Photochromic indeno-fused naphthopyran compounds, compositions, and articles containing same

Abstract

Indeno-fused naphthopyrans having the core structure (I): TIFF2025531714000032.tif54131In formula (I), R 1 is a substituted or unsubstituted alkyl group; R 2 is substituted or unsubstituted amino, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, or substituted or unsubstituted amide, urea, and carbamate; R 3 and R 4 At least one of R is an electron donating group, 3 and R 4 Hammett σ p The sum of the values ​​is less than -0.40; when R1 is a substituted alkyl group, the carbon atom of the alkyl group is directly bonded to the carbon atom at position 7, and the carbon atom of the alkyl group directly bonded to the carbon atom at position 7 is unsubstituted.

Description

[Technical Field]

[0001] FIELD OF THE INVENTION The present invention relates to fused ring photochromic compounds, such as photochromic indeno-fused naphthopyran compounds, and to photochromic compositions and articles containing such photochromic compounds. [Background technology]

[0002] Photochromic compounds are transformed from one state (or form) to another in response to electromagnetic radiation of a specific wavelength (i.e., "actinic radiation"). Each state has a characteristic absorption spectrum. For example, many photochromic compounds are transformed from an inactivated (e.g., bleached or substantially colorless) state to an activated (e.g., colored or pigmented) state upon exposure to actinic radiation. When the actinic radiation is removed, the photochromic compound reversibly returns from the activated state to the bleached, inactivated state. A "thermoreversible photochromic compound" is a photochromic compound that is transformed from an inactive state to an activated state in response to actinic radiation and returns to the inactivated state in response to thermal energy. The activation reaction (from inactive to active) is primarily photochemical, while the deactivation reaction (from active to inactive) is primarily thermal.

[0003] Known photochromic compounds, such as photochromic indeno-fused naphthopyran compounds, exhibit the advantages of not only good darkness in the activated state, but also acceptable fade rates upon transition to the bleached, inactivated state. However, in some cases, these photochromic compounds may exhibit an undesirable tint or color in the bleached, inactivated state, commonly referred to as "bleach color." This bleaching can adversely affect the aesthetics of articles, such as optical articles, that contain such photochromic compounds.

[0004] Photochromic ophthalmic lenses, when exposed to sunlight (actinic radiation), induce rapid tinting of the lens, reducing the amount of light reaching the wearer's eyes and reducing glare for the lens wearer. Upon returning to indoor environments, any remaining lens color or tint on the lens can be harmful to the wearer from both aesthetic and functional standpoints. Therefore, it is desirable to provide a photochromic lens that is clear when the lens wearer is indoors and functions as a tinted / tinted pair of sunglasses when the wearer is outdoors. This can be achieved by using a photochromic dye that provides high absorption in the activated state and rapidly switches from a clear (deactivated, indoor) state to a tinted (dark, outdoor) state and vice versa. To achieve the highest quality photochromic lenses, photochromic dyes that exhibit minimal residual color or tint when the wearer is indoors (i.e., the deactivated state) are required.

[0005] Additionally, combinations of photochromic compounds with different activation colors are often used to produce photochromic lenses that become neutral gray or brown upon activation. For example, a mixture of photochromic compounds with blue and orange activation states can be combined to produce a neutral gray color. It is desirable to have the activation and fade rates of these different compounds as similar as possible to maintain color uniformity both during activation and fade. For these reasons, a compound that is blue in its activated state should have high absorption in the activated state, a fast fade rate, and minimal color in the unactivated (clear) state.

[0006] For example, the compounds described in U.S. Patent No. 9,028,728 can exhibit a desirable level of blue coloration in the activated state, but can suffer from residual coloration in the bleached state. This residual coloration is caused by the closed form of the photochromic dye absorbing light in the high-energy visible region of the solar spectrum, resulting in a yellowness index (b *Residual coloration can also be the result of thermochromism in dyes, whereby low levels of photochromic dyes remain in an activated state indoors and do not fully revert to a deactivated state. This is often measured as a decrease in the transmittance of the deactivated state of the sample.

[0007] Furthermore, known photochromic indeno-fused naphthopyran compounds that lack a substituent at the 7-position and have a strong electron donating group on the 3,3'-aryl group can provide good bleaching, but can suffer from a poorly darkened activated state. The poor outdoor activated darkening of such compounds can be a limitation for photochromic lenses containing such compounds, especially at warm temperatures.

[0008] ΔE %T is the transparent substrate (%T) on which the photochromic layer is applied according to the following formula 1: o , a * 0, b * 0), the transmittance (%T) of the unactivated photochromic layer * value, and b * Represents a value. ΔE %T =[(%T-%T o ) 2 +(a * -a * o ) 2 +(b * -b * o ) 2 ] 0.5 formula 1 ΔE %T The lower the value, the less pigmented and colored the sample is (in this case, unactivated). Activated %T at 35°C indicates how dark a photochromic sample will become when exposed to actinic radiation in warm, summer-like conditions.

[0009] The present inventors have surprisingly found that indeno-fused naphthopyran compounds bearing an alkyl substituent at the 7-position exhibit a significantly reduced ΔE when combined with an electron-donating group on the 3,3'-aryl group compared to structurally similar compounds bearing an alkoxy group at the 7-position. %T It has also been found that the indeno-fused compounds of the present invention improve the dark color of the activated state over structurally similar compounds that do not have a substituent at the 7-position. Summary of the Invention [Means for solving the problem]

[0010] The present invention relates to indeno-fused naphthopyrans having the following core skeletal structure (I): [ka] (In the formula, R 1 is a substituted or unsubstituted alkyl group; R 2 teeth, i. substituted or unsubstituted amino, ii. substituted or unsubstituted alkyl; iii. substituted or unsubstituted alkenyl, iv. substituted or unsubstituted alkynyl, v. substituted or unsubstituted aryl, vi. Substituted or unsubstituted heteroaryl, vii. Substituted or unsubstituted alkoxy, viii. Substituted or unsubstituted aryloxy, ix. Substituted or unsubstituted alkylthio, x. substituted or unsubstituted arylthio, xi. Substituted or unsubstituted amides, xii. Substituted or unsubstituted urea, or xiii. Substituted or unsubstituted carbamates; R 3 and R 4 At least one of R is an electron donating group, 3 and R4 Hammett σ p The sum of the values ​​is less than -0.40; R 1 is a substituted alkyl group, the carbon atom of the alkyl group is directly bonded to the carbon atom at position 7, and the carbon atom of the alkyl group bonded to the carbon atom at position 7 is unsubstituted).

[0011] Compositions and articles comprising the indeno-fused naphthopyrans are also provided.

[0012] The features that characterize the 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, the advantages of its operation, and specific objects attained by its uses will be more fully understood from the following detailed description, wherein non-limiting embodiments of the invention are shown and described. [Brief explanation of the drawings]

[0013] [Figure 1] 1 shows a basic scheme, synthesis part 1, of an exemplary method for synthesizing intermediates used to prepare photochromic compounds of the present invention.

[0014] [Figure 2] 1 shows a basic scheme of an exemplary method for preparing photochromic compounds of the present invention, synthesis part 2. DETAILED DESCRIPTION OF THE INVENTION

[0015] As used herein, the articles "a," "an," and "the" include plural referents unless expressly and unambiguously limited to one referent.

[0016] As used herein, the term "includes" is synonymous with "comprises."

[0017] Unless otherwise indicated, all ranges or ratios disclosed herein should be understood to encompass every subrange or subratio subsumed therein. For example, a specified range or ratio of "1 to 10" should be considered to include every subrange between (and including) a minimum value of 1 and a maximum value of 10, i.e., all subranges or subratios beginning with a minimum value of 1 or greater and ending with a maximum value of 10 or less, such as, but not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.

[0018] As used herein, unless otherwise indicated, left-to-right representations of linking groups, such as divalent linking groups, include other suitable orientations, such as, but not limited to, right-to-left orientations. [ka] or equivalently, the left-to-right representation of -C(O)O- is equivalent to its right-to-left representation, i.e. [ka] or the equivalents -O(O)C- or -OC(O)-.

[0019] Except in the examples or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and the like used in the specification and claims are to be understood as being modified in all instances by the term "about." "About" contemplates plus or minus 25 percent of the stated value, such as plus or minus 10 percent of the stated value. However, this should not be construed as limiting the analysis of values ​​under the doctrine of equivalents.

[0020] As used herein, polymer molecular weight values, such as weight average molecular weight (Mw) and number average molecular weight (Mn), are measured by gel permeation chromatography using appropriate standards, such as polystyrene standards.

[0021] As used herein, the term "polymer" refers to homopolymers (e.g., prepared from a single monomer species), copolymers (e.g., prepared from at least two monomer species), and graft polymers.

[0022] As used herein, the term "(meth)acrylate" and similar terms such as "(meth)acrylic acid ester" refer to derivatives of acrylic acid and methacrylic acid, including acrylate esters, methacrylate esters, acrylamides, methacrylamides, acrylic acid, and methacrylic acid. As used herein, the term "(meth)acrylic acid" refers to methacrylic acid and / or acrylic acid.

[0023] In some embodiments, the photochromic compounds of the present invention are also referred to herein as photochromic-dichroic compounds (L 1 (e.g., containing one or more extender groups such as

[0024] The photochromic compounds of the present invention described herein, including but not limited to those represented by formula (I) and / or formula (Ia), may in each case optionally further comprise one or more co-products resulting from the synthesis of such compounds.

