CROSS-REFERENCE TO RELATED APPLICATION

This application is the United States national phase of International Application No. PCT/EP2017/061138 filed May 10, 2017, the disclosure of which is hereby incorporated by reference in its entirety.

FIELD

The present invention relates to photochromic indeno fused phenanthrenopyran compounds, photochromic compositions that include such compounds, and photochromic articles, such as ophthalmic articles, that include such compounds.

BACKGROUND

Photochromic compounds and materials, in response to certain wavelengths of electromagnetic radiation (or “actinic radiation”), 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 materials are transformed from a closed-form, which corresponds to an unactivated (or bleached, or substantially colorless) state of the photochromic material, to an open-form, which corresponds to an activated (or colored) state of the photochromic material. In the absence of exposure to actinic radiation, such photochromic materials 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 materials or have photochromic materials applied thereto (such as in form of a photochromic coating composition) typically display colorless (or clear) and colored states that correspond to the colorless and colored states of the photochromic materials contained therein and/or applied thereto. Photochromic compounds can provide a combination of both photochromic and dichroic properties when exposed to actinic radiation and properly aligned together, such as when including one or more lengthening groups covalently bonded thereto. Dichroic properties relate to the ability of the photochromic-dichroic compounds to linearly polarize incident unpolarized light. Photochromic compounds and materials are typically characterized with regard to various properties, such as photochromic properties, which include, but are not limited to: fade rate; change in optical density (sometimes designated as ΔOD); and dichroic properties (such as in the case of photochromic-dichroic compounds), which can be quantified with regard to absorption ratio (AR) values.

It would be desirable to develop new photochromic compounds. It would be further desirable that such newly developed photochromic compounds possess properties, such as photochromic properties and optionally dichroic properties, that are at least the same as or better than those of existing photochromic compounds.

SUMMARY

In accordance with the present invention, there is provided a photochromic compound represented by the following Formula (I),



With reference to Formula (I), R2is selected from the group consisting of, hydrogen; halogen; linear or branched C1-C20alkyl; linear or branched C1-C20perhaloalkyl; —ORa; —SRa, where each Rais independently selected from the group consisting of hydrogen, linear or branched C1-C20alkyl, and linear or branched C1-C20perhaloalkyl; —C(O)ORb, where Rbis hydrogen or linear or branched C1-C10alkyl; substituted or unsubstituted aryl, each aryl substituent being independently selected from the group consisting of hydroxyl, halogen, carbonyl, linear or branched C1-C20alkoxycarbonyl, cyano, linear or branched C1-C20haloalkyl, linear or branched C1-C20alkyl, linear or branched C1-C20alkoxy, and linear or branched C1-C20perhaloalkyl; and a group Y1(as described further herein).

With additional reference to Formula (I), R6and R7are each independently selected from the group consisting of, hydrogen; halogen; a lengthening group L1(as described in further detail herein); —ORc, and —SRc, where each Rcis independently selected from the group consisting of hydrogen, a lengthening group L2(as described in further detail herein), linear or branched C1-C20alkyl, —C(O)—Rd, and —S(O)(O)—Re, where Rdand Reare each independently selected from the group consisting of linear or branched C1-C10alkyl, linear or branched C1-C10perhaloalkyl, phenyl, linear or branched C1-C10alkyl substituted phenyl, and linear or branched C1-C10perhaloalkyl substituted phenyl. With regard to R6and R7of Formula (I), there is the proviso that at least one of R6and R7is other than hydrogen.

With reference to Formula (I), n is 1 to 3, and m is 1 to 4. With further reference to Formula (I), R1independently for each n, and R3independently for each m are each independently selected from the group consisting of: (1) hydrogen; (2) cyano; (3) a reactive substituent; (4) a lengthening group L3(as described in further detail herein); (5) halogen selected from the group consisting of fluoro, chloro, and bromo; (6) linear or branched C1-C20alkyl; (7) linear or branched C1-C20perhaloalkyl; (8) C3-C10cycloalkyl; (9) a group Y2(as described in further detail herein); (10) substituted or unsubstituted phenyl, the phenyl substituents being selected from the group consisting of at least one of hydroxyl, halogen, carbonyl, linear or branched C1-C20alkoxycarbonyl, cyano, linear or branched C1-C20haloalkyl, linear or branched C1-C20alkyl, linear or branched C1-C20alkoxy, linear or branched C1-C20perhaloalkyl, and combinations thereof; (11) —O—R10′, —S—R10′, —C(O)—R10′, —C(O)—OR10′, —OC(O)—R10′, —OC(O)O—R10′, —C(O)N(R10′)R10′, —N(R10′)C(O)N(R10′)(R10′), or —Si(OR10′)w(R10′)t, wherein each R10′ independently is hydrogen, linear or branched C1-C20alkyl, phenyl(C1-C20)alkyl, mono(C1-C20)alkyl substituted phenyl(C1-C20)alkyl, mono(C1-C20)alkoxy substituted phenyl(C1-C20)alkyl, (C1-C20)alkoxy(C2-C20)alkyl, C3-C10cycloalkyl, or mono(C1-C20)alkyl substituted C3-C10cycloalkyl, and w and t are each independently 0 to 3, provided that w+t is 3; and (12) —N(R11′)R12′, wherein R11′ and R12′ are each independently hydrogen, linear or branched C1-C20alkyl, phenyl, naphthyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, benzopyridyl, fluorenyl, linear or branched C1-C20alkylaryl, C3-C10cycloalkyl, C4-C20bicycloalkyl, C5-C20tricycloalkyl or linear or branched C1-C20alkoxyalkyl, wherein the aryl group is phenyl or naphthyl, or R11′ and R12′ come together with the nitrogen atom to form a ring, such as a C3-C20hetero-bicycloalkyl ring or a C4-C20hetero-tricycloalkyl ring.

