# US 9,006,427 B2 · Photochromic materials demonstrating improved fade rates

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 9,006,427 B2
- Document ID: US9006427B2
- Status: Granted
- Kind: B2
- Application number: 14/174,898
- Filed: 2014-02-07
- Published: 2014-06-05
- Granted: 2015-04-14
- Earliest claimed: 2006-10-30
- Assignees: Transitions Optical, Inc.
- Applicants: Transitions Optical, Inc.
- Inventors: Anu Chopra; Patrick M. Brown
- Web page: https://patentgrep.com/patent/US9006427B2

## CPC

- C07D 413/10: linked by a carbon chain containing aromatic rings
- C07D 311/94: condensed with rings other than six-membered or with ring systems containing such rings
- C09K 9/02: Organic tenebrescent materials
- G02B 5/23: Photochromic filters
- G03C 1/73: containing organic compounds
- C09K 2211/145: containing oxygen as the only heteroatom
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- 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

Various photochromic materials are provided that are essentially free of polymerizable unsaturated groups, and comprise: a) an indeno[2′,3′:3,4]naphtho[1,2-b]pyran; and b) an electron-withdrawing, non-conjugating group bonded at the 11-position of the indeno[2′,3′:3,4]naphtho[1,2-b]pyran. Alternative embodiments include various substituents at other positions of the indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

