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EP-4313996-B1 - INDENONAPHTHOPYRANS HAVING TRIALKYLSILYL AND ETHYLENICALLY UNSATURATED GROUPS

EP4313996B1EP 4313996 B1EP4313996 B1EP 4313996B1EP-4313996-B1

Inventors

  • XIAO, WENJING
  • KIM, BEON-KYU
  • WALTERS, ROBERT W.

Dates

Publication Date
20260506
Application Date
20210330

Claims (13)

  1. An indenonaphthopyran compound represented by the following Formula (I), wherein, m is from 0 to 3, n is from 0 to 3, p is 1 or 2, q is from 0 to 4, R 1 independently for each m, R 2 independently for each n, R 3 independently for each p, and R 4 independently for each q, in each case is independently, hydroxyl; cyano; (meth)acrylate or (meth)acrylamide; vinylphenyl; amino, or substituted nitrogen-containing heterocycle, or unsubstituted nitrogen-containing heterocycle; a halo group; a perhalo alkyl, or a perhalo aryl; substituted or unsubstituted alkyl; substituted or unsubstituted alkenyl; substituted or unsubstituted alkynyl; substituted or unsubstituted heterocycloalkyl; substituted or unsubstituted aryl; substituted or unsubstituted heteroaryl; substituted or unsubstituted alkoxy or substituted or unsubstituted aryloxy; substituted or unsubstituted alkylthio or substituted or unsubstituted arylthio; ketone, aldehyde, carboxylic acid ester, carboxylic acid, carboxylate, or amide; carbonate, carbamate, carbonyl amino, or urea; polyether, polyester, polycarbonate, or polyurethane; siloxy, alkoxysilane, or polysiloxane; trialkylsilyl; or combinations thereof; and R 5 and R 6 are each independently, substituted or unsubstituted alkyl; substituted or unsubstituted aryl; polyether, polyester, polycarbonate, or polyurethane; trialkylsilyl; or R 5 and R 6 together form a spirocyclic ring, wherein each nitrogen-containing heterocycle substituent, each alkyl substituent, each alkenyl substituent, each alkynyl substituent, each heterocycloalkyl substituent, each aryl substituent, each heteroaryl substituent, each alkoxy substituent, each aryloxy substituent, each alkylthio substituent, and each arylthio substituent, are in each case independently selected from, halo, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, perhaloalkyl, heterocycloalkyl, aryl, heteroaryl, hydroxyl, thiol, alkyl ether, alkyl thioether, aryl ether, aryl thioether, ketone, aldehyde, carboxylic acid ester, carboxylic acid, carboxylate, siloxane, alkoxysilane, polysiloxane, amide, amino, nitrogen-containing heterocycle, alkyl amine, aryl amine, carbamate, carbonate, urea, polyester group, polyether group, polycarbonate group, polyurethane group, trialkylsilyl, an acrylate group, a methacrylate group, an acrylamide group, a methacrylamide group, a vinylphenyl group, combinations thereof, or two or more thereof, provided that said indenonaphthopyran compound comprises, (i) at least one trialkylsilyl group, and (ii) at least one ethylenically unsaturated radically polymerizable group selected from vinylphenyl, acrylate, methacrylate, acrylamide, or methacrylamide.
  2. The indenonaphthopyran compound of claim 1 wherein, R 1 independently for each m, R 2 independently for each n, R 3 independently for each p, and R 4 independently for each q, in each case is independently, hydroxyl; cyano; (meth)acrylate or (meth)acrylamide; vinylphenyl; amino, or substituted nitrogen-containing heterocycle, or unsubstituted nitrogen-containing heterocycle; a halo group; a perhalo alkyl, or perhalo phenyl; substituted or unsubstituted alkyl; substituted or unsubstituted phenyl; substituted or unsubstituted alkoxy; ketone, aldehyde, carboxylic acid ester, carboxylic acid, carboxylate, or amide; carbonate, carbamate, carbonyl amino, or urea; polyether; siloxy, or alkoxysilane; trialkylsilyl; or combinations thereof; and R 5 and R 6 are each independently, substituted or unsubstituted alkyl, or trialkylsilyl; wherein each nitrogen-containing heterocycle substituent, each alkyl substituent, each phenyl substituent, and each alkoxy substituent, are in each case independently selected from, halo, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, perhaloalkyl, heterocycloalkyl, phenyl, heteroaryl, hydroxyl, thiol, alkyl ether, alkyl thioether, phenyl ether, phenyl