# US 11,897,894 B2 · Indolenaphthopyrans

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- Number: US 11,897,894 B2
- Document ID: US11897894B2
- Status: Granted
- Kind: B2
- Application number: 17/416,006
- Filed: 2018-12-21
- Published: 2021-10-14
- Granted: 2024-02-13
- Earliest claimed: 2018-12-21
- Assignees: Transitions Optical, Inc.
- Applicants: Transitions Optical, Ltd.
- Inventors: Ryan Stayshich; Zachary Smith; Robert W. Walters
- Web page: https://patentgrep.com/patent/US11897894B2

## CPC

- C07D 491/052: the oxygen-containing ring being six-membered
- C08K 5/0041: {Optical brightening agents, organic pigments}
- C09B 57/00: Other synthetic dyes of known constitution
- C09K 9/02: Organic tenebrescent materials
- G02B 1/041: {Lenses}
- G02B 1/043: {Contact lenses}
- C08K 5/3417: condensed with carbocyclic rings
- C09K 2211/1033: with oxygen
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- 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

## Abstract

Provided is a photochromic indolenapthtopyran having the core skeletal structure of Formula (I): wherein R1 and R2 are each independently substituted or unsubstituted alkyloxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted ether, substituted or unsubstituted thioether, amino, a nitrogen-containing heterocycle, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, —NHC(O)Ra, or —OC(O)Ra, wherein Ra is substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkylthio, or substituted or unsubstituted arylthio; R4 is selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heterocycloalkyl, allyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; and B and B′ are each independently substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, wherein each substituted aryl or substituted heteroaryl is substituted with a group having a Hammett σp value of greater than −0.50.

## Claims

### Claim 1

A photochromic indolenaphthopyran comprising the core skeletal structure represented by Formula (I):
wherein,
R1 and R2 are each independently substituted or unsubstituted alkyloxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted ether, substituted or unsubstituted thioether, amino, a nitrogen containing heterocycle, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, —NHC(O)Ra, or —OC(O)Ra,
wherein Ra is substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkylthio, or substituted or unsubstituted arylthio;
R4 is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heterocycloalkyl, allyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl; and
B and B′ are each independently substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, wherein each substituted aryl or substituted heteroaryl is substituted with a group having a Hammett σp value of greater than −0.50.

### Claim 2 (depends on 1)

The indolenaphthopyran according to claim 1, wherein,
R1 is substituted or unsubstituted alkoxy, and
R2 is substituted or unsubstituted alkyloxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted ether, substituted or unsubstituted thioether, amino, or a nitrogen-containing heterocycle.

### Claim 3 (depends on 1)

The indolenaphthopyran according to claim 1, wherein B and B′ are each independently substituted aryl or substituted heteroaryl with a group having a Hammett σp value of −0.5 to 0.8.

### Claim 4 (depends on 1)

The indolenaphthopyran according to claim 1, wherein B and B′ are each independently substituted or unsubstituted phenyl.

### Claim 5 (depends on 4)

The indolenaphthopyran according to claim 4, wherein each phenyl substituent is in each case independently alkoxy, halo, alkyl, or aryloxy.

### Claim 6 (depends on 1)

The indolenaphthopyran according to claim 1, wherein R1 and R2 form a cyclic structure.

### Claim 7 (depends on 1)

The indolenaphthopyran according to claim 1, wherein R4 is substituted or unsubstituted phenyl or substituted or unsubstituted alkyl.