[0025] As used herein, the term "photochromic" and similar terms such as "photochromic compound" refer to having an absorption spectrum for at least visible light that changes in response to the absorption of at least actinic radiation. Additionally, as used herein, the term "photochromic material" refers to any substance configured to exhibit photochromic properties (e.g., configured to have an absorption spectrum for at least visible light that changes in response to the absorption of at least actinic radiation) and that includes at least one photochromic compound.

[0026] As used herein, the term "actinic radiation" means electromagnetic radiation that is capable of producing a response in a material, such as, but not limited to, converting a photochromic material from one form or state to another, as described in more detail herein.

[0027] As used herein, the term "dichroic" means capable of absorbing at least one of two orthogonal plane polarization components of transmitted radiation more strongly than the other.

[0028] As used herein, the term "photochromic-dichroic" and similar terms such as "photochromic-dichroic compound" means having and / or providing both photochromic properties (i.e., having an absorption spectrum for at least visible light that changes in response to at least actinic radiation) and dichroic properties (i.e., being able to absorb at least one of two orthogonal plane-polarized components of transmitted radiation more strongly than the other).

[0029] As used herein, unless otherwise specified or limited, the term "photochromic material" encompasses both thermally reversible photochromic materials and compounds and non-thermally reversible photochromic materials and compounds. As used herein, the term "thermally reversible photochromic compound / material" refers to a compound / material that can convert from a first state, e.g., a "transparent state," to a second state, e.g., a "colored state," in response to actinic radiation and revert to the first state in response to thermal energy. As used herein, the term "non-thermally reversible photochromic compound / material" refers to a compound / material that can convert from a first state, e.g., a "transparent state," to a second state, e.g., a "colored state," in response to actinic radiation and revert to the first state (e.g., upon cessation of exposure to such actinic radiation) in response to actinic radiation of substantially the same wavelength as the absorption of the colored state.

[0030] As used herein, the terms "first" and "second" to modify the term "state" are not intended to refer to any particular order or chronological sequence, but rather to two different states or properties. For non-limiting illustrative purposes, the first and second states of a photochromic compound may differ with respect to at least one optical property, such as, but not limited to, the absorption of visible light and / or UV radiation. Thus, according to various non-limiting embodiments disclosed herein, the photochromic compounds of the present invention may have different absorption spectra in their first and second states. For example, but not limited to, the photochromic compounds of the present invention may be clear in their first state and colored in their second state. Alternatively, the photochromic compounds of the present invention may have a first color in their first state and a second color in their second state.

[0031] As used herein, the term "optical" means relating to or associated with light and / or vision. For example, according to various non-limiting embodiments disclosed herein, optical articles or elements or devices can be selected from ophthalmic articles, elements and devices; display articles, elements and devices; windows; mirrors; or active and passive liquid crystal cell articles, elements and devices.

[0032] As used herein, the term "ophthalmic" means relating to or associated with the eye and vision. Non-limiting examples of ophthalmic articles or elements include corrective and non-corrective lenses, including multivision lenses, which may be single vision or segmented or non-segmented multivision lenses (such as, but not limited to, bifocal lenses, trifocal lenses, and progressive lenses), and other elements used to correct, protect, or enhance vision (cosmetic or otherwise), such as, but not limited to, contact lenses, intraocular lenses, magnifying lenses, and protective lenses or visors.

[0033] As used herein, the term "display" means a visible or machine-readable representation of information in words, numbers, symbols, designs, or drawings. Non-limiting examples of display elements include screens, monitors, and security elements such as security marks.

[0034] As used herein, the term "window" means an opening adapted to allow the transmission of radiation. Non-limiting examples of windows include automobile and aircraft transparencies, windshields, filters, shutters, and optical switches.

[0035] As used herein, the term "mirror" means a surface that specularly reflects a large portion of incident light.

[0036] As used herein, the term "liquid crystal cell" refers to a structure containing liquid crystal material that can be aligned. A non-limiting example of a liquid crystal cell element is a liquid crystal display.

[0037] As used herein, spatial or directional terms such as "left," "right," "inner," "outer," "superior," "inferior," etc., refer to the invention as shown in the drawings. However, it should be understood that the invention is capable of various alternative orientations, and therefore such terms should not be considered limiting.

[0038] As used herein, the terms "formed on," "deposited on," "provided on," "coated on," "present on," or "disposed on" mean formed, deposited, provided, applied, present, or disposed on, but not necessarily in direct (or adjacent to) contact with, an underlying element or the surface of an underlying element. For example, a layer "disposed on" a substrate does not exclude the presence of one or more other layers, coatings, or films of the same or different composition located between the disposed or formed layer and the substrate.

[0039] As used herein, a reference to a ring position, such as, but not limited to, an x-position (e.g., 3-position or 13-position), refers to a specific position within a ring structure, such as the core backbone structure, of a compound, such as the indeno-fused ring photochromic compound of the present invention, and is herein indicated by a number within the ring structure of a representative chemical formula, such as, but not limited to, Formula (I) and / or (Ia), according to some embodiments.

[0040] "Core skeletal structure" means a compound comprising at least the skeletal structure shown in the associated formula. The core skeletal structure is provided for purposes of identifying the numbered ring positions. However, unless expressly indicated otherwise, it should be understood that the core skeletal structure may have one or more atoms or one or more groups (not specifically shown in the corresponding formula) attached to one or more of the numbered ring positions on the core skeletal structure, which may be the same or different from each other.

[0041] The photochromic compounds of the present invention are referred to herein by the term "core backbone structure," which can be represented by one or more formulas, such as, but not limited to, Formula (I) and / or (Ia).

[0042] All documents or portions of documents, including, but not limited to, patents and patent applications, referred to in this specification shall be deemed to be "incorporated by reference" in their entirety unless otherwise indicated.

[0043] As used herein, a "substituted" group refers to a group such as, but not limited to, an alkyl group, a heterocycloalkyl group, an aryl group, and / or a heteroaryl group, in which at least one hydrogen of the group has been replaced with a group other than hydrogen, such as, but not limited to, a halogen (e.g., F, Cl, I, and Br) group, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, a haloalkyl group, a perhaloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkoxy group, a hydroxyl group, an alkylthio group, an arylthio group, a phosphate ester group, a sulfonic acid group, a sulfonate ester group, a ketone group, an aldehyde group, an ester group, a carboxylic acid ... "Aromatic" refers to a carboxylate group, a siloxane group, an alkoxysilane group, a polysiloxane group, an amide group, an amino group, a carbamate group, a carbonate group, a urea group, a polyester group, a polyether group, a polycarbonate group, a polyurethane group, an acrylate group, a methacrylate group, an arylamino group, such as diphenylamino; an alkylamino group, such as dimethylamino; a cyclic amino, such as morpholino, piperidino, piperazino, or pyrrolidino; a heteroaromatic group, such as imidazole, pyrrole, indole, carbazole; or a combination thereof; or a group substituted or replaced with any other group so long as it does not adversely affect the performance properties of the compound, such as the photochromic performance properties of the compound.

[0044] An "aryl group" refers to an aromatic cyclic monovalent hydrocarbon radical, where the term "aromatic" refers to a cyclic conjugated hydrocarbon that has significantly greater stability (due to delocalization) than a hypothetical localized structure. Examples of aryl groups include, but are not limited to, C6-C 14 Aryl groups include, for example, phenyl, naphthyl, phenanthryl, and anthracenyl.

[0045] As used herein, the term "halo-substituted" and related terms (such as, but not limited to, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, and halo-heteroaryl) refer to a group in which at least one, and up to all, of its available hydrogen radicals have been replaced with a halo radical. The term "halo-substituted" includes "perhalo-substituted." As used herein, the term perhalo-substituted and related terms (such as, but not limited to, perhaloalkyl, perhaloalkenyl, perhaloalkynyl, perhaloaryl, or perhalo-heteroaryl) refer to a group in which all of its available hydrogen radicals have been replaced with a halo radical. For example, perhalomethyl is -CX; perhalophenyl is -CX, where X in these formulas represents one or more halo radicals, such as, but not limited to, F, Cl, or Br.

[0046] As used herein, references to "linear or branched" groups, such as linear or branched alkyl, are used herein to include methylene or methyl groups; groups that are linear (straight chain), such as linear C1-C 25 alkyl groups and the like; and suitably branched groups, such as branched chain C3-C 25 The term "alkyl group" is intended to include alkyl groups and the like.

[0047] As used herein, the term "alkyl" refers to a straight or branched chain, cyclic or non-cyclic C1-C6 alkyl group. 25 The straight or branched chain alkyl is C1 to C 25 Alkyl, e.g., C1-C 20 Alkyl, e.g., C2-C 10 Alkyl, e.g., C1-C 12 Examples of alkyl groups from which the various alkyl groups of the present invention can be selected include, but are not limited to, those further listed herein. The alkyl group can include a "cycloalkyl" group. The term "cycloalkyl" as used herein includes, but is not limited to, C3 to C6 alkyl. 12Cycloalkyl (including but not limited to cyclic C5-C7 alkyl or cyclic C3-C 10 "cycloalkyl" refers to a group that is suitably cyclic, such as a cycloalkyl group (e.g., alkyl group). Examples of cycloalkyl groups include, but are not limited to, those further enumerated herein. As used herein, the term "cycloalkyl" also encompasses bridged-ring polycycloalkyl groups (or bridged-ring polycyclic alkyl groups), such as, but not limited to, bicyclo[2.2.1]heptyl (or norbornyl) and bicyclo[2.2.2]octyl, as well as fused-ring polycycloalkyl groups (or fused-ring polycyclic alkyl groups), such as, but not limited to, octahydro-1H-indenyl and decahydronaphthalenyl.