With reference to Formula (I), R4and R5are each independently selected from the group consisting of: (i) hydrogen, hydroxyl, linear or branched C1-C20alkyl, linear or branched C1-C20haloalkyl, C3-C10cycloalkyl, allyl, benzyl, or substituted benzyl, the benzyl substituents being chosen from halogen, linear or branched C1-C20alkyl or linear or branched C1-C20alkoxy; (ii) an unsubstituted, mono- di- or tri-substituted group chosen from phenyl, naphthyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl, benzofuranyl, thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, or indolyl, the group substituents in each case being independently chosen from halogen, linear or branched C1-C20alkyl or linear or branched C1-C20alkoxy; and (iii) a group Y3; or (iv) R4and R5together form a spiro substituent selected from the group consisting of a substituted or unsubstituted spiro-carbocyclic ring containing 3 to 10 carbon atoms, a substituted or unsubstituted spiro-heterocyclic ring containing 1 or 2 oxygen atoms and 3 to 10 carbon atoms including the spirocarbon atom, the spiro-carbocyclic ring and spiro-heterocyclic ring being annellated with 0, 1 or 2 benzene rings, the substituents being hydrogen or linear or branched C1-C20alkyl.

With additional reference to Formula (I), B and B′ are each independently selected from the group consisting of unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, alkenyl, and alkynyl, or B and B′ taken together form a ring structure.

With reference to Formula (I) and the various groups thereof, each lengthening group L1, L2, and L3is independently represented by the following Formula (II):
—[S1]c-[Q1-[S2]3]d′-[Q2-[S3]e]e′-[Q3-[S4]f]f′—S5—P  Formula (II)

With reference to Formula (II), (a) Q1, Q2, and Q3for each occurrence, are independently a divalent group selected from the group consisting of unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, unsubstituted cycloalkyl, substituted cycloalkyl, unsubstituted heterocycloalky, and substituted heterocycloalkyl. The aryl substituents, heteroaryl substituents, cycloalkyl substituents, and heterocycloalkyl substituents, of Q1, Q2, and Q3, are each independently selected from the group consisting of P (as described in further detail herein), liquid crystal mesogens, halogen, poly(C1-C18alkoxy), C1-C18alkoxycarbonyl, C1-C18alkylcarbonyl, C1-C18alkoxycarbonyloxy, 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-C18alkylthio, C1-C18acetyl, C3-C10cycloalkyl, C3-C10cycloalkoxy, straight-chain C1-C18alkyl, and branched C1-C18alkyl. The straight-chain C1-C18alkyl and branched C1-C18alkyl (of the aryl substituents, heteroaryl substituents, cycloalkyl substituents, and heterocycloalkyl substituents, of Q1, Q2, and Q3,) are each independently mono-substituted with a group selected from the group consisting of cyano, halogen, and C1-C18alkoxy. Alternatively, the straight-chain C1-C18alkyl and branched C1-C18alkyl (of the aryl substituents, heteroaryl substituents, cycloalkyl substituents, and heterocycloalkyl substituents, of Q1, Q2, and Q3,) are each independently poly-substituted with at least two groups independently selected from the group consisting of 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.

With further reference to Formula (II), (b) subscripts c, d, e, and f are each independently chosen from an integer of 1 to 20; and each S1, S2, S3, S4, and S5is independently chosen for each occurrence from a spacer unit selected from the group consisting of: (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 the substitutes for the alkylene and haloalkylene are independently selected from the group consisting of C1-C18alkyl, C3-C10cycloalkyl and aryl; (ii) —N(Z)—, —C(Z)═C(Z)—, —C(Z)═N—, —C(Z′)2—C(Z)2—, —N(Z)—C(Z)2—, and a single bond, wherein Z for each occurrence is independently selected from the group consisting of hydrogen, C1-C18alkyl, C3-C10cycloalkyl and aryl, and Z′ for each occurrence is independently selected from the group consisting of C1-C18alkyl, C3-C10cycloalkyl 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-C24alkylene residue, the C1-C24alkylene residue being unsubstituted, mono-substituted by cyano or halogen, or poly-substituted by halogen. With regard to each of S1, S2, S3, S4, and S5, there is the proviso 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 S5and P is free of two heteroatoms linked to each other.

With additional reference to Formula (II), (c) P for each occurrence is independently selected from the group consisting of hydroxy, amino, C2-C18alkenyl, C2-C18alkynyl, 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-C18alkyl aminocarbonyl, aminocarbonyl(C1-C18)alkyl, C1-C18alkyloxycarbonyloxy, halocarbonyl, hydrogen, aryl, hydroxy(C1-C18)alkyl, C1-C18alkyl, C1-C18alkoxy, amino(C1-C18)alkyl, C1-C18alkylamino, di-(C1-C18)alkylamino, C1-C18alkyl(C1-C18)alkoxy, C1-C18alkoxy(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, maleimide 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-C18alkyl, C1-C18alkoxy, amino, C3-C10cycloalkyl, C1-C18alkyl(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.

With further additional reference to Formula (II), subscripts 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.

With reference to Formula (I) and the various groups thereof, each group Y1, Y2, and Y3independently comprises at least one residue of a ring-opened cyclic monomer, wherein each ring-opened cyclic monomer is independently selected from the group consisting of a ring-opened cyclic ester monomer and a ring-opened cyclic carbonate monomer.

The features that characterize the present invention are pointed out with particularity in the claims, which are annexed to and form a part of this disclosure. These and other features of the invention, its operating advantages and the specific objects obtained by its use will be more fully understood from the following detailed description in which non-limiting embodiments of the invention are illustrated and described.

