i) alkylene, substituted alkylene, haloalkylene, substituted haloalkylene, —Si(CH2)g—, and —(Si[(CH3)2]O)h—, wherein g for each occurrence is independently chosen from an integer from 1 to 20; h for each occurrence is independently chosen from an integer from 1 to 16; and said substitutes for the alkylene and haloalkylene are independently selected from C1-C18 alkyl, C3-C10 cycloalkyl and aryl;
(ii) —N(Z)—, —C(Z)═C(Z)—, —C(Z)═N—, —C(Z′)2—C(Z′)2—, and a single bond, wherein Z for each occurrence is independently selected from hydrogen, C1-C18 alkyl, C3-C10 cycloalkyl and aryl, and Z′ for each occurrence is independently selected from C1-C18 alkyl, C3-C10 cycloalkyl and aryl; and
(iii) —O—, —C(═O)—, —C≡C—, —N═N—, —S—, —S(═O)—, —(O═)S(═O)—, —(O═)S(═O)O—, —O(O═)S(═O)O— and straight-chain or branched C1-C24 alkylene residue, said C1-C24 alkylene residue being unsubstituted, mono-substituted by cyano or halogen, or poly-substituted by halogen,
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 the bond between S5 and P is free of two heteroatoms linked to each other;
(c) P for each occurrence is independently selected 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-(C1-C18)alkylamino, 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, ethylene, 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, male imide derivatives, fumaric acid derivatives, unsubstituted cinnamic acid derivatives, cinnamic acid derivatives that are substituted with at least one of methyl, methoxy, cyano and halogen, and 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(C1-C18)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, or P is a substituted or unsubstituted photochromic compound; and
(d) d′, e′ and f′ are each independently chosen from 0, 1, 2, 3, and 4, provided that the sum of d′+e′+f′ is at least 1.

### Claim 3 (depends on 2)

The photochromic compound of claim 2, wherein
independently for each group L represented by Formula (III),
(a) Q1, Q2, and Q3 for each occurrence, are independently selected from unsubstituted aryl, substituted aryl, unsubstituted cycloalkyl, and substituted cycloalkyl,
(b) each S1, S2, S3, S4, and S5 is independently chosen for each occurrence from a spacer unit selected from,
(ii) —N(Z)—, —C(Z)═C(Z)—, —C(Z)═N—, —C(Z′)2—C(Z′)2—, and a single bond, wherein Z for each occurrence is independently selected from hydrogen, C1-C8 alkyl, C3-C6 cycloalkyl and aryl, and Z′ for each occurrence is independently selected from C1-C8 alkyl, C3-C6 cycloalkyl and aryl, and
(iii) —O—, —C(═O)—, —C≡C—, —N═N—, —S—, —S(═O)—, and straight-chain or branched C1-C12 alkylene residue, said C1-C12 alkylene residue being unsubstituted, mono-substituted by cyano or halogen, or poly-substituted by halogen, and
(c) P for each occurrence is independently selected from hydrogen, hydroxy, amino, C2-C8 alkenyl, C2-C8 alkynyl, acryloyloxy, methacryloyloxy, 2-(acryloyloxy)ethylcarbamyl, 2-(methacryloyloxy)ethylcarbamyl, epoxy, carboxylic acid, carboxylic ester, acryloylamino, methacryloylamino, aminocarbonyl, C1-C8 alkyl aminocarbonyl, aminocarbonyl(C1-C8)alkyl, C1-C8 alkyloxycarbonyloxy, halocarbonyl, aryl, hydroxy(C1-C8)alkyl, C1-C8 alkyl, C1-C8 alkoxy, amino(C1-C8)alkyl, C1-C8 alkylamino, di-(C1-C8)alkylamino, C1-C8 alkyl(C1-C8)alkoxy, C1-C8 alkoxy(C1-C8)alkoxy, nitro, poly(C1-C8)alkyl ether, (C1-C8)alkyl(C1-C8)alkoxy(C1-C8)alkyl, polyethyleneoxy, polypropyleneoxy, ethylene, acryloyl, acryloyloxy(C1-C18)alkyl, methacryloyl, methacryloyloxy(C1-C8)alkyl, 2-chloroacryloyl, 2-phenylacryloyl, acryloyloxyphenyl, 2-chloroacryloylamino, 2-phenylacryloylaminocarbonyl, oxetanyl, glycidyl, cyano, isocyanato(C1-C18)alkyl, itaconic acid ester, vinyl ether, and vinyl ester.