[0048] As used herein, the term "heterocycloalkyl" includes, but is not limited to, C2-C 10 C2 to C7 heterocycloalkyl groups, etc. C2 to C heterocycloalkyl groups, etc. 12 Heterocycloalkyl groups refer to groups that are suitably cyclic and have at least one heteroatom in the cyclic ring, such as, but not limited to, O, S, N, P, and combinations thereof. Examples of heterocycloalkyl groups include, but are not limited to, imidazolyl, tetrahydrofuranyl, tetrahydropyranyl, and piperidinyl. As used herein, the term "heterocycloalkyl" encompasses bridged-ring polycyclic heterocycloalkyl groups, such as, but not limited to, 7-oxabicyclo[2.2.1]heptanyl; and fused-ring polycyclic heterocycloalkyl groups, such as, but not limited to, octahydrocyclopenta[b]pyranyl and octahydro-1H-isochromenyl.

[0049] As used herein, the term "heteroaryl" includes, but is not limited to, C3-C 18 Heteroaryl, e.g., C3-C 10Heteroaryl (including fused-ring polycyclic heteroaryl groups) refers to an aryl group having at least one heteroatom in an aromatic ring or, in the case of a fused-ring polycyclic heteroaryl group, in at least one aromatic ring. Examples of heteroaryl groups include, but are not limited to, furanyl, pyranyl, pyridinyl, isoquinoline, and pyrimidinyl.

[0050] As used herein, the term "fused-ring polycyclic aryl-alkyl group," as well as similar terms such as fused-ring polycyclic alkyl-aryl group, fused-ring polycyclo-aryl-alkyl group, and fused-ring polycyclo-alkyl-aryl group, refers to a fused-ring polycyclic group that contains at least one aryl ring and at least one cycloalkyl ring fused together to form a fused ring structure. For purposes of non-limiting illustration, examples of fused-ring polycyclic aryl-alkyl groups include, but are not limited to, indenyl, 9H-fluorenyl, cyclopentanaphthenyl, and indacenyl.

[0051] As used herein, the term "aralkyl" includes, but is not limited to, C-C 24 Aralkyl, e.g., C6-C 10 Examples of aralkyl groups include, but are not limited to, benzyl and phenethyl, which refers to an alkyl group substituted with an aryl group.

[0052] Representative alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl. Representative alkenyl groups include, but are not limited to, vinyl, allyl, and propenyl. Representative alkynyl groups include, but are not limited to, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, and 2-butynyl. Representative cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl substituents. Representative heterocycloalkyl groups include, but are not limited to, imidazolyl, tetrahydrofuranyl, tetrahydropyranyl, piperidinyl, and the like. Representative aryl groups include, but are not limited to, phenyl, naphthyl, anthracinyl, phenanthrenyl, and tetracenyl (including structural isomers thereof). Representative heteroaryl groups include, but are not limited to, furanyl, pyranyl, pyridinyl, isoquinolinyl, and pyrimidinyl. Representative aralkyl groups include, but are not limited to, benzyl and phenethyl.

[0053] As used herein, the term "nitrogen-containing heterocycle" refers to a cyclic amino group, including, but not limited to, a nitrogen-containing ring attached via a ring nitrogen. Examples of nitrogen-containing heterocycles include, but are not limited to, cyclic amino groups such as morpholino, piperidino, piperazino, and pyrrolidino; and heteroaromatics such as imidazole, pyrrole, indole, and carbazole.

[0054] As used herein, "at least one of" is synonymous with "one or more of," regardless of whether the elements are listed conjunctively or disjunctively. For example, the phrases "at least one of A, B, and C" and "at least one of A, B, or C" mean any one of A, B, or C, or any combination of any two or more of A, B, or C, respectively. For example, A only, or B only, or C only, or A and B, or A and C, or B and C, or all of A, B, and C.

[0055] As used herein, "selected from" or "chosen from" is synonymous with "at least one of," regardless of whether the elements are listed conjunctively or disjunctively. For example, the phrases "selected from A, B, and C" and "selected from A, B, or C" mean any one of A, B, or C, respectively, or any combination of any two or more of A, B, or C. For example, A only, or B only, or C only, or A and B, or A and C, or B and C, or all of A, B, and C.

[0056] The description of the invention may refer to certain features as being "particularly" or "preferably" within certain limits (e.g., "preferably," "more preferably," or "even more preferably" within certain limits). It is to be understood that the invention is not limited to these particular or preferred limits, but rather encompasses the full scope of the disclosure.

[0057] The present invention comprises, consists of, or consists essentially of the following aspects of the invention in any combination.

[0058] The indeno-fused naphthopyran compounds according to the present invention can be represented by one or more of the core skeletal structures described below. Each of the available numbered ring positions (e.g., 5, 6, 8, 9, 10, 12, and / or 13) of the core skeletal structure of formula (I) can have hydrogen or a non-hydrogen group covalently bonded thereto, such as a group described herein. Examples of such groups are described below. [ka]

[0059] With respect to formula (I), R 1 is a substituted or unsubstituted alkyl group, for example, C1 to C 20 or a substituted or unsubstituted C1 to C6 alkyl group. 1 When R is a substituted alkyl group, the carbon atom of the alkyl group is directly bonded to the carbon atom at position 7, and the carbon atom of the alkyl group directly bonded to the carbon atom at position 7 is unsubstituted. 1 R may be a substituted or unsubstituted alkyl group optionally interrupted by a heteroatom, as long as the carbon atom at position 7 is directly bonded to a carbon atom of the alkyl group. 1The alkyl groups include, but are not limited to, substituted or unsubstituted alkyl groups, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, or heptyl, each of which may be independently substituted or unsubstituted. Suitable substituents include those described above. For example, each alkyl substituent, in each instance, can be independently selected from one or more of: halogen, cyano, nitro, alkenyl, alkynyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, hydroxyl, alkylthio, arylthio, ketone, aldehyde, ester, carboxylic acid, carboxylate, siloxane, alkoxysilane, polysiloxane, amide, amino, carbamate, carbonate, urea, polyester group, polyether group, polycarbonate group, polyurethane group, acrylate group, methacrylate group, or combinations thereof, or any other group that does not adversely affect the performance properties of the compound, such as the photochromic performance properties of the compound. Furthermore, R1 may be an unsubstituted C1 to C6 alkyl group.

[0060] Furthermore, with respect to formula (I), R 2 can be a substituted or unsubstituted amino, such as a primary amino group, a secondary amino group, such as an alkylamino group or an arylamino group, or a tertiary amino group, such as a tertiary amino group having alkyl and / or aryl substituents, or a cyclic amino group, such as a substituted or unsubstituted nitrogen-containing heterocycle; a substituted or unsubstituted alkyl; a substituted or unsubstituted alkenyl; a substituted or unsubstituted alkynyl; a substituted or unsubstituted aryl; a substituted or unsubstituted heteroaryl; a substituted or unsubstituted alkoxy; a substituted or unsubstituted aryloxy; a substituted or unsubstituted alkylthio; a substituted or unsubstituted arylthio; a substituted or unsubstituted amide, such as a substituted amide having aryl or alkyl substituents; a substituted or unsubstituted urea; and a substituted or unsubstituted carbamate. For purposes of the present invention, R 2is a substituted or unsubstituted amide group or a substituted or unsubstituted carbamate group, R 2 is attached to the carbon atom in position 11 via the nitrogen atom of the amide or carbamate group, as the case may be.

[0061] R 2 can be selected from the group consisting of substituted or unsubstituted aryl, substituted or unsubstituted amino, substituted or unsubstituted alkyoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkylthio, and substituted or unsubstituted arylthio. 2 can be substituted or unsubstituted aryl.

[0062] Suitable substituents include those mentioned above in this specification. For example, each alkyl substituent, each heterocycloalkyl substituent, each aryl substituent, and each heteroaryl substituent in this specification can be, in each case, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, perhaloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, hydroxyl, alkylthio, arylthio, phosphate ester, sulfonic acid group, sulfonate ester, ketone, aldehyde, ester, carboxylic acid, carboxylate, siloxane, alkoxysilane, polysiloxane, amide, amine, carbamate, carbonate , urea, polyester groups, polyether groups, polycarbonate groups, polyurethane groups, acrylate groups, methacrylate groups, arylamino, such as diphenylamino; alkylamino, such as dimethylamino; cyclic amino, such as nitrogen-containing heterocycles, such as morpholino, piperidino, piperazino, or pyrrolidino; heteroaromatic, such as imidazole, pyrrole, indole, or carbazole; or combinations thereof; or any other group so long as it does not adversely affect the performance properties of the compound, such as the photochromic performance properties of the compound.