thioether, ketone, aldehyde, carboxylic acid ester, carboxylic acid, carboxylate, siloxane, alkoxysilane, amide, amino, nitrogen-containing heterocycle, alkyl amine, phenyl amine, carbamate, carbonate, urea, polyether group, trialkylsilyl, an acrylate group, a methacrylate group, an acrylamide group, a methacrylamide group, a vinylphenyl group, combinations thereof, or two or more thereof, provided that said indenonaphthopyran compound comprises, (i) at least one trialkylsilyl group, and (ii) at least one ethylenically unsaturated radically polymerizable group selected from vinylphenyl, acrylate, methacrylate, acrylamide, or methacrylamide.
  3. The indenonaphthopyran compound of claim 1 wherein: m is at least one, and one R 1 is trialkylsilyl; and p is 2.
  4. The indenonaphthopyran compound of claim 1 wherein, R 3 independently for each p is selected from, alkoxy, amino, unsubstituted nitrogen-containing heterocycle, or substituted nitrogen-containing heterocycle, wherein each substituent of the substituted nitrogen-containing heterocycle independently comprises acrylate, methacrylate, acrylamide, or methacrylamide.
  5. The indenonaphthopyran compound of claim 4 wherein, p is 2, R 3 at postion-6 is alkoxy; and R 3 at position-7 is selected from, amino, unsubstituted nitrogen-containing heterocycle, or substituted nitrogen-containing heterocycle, wherein each substituent of the substituted nitrogen-containing heterocycle independently comprises acrylate, methacrylate, acrylamide, or methacrylamide.
  6. The indenonaphthopyran compound of claim 1 wherein one of: m is at least 1, and one R 1 is selected from trialkylsilyl group; or q is at least 1, and R 4 at position-11 is selected from trialkylsilyl group, or trialkylsilyl mono-substituted phenyl group.
  7. The indenonaphthopyran compound of claim 1 wherein one of: (A) m is at least 1, and one R 1 is represented by one of the following Formula (V) or Formula (VI), wherein for Formula (V), R 15 is hydrogen or methyl, X 1 is O or NH, u is 0 to 4, R 16 independently for each u is alkyl or cycloalkyl, and L 1 is divalent alkyl, or a divalent group represented by the following Formula (Va), wherein for Formula (Va), R a and R b are each independently selected from divalent alkyl, or wherein for Formula (VI), R 15 is hydrogen or methyl, y is 1 to 20, and R 17 independently for each y is divalent alkyl; or (B) p is at least 1, and R 3 at position-7 is represented by the following Formula (VII), wherein for Formula (VII), R 18 is hydrogen or methyl, X 2 is O or NH, L 2 is a single bond or divalent alkyl, u is 0 to 4, and R 19 independently for each u is alkyl or cycloalkyl.
  8. The indenonaphthopyran compound of claim 1 wherein: p is 2, R 3 at position-6 is alkoxy, and R 3 at position-7 is unsubstituted nitrogen-containing heterocycle; q is at least one, and R 4 at position-11 is trialkylsilyl or trialkylsilyl mono-substituted phenyl; and m is at least one, and one R 1 is represented by one of the following Formula (V) or Formula (VI), wherein for Formula (V), R 15 is hydrogen or methyl, X 1 is O or NH, u is 0 to 4, R 16 independently for each u is alkyl or cycloalkyl, and L 1 is divalent alkyl, or a divalent group represented by the following Formula (Va), wherein for Formula (Va), R a and R b are each independently selected from divalent alkyl, or wherein for Formula (VI), R 15 is hydrogen or methyl, y is 1 to 20, and R 17 independently for each y is divalent alkyl.
  9. The indenonaphthopyran compound of any one of claims 1 to 8, wherein each trialkylsilyl group is a trimethylsilyl group.
  10. A photochromic composition comprising the indenonaphthopyran compound of claim 1.
  11. The photochromic composition of claim 10, wherein said photochromic composition is a polymerizable photochromic composition further comprising (meth)acrylate functional polydimethylsiloxane.
  12. A photochromic article comprising the indenonaphthopyran compound of 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.
  13. The photochromic article of claim 12, wherein the ophthalmic articles are selected from corrective lenses, non-corrective lenses, contact lenses, intra-ocular lenses, magnifying lenses, protective lenses, and visors.