### Claim 4 (depends on 3)

The photochromic compound of claim 3, wherein
independently for each group L represented by Formula (III),
(b) each S1, S2, S3, S4, and S5 is independently chosen for each occurrence from a spacer unit selected from,
(ii) —N(Z)—, —C(Z)═C(Z)—, and a single bond, wherein Z for each occurrence is independently selected from hydrogen, C1-C8 alkyl, C3-C6 cycloalkyl and aryl, and Z′ for each occurrence is independently selected from C1-C8 alkyl, C3-C6 cycloalkyl and aryl, and
(iii) —O—, —C(═O)—, —C≡C—, and straight-chain or branched C1-C6 alkylene residue, said C1-C6 alkylene residue being unsubstituted, mono-substituted by cyano or halogen, or poly-substituted by halogen, and
(c) P for each occurrence is independently selected from hydrogen, hydroxy, amino, C2-C8 alkenyl, C2-C8 alkynyl, and aryl.

### Claim 5 (depends on 2)

The photochromic compound of claim 2, wherein each group L is independently selected from,

### Claim 6 (depends on 1)

A photochromic compound represented by the following Formula (IV)
L1-(PC)n′ Formula (IV)
wherein,
n′ is at least 2,
PC independently for each n is a residue of said photochromic compound of claim 1, and
L1 is a multivalent linking group selected from,
a multivalent polymer,
a multivalent hydrocarbyl group,
a multivalent substituted hydrocarbyl group,
a multivalent interrupted hydrocarbyl group, and
a multivalent substituted interrupted hydrocarbyl group,
wherein each multivalent interrupted hydrocarbyl group and each multivalent substituted interrupted hydrocarbyl group, are each independently interrupted with at least one interrupting group selected from the group consisting of —O—, —S—, —C(O)—, —C(O)O—, —OC(O)O—, —B(R11′)—, —P(R11′)—, —P(O)(R11′)— —S(O)—, —SO2—, —N═N—, —C(O)N(R11′)—, —OC(O)N(R11′)—, —N(R11′)C(O)N(R11′)—, —N(R11′)— where R11′ in each case is independently selected from hydrogen, hydrocarbyl or substituted hydrocarbyl, —Si(OR8′)w(R8′)t—, where w and t are each independently selected from 0 to 2, provided that the sum of w and t is 2, and each R8′ is independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations of two or more interrupting groups thereof.

### Claim 7 (depends on 6)

The photochromic compound of claim 6, wherein
said multivalent polymer is selected from multivalent polyurethane, multivalent polyester, multivalent polyether, multivalent poly(meth)acrylate, multivalent polyvinylalcohol, multivalent polycarbonate, multivalent polysiloxane, and multivalent cyclic polysiloxane, and
said multivalent hydrocarbyl group, said multivalent substituted hydrocarbyl group, said multivalent interrupted hydrocarbyl group, and said multivalent substituted interrupted hydrocarbyl group, each independently comprise a residue selected from, a residue of a polyisocyanate, a residue of a polyol, a residue of a polycarboxylic acid, a residue of a polycarbonate functional material, and combinations thereof.

### Claim 8 (depends on 1)

A photochromic composition comprising the photochromic compound of claim 1.

### Claim 9 (depends on 1)

A photochromic article comprising the photochromic compound of claim 1.

### Claim 10 (depends on 9)

The photochromic article of claim 9, wherein said photochromic article is selected from ophthalmic articles, display articles, windows, mirrors, active liquid crystal cell articles, and passive liquid crystal cell articles.

### Claim 11 (depends on 10)

The photochromic article of claim 10, wherein said photochromic article is selected from ophthalmic articles, and said ophthalmic articles are selected from corrective lenses, non-corrective lenses, contact lenses, intra-ocular lenses, magnifying lenses, protective lenses, and visors.

### Claim 12 (depends on 10)

The photochromic article of claim 10, wherein said photochromic article is selected from display articles, and said display articles are selected from screens, monitors, and security elements.