[0063] Further, with respect to formula (I), R 3 and R4 At least one of R is an electron donating group; 3 and R 4 Hammett σ p The sum of the values ​​is less than -0.40. The relative strength of electron donating groups is often expressed as a Hammett sigma value, or σ p The Hammett σ values ​​for various substituents are p A list of values ​​can be found in C. Hansch, A. Leo, and R.W. Taft, "A Survey of Hammett Substituent Constants and Resonance and Field Parameters," Chem. Rev., 1991, 91, 165-195, the disclosure of which is incorporated herein by reference. p The values ​​are listed in Table 1 below. [Table 1]

[0064] For example, R 3 and R 4 At least one of R3 and R4 may be a substituted or unsubstituted amino. At least one of R3 and R4 may be a cyclic amino group, such as a substituted or unsubstituted nitrogen-containing heterocycle, for example, a nitrogen-containing heterocycle selected from the group consisting of morpholino, piperidino, substituted piperazino, and pyrrolidino. 3 and R 4 may be the same or different and may each independently be a substituted or unsubstituted alkoxy or a substituted or unsubstituted amino. 3 and R 4 At least one of may be selected from the group consisting of methoxy, morpholino, piperazino, substituted piperazino, and dialkyl(C1-C6)amino.

[0065] Additionally or alternatively, the indeno-fused naphthopyran compounds of the present invention can be represented by a core skeletal structure of formula (Ia): [ka]

[0066] With respect to formula (Ia), R 1 , R 2 , R 3 , and R 4 is as described above with respect to formula (I).

[0067] As noted above, the remaining numbered ring positions (e.g., 5, 6, 8, 9, 10, and / or 12) of the core skeletal structure of Formula (Ia) that are not specifically shown to have a substituent can have hydrogen or a group other than hydrogen covalently bonded thereto, such as a group described herein.

[0068] Further with respect to formula (Ia), R 5 and R 6 Each of the following is independent: (i) hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heterocycloalkyl, aryl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; (ii) alkoxy, hydroxyl, alkylthio, ketone, aldehyde, ester, carboxylic acid, carboxylate, siloxane, alkoxysilane, or polysiloxane; (iii) a group comprising a polyester, a polyether, a polycarbonate, a polyurethane, or a combination thereof; or (iv)R 5 and R 6 are taken together with the carbon atom at position 13 bonded thereto to form an aliphatic ring having 3 to 20 ring carbon atoms, a fused polycyclic ring having an aromatic ring or a heteroaromatic ring fused to the aliphatic ring, a heterocyclic ring having 3 to 20 ring atoms, or a fused polycyclic ring having an aromatic ring or a heteroaromatic ring fused to the heterocyclic ring.

[0069] R 5 and R 6 Each of R can independently be a substituted or unsubstituted alkyl. For example, R5 and R 6 are independently C1 to C6 linear or branched alkyl, and C5 to C 10 The substituents may be selected from the group consisting of cycloalkyl, cycloalkyl, aryl, and heteroaryl. Suitable substituents may include those described above. For example, each alkyl, heterocycloalkyl, aryl, and heteroaryl substituent in this specification may, in each instance, independently be selected from halogen, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, perhaloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, hydroxyl, alkylthio, arylthio, phosphate ester, sulfonic acid group, sulfonate ester, ketone, aldehyde, ester, carboxylic acid, carboxylate, siloxane, alkoxysilane, polysiloxane, amide, and amine. , carbamate, carbonate, urea, polyester groups, polyether groups, polycarbonate groups, polyurethane groups, acrylate groups, methacrylate groups, arylamino, such as diphenylamino; alkylamino, such as dimethylamino; cyclic amino, such as morpholino, piperidino, or pyrrolidino; heteroaromatic, such as imidazole, pyrrole, indole, or carbazole; or combinations thereof; or any other group that does not adversely affect the performance properties of the compound, such as the photochromic performance properties of the compound.

[0070] With respect to formula (Ia), R 1 may be unsubstituted C1-C6 alkyl, R 2 may be substituted or unsubstituted phenyl, R 3 and R 4 may each independently be a C1-C4 alkoxy or a nitrogen-containing heterocycle, and R 5 and R 6 can each independently be C1 to C4 alkyl.

[0071] The indeno-fused naphthopyran compounds of the present invention can be prepared according to art-recognized methods. For non-limiting illustrative purposes, with reference to Figures 1 and 2, synthesis part 1 and synthesis part 2 of the basic synthetic scheme for producing the photochromic compounds of the present invention are described below.

[0072] Synthesis Part 1 Step 1: Aryl bromides can be prepared as Grignard reagents, which can then be reacted with acid chlorides to form the corresponding benzophenones. [ka]

[0073] Step 2: The benzophenone can be subjected to Stobbe condensation to form Stobbe acid. [ka]

[0074] Step 3: The carboxylic acids can undergo acid-catalyzed cyclization using acetic anhydride and a co-solvent at elevated temperatures. [ka]

[0075] Step 4: The acetoxy group can undergo acid-catalyzed methanolysis in methanol at elevated temperatures to give naphthol. [ka]

[0076] Step 5: The tertiary alcohol is formed by reacting the methyl ester with 2 to 6 equivalents of a Grignard reagent, optionally in the presence of lanthanum(III) chloride-lithium chloride salt (LaCl3-2LiCl). [ka]

[0077] Step 6: The tertiary alcohol then undergoes acid-catalyzed dehydration followed by an intramolecular Friedel-Crafts reaction to afford the indeno-fused naphthol, which serves as an intermediate to achieve various substitutions at the 11 and 3 positions of the target compounds, as shown in Synthesis Part 2 below. [ka]

[0078] Synthesis Part 2 Bromine can undergo cross-coupling with arylboronic acids using standard Suzuki cross-coupling conditions. Alternatively, thioether substituents can be generated by palladium-catalyzed cross-coupling of bromine with alkyl or aryl thiols at elevated temperatures using tris(dibenzylideneacetone)dipalladium(0) and Xantphos ligands. To introduce amines at this position, palladium-catalyzed cross-coupling of bromine with primary or secondary amines using standard Buchwald-Hartwig cross-coupling conditions can be employed.

[0079] Each of the resulting naphthols can be reacted with diarylpropargyl alcohols under known conditions to give the desired indeno-fused naphthopyrans.

[0080] Figure 1 illustrates a procedure for synthesizing an indeno-fused naphthol intermediate compound used to prepare an indeno-fused naphthopyran compound of the present invention, according to the steps described above in Synthesis Part 1. Figure 2 illustrates a procedure for introducing desired substituents at the 7- and 11-positions of an indeno-fused naphthopyran compound of the present invention, according to the steps described above in Synthesis Part 2.

[0081] The present invention also provides photochromic compositions comprising at least one indeno-fused naphthopyran compound according to the present invention, such as those represented by formula (I) and / or (Ia) hereinbefore.

[0082] The photochromic composition may contain (i) an organic material, which may be at least one of a polymeric material, an oligomeric material, or a monomeric material, and (ii) a photochromic indeno-fused naphthopyran compound according to the present invention incorporated into at least a portion of the organic material. The photochromic compound may be incorporated into a portion of the organic material by at least one of, but not limited to, blending or bonding the photochromic compound with the organic material or a precursor of the organic material. As used herein, the terms "blend" and "blended" in relation to incorporating the photochromic compound into the organic material mean that the photochromic compound / material is mixed or intermixed with at least a portion of the organic material but is not bonded to the organic material. Furthermore, as used herein, the terms "bond" or "bonded" in relation to incorporating the photochromic compound into the organic material mean that the photochromic compound / material is linked to a portion of the organic material or its precursor, for example, by one or more covalent bonds. For example, but not limited to, the photochromic material may be linked to the organic material via a reactive substituent.

[0083] When the organic material is a polymeric material, the photochromic indeno-fused naphthopyran compound can be incorporated into at least a portion of the polymeric material, or at least a portion of the monomeric or oligomeric material for forming the polymeric material.For example, the photochromic indeno-fused naphthopyran compound according to the present invention having a reactive substituent can be bonded to an organic material such as a monomer, oligomer, or polymer having a group with which the reactive moiety can react, or the reactive moiety can react as a comonomer in a polymerization reaction, for example, a copolymerization process, to form an organic material.

[0084] As described above, in some embodiments, the photochromic composition according to the present invention can include an organic material selected from polymeric materials, oligomeric materials, and / or monomeric materials. Examples of polymeric materials that can be used in the photochromic composition of the present invention include, but are not limited to, poly(carbonate), ethylene and vinyl acetate copolymers, ethylene and vinyl alcohol copolymers, ethylene, vinyl acetate, and vinyl alcohol copolymers (such as those obtained by partial saponification of ethylene and vinyl acetate copolymers), cellulose acetate butyrate, poly(urethane), poly(acrylate), poly(methacrylate), epoxy, aminoplast functional polymers, poly(anhydride), poly(urea urethane), N-alkoxymethyl(meth)acrylamide functional polymers, poly(siloxane), poly(silane), and combinations and mixtures thereof. Additional classes and examples of polymeric materials that can be used with the photochromic compositions of the present invention include, but are not limited to, those disclosed in U.S. Pat. No. 9,028,728 B2 at column 39, line 45 to column 40, line 67, the citations of which are incorporated herein by reference.

[0085] Furthermore, the indeno-fused naphthopyran photochromic compounds of the present invention can be used in combination with one or more complementary conventional polymerizable or compatible photochromic compounds, such as those disclosed in U.S. Pat. Nos. 6,113,814 (column 2, line 39 to column 8, line 41) and 6,555,028 (column 2, line 65 to column 12, line 56), the cited portions of which are incorporated herein by reference. The indeno-fused naphthopyran photochromic compounds of the present invention can be used in combination with mixtures of other photochromic compounds. For example, but not limited to, a mixture of photochromic compounds can be used to achieve a certain activated color, such as a nearly neutral gray or a nearly neutral brown. See, for example, U.S. Pat. No. 5,645,767, column 12, line 66 to column 13, line 19 (the cited portions of which are incorporated herein by reference), which describes parameters defining neutral gray and brown colors.