## Claims

### Claim 1

A photochromic material that is free of polymerizable unsaturated groups, said photochromic material represented by:
wherein:
B and B′ are each independently:
a metallocenyl group;
an aryl group that is mono-substituted with a reactive substituent or a compatibilizing substituent;
9-julolidinyl, an unsubstituted, mono-, di- or tri-substituted aryl group chosen from phenyl and naphthyl, 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 or fluorenyl, wherein the aryl and heteroaromatic substituents are each independently:
hydroxy, aryl, mono- or di-(C1-C12)alkoxyaryl, mono- or di-(C1-C12)alkylaryl, 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- or di-(C1-C12)alkylamino, diarylamino, piperazino, N-(C1-C12)alkylpiperazino, N-arylpiperazino, aziridino, indolino, piperidino, morpholino, thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino, pyrrolidino, C1-C12 alkyl, C1-C12 haloalkyl, C1-C12 alkoxy, mono(C1-C12)alkoxy(C1-C12)alkyl, halogen or —C(═O)R22, wherein R22 is —OR23, —N(R24) R25, piperidino or morpholino, wherein R23 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) alkylor C1-C6 haloalkyl, and R24 and R25 are each independently C1-C6 alkyl, C5-C7 cycloalkyl or a substituted or an unsubstituted phenyl, wherein said phenyl substituents are each independently C1-C6 alkyl or C1-C6 alkoxy;
an unsubstituted or mono-substituted group chosen from pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolidino, phenothiazinyl, phenoxazinyl, phenazinyl and acridinyl, said wherein said substituents are each independently C1-C12 alkyl, C1-C12 alkoxy, phenyl or halogen;
a 4-substituted phenyl, the substituent being a dicarboxylic acid residue, a diamine residue, an amino alcohol residue, a polyol residue, —(CH2)—, —(CH2)e— or —[O—(CH2)e]f—, wherein e is an integer ranging from 2 to 6 and f is an integer ranging from 1 to 50, and wherein the substituent is connected to an aryl group of another photochromic material;
a group represented by:
wherein P is —CH2— or —O—; Q′″ is —O— or substituted nitrogen, the substituted nitrogen substituents being hydrogen, C1-C12 alkyl or C1-C12 acyl, provided that when Q′″ is substituted nitrogen, P is —CH2—; each R26 is independently C1-C12 alkyl, C1-C12 alkoxy, hydroxy or halogen;
R27 and R28 are each independently hydrogen or C1-C12 alkyl; and j is an integer ranging from 0 to 2;
R5, R8, R9 and R12 are each independently:
hydrogen, C1-C6 alkyl, chloro, fluoro, bromo, C3-C7 cycloalkyl or a unsubstituted, mono- or di-substituted phenyl, wherein said phenyl substituents are each independently C1-C6 alkyl or C1-C6 alkoxy;
—OR40 or —OC(═O)R40, wherein R40 is hydrogen, amine, alkylene glycol, polyalkylene glycol, 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 or an unsubstituted, mono- or di-substituted phenyl, wherein said phenyl substituents are each independently C1-C6 alkyl or C1-C6 alkoxy;
a 4-substituted phenyl, the substituent being a dicarboxylic acid residue, a diamine residue, an amino alcohol residue, a polyol residue, —(CH2)—, —(CH2)e— or —[O—(CH2)e]f—, wherein e is an integer ranging from 2 to 6, and f is an integer ranging from 1 to 50, and wherein the substituent is connected to another photochromic material;
—N(R41)R42, wherein R41 and R42 are each independently hydrogen, C1-C8 alkyl, phenyl, naphthyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, benzopyridyl, fluorenyl, C1-C8 alkylaryl, C3-C8 cycloalkyl, C4-C16 bicycloalkyl, C5-C20 tricycloalkyl or C1-C20 alkoxy(C1-C6)alkyl, or R41 and R42 come together with the nitrogen atom to form a C3-C20 hetero-bicycloalkyl ring or a C4-C20 hetero-tricycloalkyl ring;
a nitrogen containing ring represented by:
wherein each —V— is independently chosen for each occurrence from —CH2—, —CH(R43)—, —C(R43)2—, —CH(aryl)-, —C(aryl)2- and —C(R43)(aryl)-, wherein each R43 is independently C1-C6 alkyl and each aryl is independently phenyl or naphthyl; —W— is —V—, —O—, —S—, —S(O)—, —SO2—, —NH—, —N(R43)— or —N(aryl)-; s is an integer ranging from 1 to 3; and r is an integer ranging from 0 to 3, provided that if r is 0, then —W— is the same as —V; or a group represented by:
wherein each R44 is independently C1-C6 alkyl, C1-C6 alkoxy, fluoro or chloro; R45, R46 and R47 are each independently hydrogen, C1-C6 alkyl, phenyl or naphthyl, or R45 and R46 together form a ring of 5 to 8 carbon atoms, and p is an integer ranging from 0 to 3;
R6 and R7 are each independently a moderate to strong electron-donating group selected from:
(i) the group —OR8′, wherein R8′ is phenyl(C1-C3)alkyl, C1-C6 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, or R8′ is the group, —CH(R9′)Q″, wherein R9′ is hydrogen or C1-C3 alkyl and Q″ is —CN, —COOH, —COOCH3, or —COOCH2CH3;
(ii) —N(R15)R16, wherein R15 and R16 each independently comprises hydrogen, C1-C8 alkyl, phenyl, naphthyl, the heteroaromatic groups furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, benzopyridyl and fluorenyl, C1-C8 alkylaryl, C3-C20 cycloalkyl, C4-C20 bicycloalkyl, C5-C20 tricycloalkyl and C1-C20 alkoxyalkyl, wherein said aryl group is phenyl or naphthyl;
(iii) a nitrogen containing ring represented by the following graphic formula:
wherein Y is selected from the group consisting of —CH2—, —CH(R17)-, —C(R17)(R17)-, —CH(aryl)-, —C(aryl)2-, and —C(R17)(aryl)-, and X is selected from the group consisting of —Y—, —O—, —S—, —S(O)—, —S(O2)-, —NH—, —NR17- and —N-aryl, wherein R17 is C1-C6 alkyl, said aryl substituent is phenyl or naphthyl, m is the integer 1, 2 or 3, and p is the integer 0, 1, 2, or 3, provided that when p is 0, X is Y; or
(iv) a group represented by one of the following graphic formulae:
wherein R19, R20 and R21 are each hydrogen, C1-C5 alkyl, phenyl or naphthyl, or the groups R19 and R20 may come together to form a ring of 5 to 8 carbon atoms; and R18 is C1-C6 alkyl, C1-C6 alkoxy, fluoro or chloro;
R10 is any of the groups of R5, R8, R9 and R12 or a metallocenyl group;
R11 is an is an α-haloalkyl, α,α-dihaloalkyl, trihalomethyl group, a perhalo(C2-C10)alkyl group, a perhaloalkoxy group, or the group —O—C(O)—R, wherein R is a linear or branched group chosen from C1-C10 alkyl, C1-C10 haloalkyl , or C1-C10 perhaloalkyl;
R13 and R14 do not form a spirocyclic group and are each independently a (C1-C6)alkyl group, a (C1-C6)alkoxy group, a hydroxy(C1-C6)alkyl or the polyalkoxylated 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 —C(O)— or —CH2— and Z′ is hydroxy, epoxy or C1-C3 alkoxy and letters x, y and z are each an integer between 0 and 50 and the sum of x, y and z is an integer between 2 and 50.

### Claim 2 (depends on 1)

The photochromic material of claim 1, wherein each of R13 and R14 independently is a (C1to C6) alkyl group or a (C1to C6) alkoxy group.