### Claim 8 (depends on 1)

The indolenaphthopyran of according to claim 1, having the core skeletal structure represented by Formula (Ia):
wherein,
m is 0 to 4; and
R3 independently for each m is
i. hydroxyl;
ii. cyano;
iii. (meth)acrylate;
iv. amino or nitrogen-containing heterocycle;
v. a mesogen-containing group L1;
vi. substituted or unsubstituted alkyl;
vii. substituted or unsubstituted alkenyl;
viii. substituted or unsubstituted alkynyl;
ix. a halo group;
x. a perhalo group;
xi. boronic ester or boronic acid;
xii. polyether, polyester, polycarbonate, or polyurethane;
xiii. substituted or unsubstituted aryl;
xiv. substituted or unsubstituted heterocycloalkyl;
xv. substituted or unsubstituted heteroaryl;
xvi. substituted or unsubstituted alkoxy or substituted or unsubstituted aryloxy;
xvii. substituted or unsubstituted alkylthio or substituted or unsubstituted arylthio;
xviii. ketone, aldehyde, ester, carboxylic acid, carboxylate, or amide;
xix. carbonate, carbamate, or urea; or
xx. siloxane, alkoxysilane, or polysiloxane.

### Claim 9 (depends on 8)

The indolenaphthopyran according to claim 8, wherein R3 is at the 11-position.

### Claim 10 (depends on 8)

The indolenaphthopyran according to claim 8, wherein R3 is at the 10-position and is a mesogen-containing group L1.

### Claim 11 (depends on 8)

The indolenaphthopyran of according to claim 8, wherein R3 is cyano; a halo group; haloalkyl; perhaloalkyl; substituted or unsubstituted aryl; or substituted or unsubstituted heteroaryl.

### Claim 12 (depends on 8)

The indolenaphthopyran of according to claim 8, wherein each the mesogen-containing group L1, at one or more of positions 9, 10, 11, or 12, is independently represented by the following Formula (II),
—[S1]c—[Q1—[S2]d]d′—[Q2—[S3]e]e′—[Q3—[S4]f]f′—R Formula (II)
wherein,
(a) Q1, Q2, and Q3 for each occurrence, are independently a divalent group selected from the group consisting of unsubstituted aryl, substituted aryl, unsubstituted cycloalkyl, and substituted cycloalkyl;
wherein the aryl substituents and cycloalkyl substituents are each independently selected from the group consisting of liquid crystal mesogens, halogen, alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkoxycarbonyl, alkylcarbonyl, alkoxycarbonyloxy, aryloxycarbonyloxy, perfluoroalkyl, and perfluoroalkoxy;
(b) c, d, e, and f are each independently an integer of 0 to 3; and each S1, S2, S3 and S4 is independently chosen for each occurrence from a spacer unit selected from the group consisting of:
(i) —C(Z)2—, —N(Z)—, —C(Z)═C(Z)—, —C(Z)═N—, wherein Z for each occurrence is independently selected from the group consisting of hydrogen, alkyl, and aryl;
(ii) Si(CH3)2—, —Si(CH3)2O—; and
(iii) —O—, —C(═O)—, —C≡C—, —N═N—, —S—, —S(═O)—, —(O═)S(═O)—, —(O═)S(═O)O—, —O(O═)S(═O)O—
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;
(c) R is alkyl; and
(d) d′, e′ and f′ are each independently 0, 1, 2, 3, and 4, provided that the sum of d′+e′+f′ is at least 1.

### Claim 13 (depends on 1)

The indolenaphthopyran of according to claim 1, having a bimodal absorption profile having an A band to B band absorption ratio ranging from 3.0 to 7.0:1.

### Claim 14 (depends on 1)

A photochromic composition comprising the indolenaphthopyran according to claim 1.

### Claim 15 (depends on 1)

A photochromic article comprising the indolenaphthopyran according to claim 1, wherein the photochromic article is selected from the group consisting of ophthalmic articles, display articles, windows, mirrors, active liquid crystal cell articles, and passive liquid crystal cell articles; or
wherein the photochromic article is an ophthalmic article selected from the group consisting of corrective lenses, non-corrective lenses, contact lenses, intra-ocular lenses, magnifying lenses, protective lenses, and visors; or
wherein the photochromic article is a display article selected from the group consisting of screens, monitors, and security elements.