[0086] Examples of other photochromic compound classes that can be used in combination with the photochromic compounds of the present invention include, but are not limited to, indeno-fused naphthopyrans, naphtho[1,2-b]pyrans, naphtho[2,1-b]pyrans, spirofluoroeno[1,2-b]pyrans, phenanthrenopyrans, quinolinopyrans, fluoroanthenopyrans, spiropyrans, benzoxazines, naphthoxazines, spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines, spiro(indoline)fluoranthenoxazines, spiro(indoline)quinoxazines, fulgides, fulgimides, diarylethenes, diarylalkylethenes, diarylalkenylethenes, thermally reversible photochromic compounds, and non-thermally reversible photochromic compounds, and mixtures thereof. Further examples of other photochromic compounds that can be used in combination with the photochromic compounds of the present invention include, but are not limited to, those disclosed in U.S. Pat. No. 9,028,728 B2 at column 34, line 20 to column 35, line 13, the cited portions of which are incorporated herein by reference.

[0087] The photochromic compositions of the present invention can include at least one of a complementary photochromic material (including one or more of the other photochromic materials and compounds described herein), a photoinitiator, a thermal initiator, a polymerization inhibitor, a solvent, a light stabilizer, a heat stabilizer, a mold release agent, a rheology control agent, a leveling agent, a free radical scavenger, and / or an adhesion promoter.

[0088] The photochromic composition according to the present invention can be a photochromic coating composition. The photochromic coating composition according to the present invention can comprise a photochromic indeno-fused naphthopyran compound according to the present invention, as described herein above with respect to formula (I) and / or (Ia); an optionally curable resin composition; and, optionally, a solvent. The photochromic coating composition can be in the form of a liquid coating or a powder coating, as recognized in the art. The photochromic coating composition according to the present invention can be a thermoplastic or thermosetting coating composition. The photochromic coating composition can be a curable or thermosetting coating composition.

[0089] The curable resin composition of a curable photochromic coating composition according to the present invention may include a first reactant (or component) having a functional group, such as an epoxide-functional polymeric reactant, and a second reactant (or component) that is a crosslinker having a functional group reactive with and capable of forming a covalent bond with the functional group of the first reactant. The first and second reactants of the curable resin composition of the curable photochromic coating composition may each independently comprise one or more functional species, and each is present in an amount sufficient to obtain a cured photochromic coating having a desired combination of physical properties, such as smoothness, optical clarity, solvent resistance, and hardness.

[0090] Examples of curable resin compositions that can be used with the curable photochromic coating composition of the present invention include, but are not limited to, curable resin compositions comprising an epoxide-functional polymer (e.g., a (meth)acrylic polymer containing residues of glycidyl (meth)acrylate) and an epoxide-reactive crosslinker (e.g., containing active hydrogens such as hydroxyl, thiol, and amine); and curable resin compositions comprising an active hydrogen-functional polymer (e.g., a hydroxy-, thiol-, and / or amine-functional polymer) and a capped (or blocked) isocyanate-functional crosslinker. A "capped (or blocked) isocyanate-functional crosslinker" refers to a crosslinker having two or more capped isocyanate groups that can be uncapped (or unblocked) under curing conditions (e.g., elevated temperatures) to form a free isocyanate group and a free capping group. The free isocyanate group formed by uncapping of the crosslinker can preferably react with the active hydrogen group of the active hydrogen-functional polymer (e.g., with the hydroxy group of a hydroxy-functional polymer) to form a substantially permanent covalent bond. Further examples of curable resin compositions that can be used with the curable photochromic coating composition according to the present invention include, but are not limited to, those disclosed in WO 2016 / 142496 A1, paragraphs

[0176] to

[0190] , and WO 2017 / 030545 A1, paragraphs

[0005] ,

[0037] to

[0051] ,

[0056] to

[0059] , and

[0063] to

[0065] , the cited portions of which are incorporated herein by reference.

[0091] Curable photochromic coating compositions according to the present invention can optionally contain additives such as waxes for flow and wetting, flow control agents such as poly(2-ethylhexyl)acrylate, auxiliary resins for modifying and optimizing coating properties, antioxidants, and ultraviolet (UV) light absorbers. Examples of useful antioxidants and UV absorbers include those available from BASF under the trademarks IRGANOX and TINUVIN. These optional additives, when used, are typically present in an amount of up to 20 weight percent (e.g., 0.5 to 10 weight percent), based on the total weight of resin solids of the curable resin composition.

[0092] The photochromic compositions, photochromic articles, and photochromic coating compositions according to the present invention may further comprise art-recognized additives that aid or assist in the processing and / or performance of the composition or article. Non-limiting examples of such additives include photoinitiators, thermal initiators, polymerization inhibitors, solvents, light stabilizers (including but not limited to UV absorbers and light stabilizers, e.g., hindered amine light stabilizers (HALS)), heat stabilizers, mold release agents, rheology control agents, leveling agents (including but not limited to surfactants), free radical scavengers, adhesion promoters (such as hexanediol diacrylate and coupling agents), and combinations and mixtures thereof.

[0093] The photochromic indeno-fused naphthopyran compounds of the present invention can be used in amounts (or proportions) such that the compositions, organic materials, or substrates (e.g., photochromic articles and photochromic coatings) incorporating or otherwise associated with the photochromic indeno-fused naphthopyran compounds exhibit the desired optical properties. The amount and type of photochromic material can be selected so that the composition, organic material, or substrate is clear or colorless when the photochromic indeno-fused naphthopyran compound is in its closed ring form (e.g., in a bleached or inactivated state) and exhibits the desired resultant color when the photochromic compound (such as the photochromic indeno-fused naphthopyran of the present invention) is in its open ring form (e.g., when activated by actinic radiation). The exact amount of photochromic material utilized in the various photochromic compositions and articles described herein is not critical, so long as a sufficient amount is used to achieve the desired effect. The specific amount of photochromic material used can depend on various factors, including, but not limited to, the absorption characteristics of the photochromic compound, the color and color intensity desired upon activation, and the method used to incorporate or bond the photochromic material to the substrate.

[0094] Photochromic compositions according to the present invention may comprise indeno-fused naphthopyran compounds according to the present invention, such as compounds represented by Formula (I) and / or (Ia), in an amount of 0.01 to 40 weight percent, for example, 0.05 to 15 weight percent, for example, 0.1 to 5 weight percent, based on the weight of the photochromic composition. By way of further non-limiting example, the amount of photochromic compound / material, including compounds represented by Formula (I) and / or (Ia), incorporated into an organic material may range from 0.01 to 40 weight percent, for example, 0.05 to 15 weight percent, for example, 0.1 to 5 weight percent, based on the weight of the organic material.

[0095] The present invention also relates to photochromic articles comprising one or more indeno-fused naphthopyran compounds according to the present invention, such as those represented by formula (I) and / or (Ia). Photochromic articles can be manufactured by art-recognized methods such as imbibition, cast-in-place, coating, in-mold coating, overmolding, and lamination.

[0096] For example, the optical article can be selected from an ophthalmic article, a display article, a window, a mirror, an active liquid crystal cell article, and a passive liquid crystal cell article.

[0097] The optical article of the present invention may also be an ophthalmic article, which may be selected from corrective lenses, non-corrective lenses, contact lenses, intraocular lenses, magnifying lenses, protective lenses, and visors.

[0098] Additionally, the photochromic article of the present invention can be a display article, which can be selected from screens, monitors, and security elements.

[0099] The present invention is more particularly described in the following examples, which are intended to be illustrative only, since numerous modifications and variations therein will be apparent to those skilled in the art. [Example]

[0100] The following examples are provided to illustrate the preparation of the indeno-fused naphthopyran compounds of the present invention.

[0101] Example 1 Step 1: Under nitrogen, magnesium turnings (5.33 g) and a catalytic amount of iodine were vigorously stirred in anhydrous tetrahydrofuran (50 mL) for 30 minutes. The mixture was then cooled to -5°C in an ice bath with brine. 3.75 g of 3-bromotoluene (10 mL) was then added dropwise to the reaction mixture. After 15 minutes, an exotherm was observed. Additional 21.25 g of 3-bromotoluene (30 mL) was added dropwise at a rate that maintained the temperature below 5°C. Upon completion, the mixture was held for 1 hour and then decanted into a second reaction vessel, leaving behind unreacted magnesium turnings. The second reaction vessel was stirred under nitrogen and placed in an ice bath. 23.42 g of bis[2-(N,N-dimethylaminoethyl)]ether (23.42 g) dissolved in anhydrous tetrahydrofuran (20 mL) was added dropwise over 10 minutes, maintaining the temperature below 5°C. Upon completion, the mixture was held for 1 hour. 4-Bromobenzoyl chloride (32.08 g) was then added portionwise to the reaction mixture over 15 minutes, maintaining the temperature below 5°C. The reaction was held for 2 hours, then warmed to room temperature, and held for 16 hours. The reaction mixture was poured into a mixture of 10% aqueous hydrochloric acid (v / v) and ice and extracted twice with dichloromethane. The combined organic layers were washed with saturated aqueous sodium bicarbonate, dried over sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified using silica gel flash chromatography, eluting with a mixture of 95% hexane and 5% ethyl acetate. Fractions containing the desired product were combined and concentrated under reduced pressure. The resulting solid was triturated with a mixture of 93% hexane and 7% ethyl acetate, then collected by filtration to give (4-bromophenyl)(m-tolyl)methanone as a white solid (27.80 g, 69% yield).