Description

FIELD The present invention relates to indenonaphthopyran compounds having at least one trialkylsilyl group and at least one ethylenically unsaturated radically polymerizable group, and to photochromic compositions and photochromic articles including such indenonaphthopyran compounds. BACKGROUND In response to certain wavelengths of electromagnetic radiation (or "actinic radiation"), photochromic compounds, such as indenonaphthopyrans (or indeno-fused naphthopyrans), typically undergo a transformation from one form or state to another form, with each form having a characteristic or distinguishable absorption spectrum associated therewith. Typically, upon exposure to actinic radiation, many photochromic compounds are transformed from a closed-form, which corresponds to an unactivated (or bleached, e.g., substantially colorless) state of the photochromic compound, to an open-form, which corresponds to an activated (or colored) state of the photochromic compound. In the absence of exposure to actinic radiation, such photochromic compounds are reversibly transformed from the activated (or colored) state, back to the unactivated (or bleached) state. Compositions and articles, such as eyewear lenses, that contain photochromic compounds or have photochromic compounds applied thereto (e.g., in form of a photochromic coating composition) typically display colorless (e.g., clear) and colored states that correspond to the colorless and colored states of the photochromic compounds contained therein or applied thereto. Photochromic compounds can be incorporated into a polymeric matrix, which can result in the formation of a photochromic article, such as a photochromic ophthalmic lens. It is generally desirable that the photochromic compound have good compatibility with the polymeric matrix into which it is incorporated, which can result in, for example, efficient transitions between open and closed forms of the photochromic compound, and correspondingly improved photochromic performance. With some applications, it is also desirable that the photochromic compound undergoes minimal to no migration out of the polymeric matrix into which it is incorporated, such as from a layer or portion containing the photochromic compound into an adjacent layer or portion that is free of the photochromic compound. It would be desirable to develop new indenonaphthopyran compounds that are photochromic, have good compatibility with the polymeric matrices into which they are incorporated, and which undergo minimal to no migration within and/or out of a polymeric matrix into which they are incorporated. Additionally, it would be desirable that such newly developed indenonaphthopyran compounds possess photochromic properties, such as but not limited to fade rate and/or optical density properties, that are at least the same as those of conventional indenonaphthopyran compounds. EP 2 725 017 A1 discloses compounds used in chromic compositions. SUMMARY In accordance with the present invention, there is provided an indenonaphthopyran compound represented by the following Formula (I), With reference to Formula (I): m is from 0 to 3; n is from 0 to 3; p is 1 or 2; and q is from 0 to 4. With further reference to Formula (I), R1 independently for each m, R2 independently for each n, R3 independently for each p, and R4 independently for each q, in each case is independently, hydroxyl;cyano;(meth)acrylate or (meth)acrylamide;vinylphenyl;amino, or substituted nitrogen-containing heterocycle, or unsubstituted nitrogen-containing heterocycle;a halo group;a perhalo alkyl, or a perhalo aryl,substituted or unsubstituted alkyl;substituted or unsubstituted alkenyl;substituted or unsubstituted alkynyl;substituted or unsubstituted heterocycloalkyl;substituted or unsubstituted aryl;substituted or unsubstituted heteroaryl;substituted or unsubstituted alkoxy or substituted or unsubstituted aryloxy;substituted or unsubstituted alkylthio or substituted or unsubstituted arylthio;ketone, aldehyde, carboxylic acid ester, carboxylic acid, carboxylate, or amide;carbonate, carbamate, carbonyl amino, or urea;polyether, polyester, polycarbonate, or polyurethane;siloxy, alkoxysilane, or polysiloxane;trialkylsilyl; orcombinations thereof; andR5 and R6 are each independently, substituted or unsubstituted alkyl;substituted or unsubstituted aryl;polyether, polyester, polycarbonate, or polyurethane;trialkylsilyl; orR5 and R6 together form a spirocyclic ring. With additional reference to Formula (I), each nitrogen-containing heterocycle substituent, each alkyl substituent, each alkenyl substituent, each alkynyl substituent, each heterocycloalkyl substituent, each aryl substituent, each heteroaryl substituent, each alkoxy substituent, each aryloxy substituent, each alkylthio substituent, and each arylthio substituent are in each case independently selected from, halo, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, perhaloalkyl, heterocycloalkyl, aryl, heteroaryl, hydroxyl, thiol,