[0102] Step 2: The product from Step 1 (27.80 g) and dimethyl succinate (20.67 g) were combined in toluene (556 mL) and vigorously stirred in an ice bath. Potassium tert-pentoxide solution (1.7 M in toluene, 101 mL) was added dropwise over 30 minutes. After an additional 2 hours, the reaction mixture was poured into ice water. Concentrated hydrochloric acid was added to the aqueous layer and ice until the pH reached 1. The aqueous layer was then extracted twice with dichloromethane. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give (E)-4-(4-bromophenyl)-3-(methoxycarbonyl)-4-(m-tolyl)but-3-enoic acid (39.3 g, 100% yield) as an amber oil.

[0103] Step 3: The product of Step 2 (39.3 g) and acetic anhydride (41.2 g) were stirred in xylene (118 mL). The solution was heated to 90°C under a nitrogen atmosphere for 2 hours. The temperature was then increased to 140°C for 1 hour. The solution was cooled to room temperature and concentrated under reduced pressure to give methyl 4-acetoxy-1-(4-bromophenyl)-7-methyl-2-naphthoate as an amber oil (37.5 g, 90% yield).

[0104] Step 4: The product of Step 3 (37.5 g) was dissolved in methanol (563 mL) and concentrated hydrochloric acid (3.75 mL) was added. The solution was heated to 65°C under nitrogen for 4 hours, then cooled to room temperature and poured slowly into a mixture of saturated aqueous sodium bicarbonate and ice with vigorous stirring. The mixture was extracted twice with dichloromethane. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The resulting residue was subjected to silica gel chromatography eluting with methylene chloride. Pure fractions, as determined by HPLC area %, were combined and concentrated under reduced pressure. The resulting oil was recrystallized in a mixture of 90% hexane and 10% ethyl acetate to give methyl 1-(4-bromophenyl)-4-hydroxy-7-methyl-2-naphthoate as a white crystalline solid (6.5 g, 19% yield).

[0105] Step 5: Under nitrogen, lanthanum chloride (7.93 g) and lithium chloride (4.11 g) were stirred in anhydrous tetrahydrofuran (90 mL). The mixture was heated to 55°C for 16 hours and then cooled to room temperature. The product of Step 4 (6.00 g) was added to the reaction mixture, and the vessel was then cooled to -15°C. Propylmagnesium chloride solution (2.0 M in diethyl ether, 49 mL) was added dropwise to the reaction over 50 minutes, maintaining the temperature between -15°C and -10°C. After holding at this temperature for 2 hours, the reaction mixture was poured into a mixture of 10% aqueous hydrochloric acid (v / v) and ice and extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, and then passed through a short plug of silica gel, rinsing with ethyl acetate. The mother liquor was concentrated under reduced pressure to give 4-(4-bromophenyl)-3-(4-hydroxyheptan-4-yl)-6-methylnaphthalen-1-ol as an amber oil (6.0 g, 87% yield).

[0106] Step 6: The product of Step 5 (6.91 g) and p-toluenesulfonic acid monohydrate (0.03 g) were dissolved in toluene (104 mL) and heated to 110 °C under nitrogen for 3 h using a Dean-Stark trap. The solution was then cooled to 60 °C. Bismuth triflate (0.11 g) was added, and the solution was heated to 90 °C for 45 min, then cooled to room temperature and filtered through a plug of silica gel, washing with dichloromethane. The mother liquor was concentrated under reduced pressure, followed by recrystallization from hexane to give 9-bromo-2-methyl-7,7-dipropyl-7H-benzo[c]fluoren-5-ol as a white solid (5.3 g, 80% yield).

[0107] Step 7: The product of Step 6 (1.67 g), 1-(3-fluoro-4-methoxyphenyl)-1-(4-morpholinophenyl)prop-2-yn-1-ol (2.79 g), and 4-dodecylbenzenesulfonic acid (0.13 g) were stirred in 1,2-dichloroethane (33 mL) and heated to 83 °C under a nitrogen atmosphere for 6 h. The mixture was then cooled to room temperature and filtered through a silica gel plug, rinsing with dichloromethane. The mother liquor was concentrated under reduced pressure to give 11-bromo-3-(3-fluoro-4-methoxyphenyl)-7-methyl-3-(4-morpholinophenyl)-13,13-dipropyl-3H,13H-indeno[2',3',3,4]naphtho[1,2-b]pyran as a dark oil (2.80 g, 94% yield).

[0108] Step 8: The product of Step 7 (0.90 g), phenylboronic acid (0.18 g), and potassium carbonate (0.37 g) were stirred in a mixture of N,N-dimethylacetamide (4 mL), deionized water (1.5 mL), and ethanol (1.5 mL). The mixture was sparged with nitrogen for 20 minutes and placed under nitrogen. Tetrakis(triphenylphosphine)palladium(0) (0.07 g) was added, and the mixture was heated at 85°C for 2 hours. It was then cooled to room temperature and poured into a mixture of 10% aqueous hydrochloric acid (v / v) and ice. This was then extracted twice with ethyl acetate. The combined organic layers were washed twice with brine, dried over sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified using silica gel flash chromatography, eluting with a mixture of 75% hexane and 25% ethyl acetate. Fractions containing the desired product were combined and concentrated under reduced pressure. The resulting residue was triturated with methanol and then collected by vacuum filtration to give a pale blue solid (0.69 g, 77% yield). 1 1 H NMR is consistent with the following structure: [ka]

[0109] Example 2 Step 1: The same conditions as in Example 1, steps 7 and 8 were applied to the product of Example 1, step 6 (1.00 g), except that in step 7, 1-(3-fluoro-4-methoxyphenyl)-1-(4-morpholinophenyl)prop-2-yn-1-ol was replaced with an equimolar amount of 1-(4-methoxyphenyl)-1-(4-(4-((trifluoromethyl)sulfonyl)piperazin-1-yl)phenyl)prop-2-yn-1-ol. A white solid was obtained (0.50 g, 45% yield). 1 1 H NMR is consistent with the following structure: [ka]

[0110] Example 3 Step 1: The product of Example 1, Step 6 was subjected to the conditions of Example 1, Step 8, using an equimolar amount of (4-trifluoromethyl)phenylboronic acid in place of phenylboronic acid. Purification by silica gel flash chromatography gave 2-methyl-7,7-dipropyl-9-(4-(trifluoromethyl)phenyl)-7H-benzo[c]fluoren-5-ol (0.96 g, 83% yield) as a white solid.

[0111] Step 2: The product of Step 1 (0.45 g), 1-(3-fluoro-4-methoxyphenyl)-1-(4-morpholinophenyl)prop-2-yn-1-ol (0.65 g), and 4-dodecylbenzenesulfonic acid (0.03 g) were stirred in 1,2-dichloroethane (9 mL) and heated to 83 °C under nitrogen for 6 h, then cooled to room temperature and filtered through a silica gel plug with dichloromethane. The mother liquor was concentrated under reduced pressure and purified using silica gel flash chromatography eluting with a mixture of 80% hexane and 20% ethyl acetate. The resulting residue was recrystallized from hexane to give a white solid (0.13 g, 17% yield). 1 1 H NMR is consistent with the following structure: [ka]

[0112] Example 4 Step 1: The product of Example 1, Step 6 (3.26 g) was subjected to the same conditions as in Example 1, Step 8, except that phenylboronic acid was replaced with an equimolar amount of 4-methoxyphenylboronic acid, to give solid 9-(4-methoxyphenyl)-2-methyl-7,7-dipropyl-7H-benzo[c]fluoren-5-ol (2.44 g, 70% yield).

[0113] Step 2: The same conditions as in Example 3, Step 2 were applied to the product of Step 1 (5.00 g), replacing 1-(3-fluoro-4-methoxyphenyl)-1-(4-morpholinophenyl)prop-2-yn-1-ol with an equimolar amount of 1-(4-butoxyphenyl)-1-(4-morpholinophenyl)prop-2-yn-1-ol. The residue was recrystallized from a mixture of 35% ethyl acetate and 65% methanol to give a crystalline solid (5.93 g, 66% yield). 1 1 H NMR is consistent with the following structure: [ka]

[0114] Example 5 Step 1: The product of Example 1, Step 6 (3.00 g) was subjected to the same conditions as in Example 1, Step 8, except that phenylboronic acid was replaced with an equimolar amount of (2,4-dimethoxyphenyl)boronic acid to give solid 9-(2,4-dimethoxyphenyl)-2-methyl-7,7-dipropyl-7H-benzo[c]fluoren-5-ol (2.72 g, 80% yield).

[0115] Step 2: The product of step 1 (0.90 g) was subjected to the same conditions as in example 1, step 7, except that 1-(3-fluoro-4-methoxyphenyl)-1-(4-morpholinophenyl)prop-2-yn-1-ol was replaced with an equimolar amount of 1-(4-methoxyphenyl)-1-(4-morpholinophenyl)prop-2-yn-1-ol, to give a white solid (0.76 g, 51% yield). 1 1 H NMR is consistent with the following structure: [ka]

[0116] Example 6 Step 1: Applying the same conditions as in Example 1, Step 8 to the product of Example 1, Step 6 yields a product consistent with 2-methyl-9-phenyl-7,7-dipropyl-7H-benzo[c]fluoren-5-ol. 1 A white solid was obtained with 1 H NMR.

[0117] Step 2: The product of step 1 (0.40 g) was subjected to the same conditions as in example 3, step 2, except that 1-(3-fluoro-4-methoxyphenyl)-1-(4-morpholinophenyl)prop-2-yn-1-ol was replaced with an equimolar amount of 1-(4-methoxyphenyl)-1-(4-morpholinophenyl)prop-2-yn-1-ol, to give a white solid (0.37 g, 53% yield). 1 1 H NMR is consistent with the following structure: [ka]

[0118] Example 7 Step 1: The product of Example 1, Step 6 (5.00 g) and N,N-diisopropylethylamine (4.74 g) were stirred in toluene (30 mL). The mixture was sparged with nitrogen for 20 minutes and then placed under a nitrogen blanket. Tris(dibenzylideneacetone)dipalladium(0) (0.78 g) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (1.06 g) were added to the reaction mixture. 2,6-dimethylbenzenethiol (3.38 g) was then added dropwise to the mixture. The reaction mixture was rapidly heated to 110°C and maintained at that temperature for 17 hours. It was then cooled to room temperature and filtered through a silica gel plug, washing with a mixture of 75% hexane and 25% ethyl acetate. The mother liquor was concentrated under reduced pressure. The resulting residue was purified using silica gel flash chromatography, eluting with a mixture of 80% hexane and 20% ethyl acetate. Fractions containing the desired product were combined and concentrated under reduced pressure to give an oily product, 9-((2,6-dimethylphenyl)thio)-2-methyl-7,7-dipropyl-7H-benzo[c]fluoren-5-ol.

[0119] Step 2: The product of step 1 was precipitated from methanol under the same conditions as in step 2 of Example 5 to obtain a solid. 1 1 H NMR is consistent with the following structure: [ka]

[0120] Example 8 Step 1: The product from Example 1, Step 6 (5.00 g), morpholine (2.13 g), and potassium tert-butoxide (2.74 g) were stirred in 1,2-dimethoxyethane (40 mL), sparged with nitrogen for 20 minutes, and maintained under a nitrogen atmosphere. Bis(tri-tert-butylphosphine)palladium(0) (0.44 g) was then added, and the mixture was heated at 85°C for 16 hours. The mixture was then cooled to room temperature, and water (100 mL), citric acid (15 g), and toluene (100 mL) were added. The resulting organic layer was filtered through a plug of magnesium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel flash chromatography, eluting with a mixture of 70% hexane and 30% ethyl acetate. Fractions containing the desired product were combined and concentrated under reduced pressure to give 2-methyl-9-morpholino-7,7-dipropyl-7H-benzo[c]fluoren-5-ol as a white solid.

[0121] Step 2: The product of Step 1 (3.56 g) was subjected to the same conditions as in Example 5, Step 2 to give a solid. 1 1 H NMR is consistent with the following structure: [ka]

[0122] Example 9 Step 1: 2-Bromo-9-methoxy-7,7-dipropyl-7H-benzo[c]fluoren-5-ol (5.0 g) was stirred in toluene (20 mL / g). The mixture was sparged with nitrogen for 20 minutes and placed under nitrogen. 1,1-bis(diphenylphosphino)ferrocenedichloropalladium(II) (0.20 g) and tris(dibenzylideneacetone)dipalladium(0) (0.11 g) were added to the mixture. A 1.4 M solution of methylmagnesium bromide in THF / toluene (26 mL) was added dropwise over 10 minutes. The reaction mixture was then heated to 90°C for 15 minutes, cooled to room temperature, and then placed in ice water and acidified with dilute hydrochloric acid until the pH reached 5. The reaction mixture was then extracted with ethyl acetate. The organic layer was concentrated to dryness under reduced pressure. The resulting residue was dissolved in a minimum amount of dichloromethane and then filtered through a plug of silica gel, rinsing with dichloromethane. The mother liquor was concentrated under reduced pressure to give a white solid, 9-methoxy-2-methyl-7,7-dipropyl-7H-benzo[c]fluoren-5-ol (4.1 g, 97% yield).

[0123] Step 2: Applying the same conditions as in Example 5, Step 2 to the product from Step 1 gave a solid. 1 1 H NMR is consistent with the following structure: [ka]

[0124] Example 10 Step 1: The same conditions as in Example 1, Step 7 were applied to the product of Example 1, Step 6 (2.00 g), except that 1-(3-fluoro-4-methoxyphenyl)-1-(4-morpholinophenyl)prop-2-yn-1-ol was replaced with an equimolar amount of 1-(4-butoxyphenyl)-1-(4-morpholinophenyl)prop-2-yn-1-ol, to give 11-bromo-3-(4-butoxyphenyl)-7-methyl-3-(4-morpholinophenyl)-13,13-dipropyl-3H,13H-indeno[2′,3′,3,4]naphtho[1,2-b]pyran (3.64 g, 98% yield) as a dark oil.

[0125] Step 2: The product from Step 1 (3.64 g), 2-pyrrolidinone (2.05 g), and tripotassium phosphate (3.06 g) were stirred in 1,4-dioxane (55 mL). The mixture was sparged with nitrogen for 20 minutes and then placed under a nitrogen atmosphere. 2-Di-tert-butylphosphino-2',4',6'-triisopropylbiphenyl (0.51 g) and tris(dibenzylideneacetone)dipalladium(0) (0.44 g) were added, and the mixture was then heated to 90°C for 2 hours. The mixture was then cooled to room temperature and poured into a mixture of dilute aqueous hydrochloric acid and ice. This mixture was then extracted twice with ethyl acetate. The combined organic layers were then washed with saturated aqueous sodium bicarbonate, dried over sodium sulfate, and concentrated to dryness under reduced pressure. The resulting residue was purified by silica gel flash chromatography eluting with a mixture of 35% ethyl acetate and 65% hexane. Fractions containing the desired product were combined and concentrated to dryness under reduced pressure. The resulting residue was recrystallized from a mixture of 25% ethyl acetate and 75% methanol, and the pale blue crystalline solid was isolated by vacuum filtration to give (2.00 g, 55% yield). 1 1 H NMR is consistent with the following structure: [ka]

[0126] Example 11 Step 1: Using the same conditions as in Example 1, Step 1, except that 3-bromotoluene was replaced with 1-bromo-3-(tert-butyl)benzene, a white solid, (4-bromophenyl)(3-(tert-butyl)phenyl)methanone, was obtained (18.99 g, 74% yield).

[0127] Step 2: The product of Step 1 (18.90 g) was treated under the conditions of Example 1, Step 2 to give (E)-4-(4-bromophenyl)-4-(3-(tert-butyl)phenyl)-3-(methoxycarbonyl)but-3-enoic acid (22.1 g, 86% yield) as an amber oil.

[0128] Step 3: The product of Step 2 (22.05 g) was treated using the conditions of Example 1, Step 3 to give methyl-4-acetoxy-1-(4-bromophenyl)-7-(tert-butyl)-2-naphthoate (18.25 g, 78% yield) as an amber oil.

[0129] Step 4: The product of Step 3 (37.5 g) was treated under the conditions of Example 1, Step 4 to give methyl 1-(4-bromophenyl)-7-(tert-butyl)-4-hydroxy-2-naphthoate (3.4 g, 21% yield) as a white solid.

[0130] Step 5: The product of Step 4 (3.31 g) was treated under the same conditions as in Example 1, Step 5 to give amber oil, 4-(4-bromophenyl)-6-(tert-butyl)-3-(4-hydroxyheptan-4-yl)naphthalen-1-ol (3.62 g, 96% yield).

[0131] Step 6: The product of Step 5 (3.60 g) was treated under the conditions of Example 1, Step 6 to give 9-bromo-2-(tert-butyl)-7,7-dipropyl-7H-benzo[c]fluoren-5-ol as a white solid (3.00 g, 87% yield).

[0132] Step 7: The product of step 6 (0.80 g) was subjected to the same conditions as in example 3, step 1, except that (4-trifluoromethyl)phenylboronic acid was replaced with an equimolar amount of (2,4-dimethoxyphenyl)boronic acid, to give a white solid, 2-(tert-butyl)-9-(2,4-dimethoxyphenyl)-7,7-dipropyl-7H-benzo[c]fluoren-5-ol (0.81 g, 90% yield).

[0133] Step 8: The product of step 7 (0.81 g) was subjected to the same conditions as in example 4, step 2, except that 1-(4-butoxyphenyl)-1-(4-morpholinophenyl)prop-2-yn-1-ol was replaced with an equimolar amount of 1-(4-methoxyphenyl)-1-(4-morpholinophenyl)prop-2-yn-1-ol to give a solid (55 g, 42% yield). 1 1 H NMR is consistent with the following structure: [ka]

[0134] Part 2: Results Each of the photochromic dyes of Examples 1-11 and Comparative Examples CE1-CE10 was incorporated at the same mole percent into a polyurethane coating system, as described in Examples 1-3 of U.S. Patent No. 8,608,988, and applied to a 2-inch by 2-inch test chip made from CR-39® monomer (PPG Industries, Inc.) at the same coating thickness. All coated test chips were cured at 125°C for 1 hour.

[0135] Each coated test chip (hereafter referred to as "test sample") was first conditioned by irradiating it with 365-nanometer ultraviolet light for 10 minutes at a distance of approximately 14 centimeters to activate the photochromic material within the coating. The UVA (315-380 nm) irradiance on the test samples was measured with a LICOR® Model Li-1800 spectroradiometer and found to be 22.2 watts per square meter. Each test sample was then placed under a 500-watt high-intensity halogen lamp at a distance of approximately 36 centimeters for approximately 10 minutes to bleach (deactivate) the photochromic material. The irradiance on the test samples was measured with the LICOR® spectroradiometer and found to be 21.9 Klux. The test samples were then placed in a dark environment at room temperature (i.e., 70-75°F, i.e., 21-24°C) for at least one hour before being tested on an optical bench. Prior to the optical bench measurement, the test samples were measured for 390-nanometer ultraviolet absorbance.

[0136] The percent transmittance of Examples 1-11 and each of Comparative Examples CE1-CE10 was determined using CIE Y values ​​according to the CIE 15:2004 colorimetry method using a D65 illuminant and a 10° observer. * and b * The values ​​were measured using a Hunter UltraScan Pro unit according to CIE 15:2004 spatial colorimetry using a D65 illuminant and a 10° observer. * and b * Refers to the value. %T, a * , and b * The values ​​of %T are for samples containing photochromic dyes. o , a * o , and b * o The values ​​are for samples prepared without photochromic dye in the polyurethane coating. ΔE %T was calculated according to the following formula: ΔE %T =[(%T-%T o )2 +(a * -a * o ) 2 +(b * -b * o ) 2 ] 0.5

[0137] The BMP optical bench was equipped with two 150-watt ORIEL® Model #66057 xenon arc lamps, positioned at right angles to each other. The light path from Lamp 1 was directed through a 3 mm SCHOTT® KG-2 bandpass filter and appropriate neutral density filters to contribute the required UV and partial visible irradiance levels. The light path from Lamp 2 was directed through a 3 mm SCHOTT® KG-2 bandpass filter, a SCHOTT® shortwave 400 nm cutoff filter, and appropriate neutral density filters to provide supplemental visible irradiance. A 45° 2-inch x 2-inch 50 percent polka dot beam splitter was used for each lamp to mix the two beams. The irradiance intensity was adjusted using a combination of neutral density filters and the voltage control of the xenon arc lamps. Dedicated software, namely BMPSoft version 2.1e, was used in the BMP to control timing, irradiance, air cell and sample temperature, shutter, filter selection, and response measurements. A ZEISS® spectrophotometer, model MCS501, with a fiber optic cable to transmit light through the test sample was used for response and color measurements. Photopic response measurements were collected for each test sample. The output of the optical bench, i.e., the amount of light the test sample was exposed to, was 6.7 watts per square meter (W / m), integrated from 315 to 380 nm. 2The UVA and UVB wavelengths were adjusted to 50 klux, integrated from 380 to 780 nm. Measurements of this output setpoint were performed using an irradiance probe and a calibrated Zeiss spectrophotometer. The sample cell was fitted with a quartz window and a self-centering sample holder. The temperature within the sample cell was controlled at 23 °C by a modified Facis Model FX-10 instrument and software equipped with an environmental simulator. Measurements of the dynamic photochromic response and color of the test samples were performed using the same Zeiss spectrophotometer equipped with a fiber optic cable to transmit light from a tungsten halogen lamp through the test sample. A collimated monitor light beam from the fiber optic cable was maintained perpendicular to the test sample during its passage through the sample and directed toward a receiving fiber optic cable assembly attached to the spectrophotometer. The exact location of the sample placement within the sample cell was where the activating xenon arc beam and the monitor light beam intersected to form two concentric circles of light. The angle of incidence of the xenon arc beam at the sample placement point was approximately 30° from normal.

[0138] Response measurements of the change in optical density (ΔOD) from the unactivated or bleached state to the activated or colored state were determined by identifying the initial unactivated transmittance, opening the shutter from the xenon lamp, and measuring the activated transmittance at selected time intervals. The ΔOD at saturation is after 15 minutes of activation, and the fade half-life ("T") value is the time in seconds for the ΔOD of the activated form of the photochromic material in the coating to reach half of the ΔOD at 15 minutes at 73.4°F (23°C) after the activating light source is removed.

[0139] [Table 2]

[0140] [Table 3]

[0141] [Table 4]

[0142] [Table 5]

[0143] [Table 6]

[0144] The results shown in Table A above demonstrate that the use of the photochromic indeno-fused naphthopyran compounds of the present invention significantly reduced ΔE %T These low delta Δ %T The 7-position alkyl substituents provide photochromic articles with excellent indoor clarity for improved visibility in low-light conditions and desirable aesthetics. The 7-position alkyl group also demonstrates improved activated-state darkening over compounds without a 7-position substituent, which is necessary to provide comfort and protection when wearing lenses outdoors. The unexpected combination of excellent bleaching and darkening properties makes the indeno-fused naphthopyran compounds of the present invention with alkyl substituents at the 7-position ideal candidates for use in photochromic lenses.

[0145] The present invention has been described with reference to specific details of particular embodiments thereof. It is not intended that such details be considered limitations on the scope of the invention except insofar as they are included in the appended claims.

Claims

1. An indeno-fused naphthopyran having the following core skeletal structure (I): 【Chemical 1】 (In the formula, R １ is a substituted or unsubstituted alkyl group; R ２ represents a substituted or unsubstituted amino; substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted amides, substituted or unsubstituted urea, or a substituted or unsubstituted carbamate; R ３ and R ４ At least one of R is an electron-donating group, ３ and R ４ Hammett σ ｐ The sum of the values ​​is less than −0.40; R １ is a substituted alkyl group, the carbon atom of the alkyl group is directly bonded to the carbon atom at position 7, and the carbon atom of the alkyl group directly bonded to the carbon atom at position 7 is unsubstituted).

2. R １ is C １ ~C ２０ 2. The indeno-fused naphthopyran according to claim 1, wherein the alkyl group is a substituted or unsubstituted alkyl group represented by the formula:

3. R １ is unsubstituted C １ ~C ６ 3. The indeno-fused naphthopyran according to claim 1, wherein the indeno-fused naphthopyran is an alkyl group.

4. R ２ is selected from the group consisting of substituted or unsubstituted aryl, substituted or unsubstituted amino, substituted or unsubstituted alkyloxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkylthio, and substituted or unsubstituted arylthio.

5. R ２ The indeno-fused naphthopyran according to any one of claims 1 to 4, wherein is a substituted or unsubstituted aryl.

6. R ３ and R ４ The indeno-fused naphthopyran according to any one of claims 1 to 5, wherein at least one of the following is a substituted or unsubstituted amino group.

7. R ３ and R ４ The indeno-fused naphthopyran according to any one of claims 1 to 6, wherein at least one of the following is a substituted or unsubstituted cyclic amino group.

8. R ３ and R ４ 8. The indeno-fused naphthopyran of claim 7, wherein at least one of the following is a cyclic amino group that is a nitrogen-containing heterocycle selected from the group consisting of morpholino, piperidino, substituted piperazino, and pyrrolidino.

9. R ３ and R ４ are the same or different and each independently represent a substituted or unsubstituted alkoxy, or a substituted or unsubstituted amino.

10. R ３ and R ４ At least one of methoxy, morpholino, piperazino, substituted piperazino, and dialkyl(C １ ~C ６ 10. The indeno-fused naphthopyran according to any one of claims 1 to 9, wherein the indeno-fused naphthopyran is selected from the group consisting of:

11. An indeno-naphthopyran according to any one of claims 1 to 10, having the following core skeleton structure (Ia): 【Chemistry 2】 (In the formula, R １ , R ２ , R ３ , and R ４ are each as described above for core framework structure (I); R ５ and R ６ are each independently (i) hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heterocycloalkyl, aryl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; (ii) an alkoxy, hydroxyl, alkylthio, ketone, aldehyde, ester, carboxylic acid, carboxylate, siloxane, alkoxysilane, or polysiloxane; (iii) a group comprising a polyester, a polyether, a polycarbonate, a polyurethane, or a combination thereof; or (iv) R ５ and R ６ are taken together with the carbon atom at position 13 bonded thereto to form an aliphatic ring having 3 to 20 ring carbon atoms, a fused polycyclic ring having an aromatic ring or a heteroaromatic ring fused to the aliphatic ring, a heterocyclic ring having 3 to 20 ring atoms, or a fused polycyclic ring having an aromatic ring or a heteroaromatic ring fused to the heterocyclic ring).

12. R ５ and R ６ and each independently represents a substituted or unsubstituted alkyl.

13. R １ is unsubstituted C １ ~C ６ is alkyl; R ２ is substituted or unsubstituted phenyl; R ３ and R ４ However, each independently, C １ ~C ４ alkoxy or a nitrogen-containing heterocycle; R ５ and R ６ However, each independently C １ ~C ４ is alkyl; The indeno-fused naphthopyran of claim 11.

14. A photochromic composition comprising the indeno-fused naphthopyran according to any one of claims 1 to 13.

15. A photochromic article comprising the indeno-fused naphthopyran of any one of claims 1 to 13, the photochromic article is selected from an ophthalmic article, a display article, a window, a mirror, an active liquid crystal cell article, or a passive liquid crystal cell article; or the photochromic article is selected from an ophthalmic article, the ophthalmic article being selected from a corrective lens, a non-corrective lens, a contact lens, an intraocular lens, a magnifying lens, a protective lens, or a visor; or the photochromic article is selected from a display article, and the display article is selected from a screen, a monitor, or a security element; Photochromic articles.

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