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

Abstract

An indeno-fused naphthopyran having a core framework structure (I): (I) wherein R1 is a substituted or unsubstituted alkyl group; r2 is a substituted or unsubstituted amino group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted alkylthio group; a substituted or unsubstituted arylthio group; or substituted or unsubstituted amides, urea and carbamates; and at least one of R3 and R4 is an electron donating group wherein the sum of Hammett [sigma] p values of R3 and R4 is less than-0.40 wherein when R1 is a substituted alkyl group, the carbon atom of the alkyl group is directly bonded to the 7-position carbon atom and the carbon atom of the alkyl group directly bonded to the 7-position carbon atom is unsubstituted. # imgabs0 #

Description

Technical Field

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

[0002] Photochromic compounds undergo a transition 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 transition from an unactivated (e.g., whitish or substantially colorless) state to an activated (e.g., colored or dyed) state when exposed to actinic radiation. When the actinic radiation is removed, the photochromic compound reversibly transitions from the activated state back to a whitish unactivated state. "Thermoreversible photochromic compounds" are photochromic compounds that transition from an unactivated state to an activated state in response to actinic radiation, and return to an unactivated state in response to thermal energy. The activation reaction (from unactivated to activated) is primarily a photochemical reaction, while the deactivation reaction (from activated to unactivated) is primarily a thermal reaction.

[0003] Known photochromic compounds, such as photochromic indeno-fused naphthopyran compounds, exhibit the following advantages: good darkness in the activated state, and acceptable fading rate when converted back to the whitish unactivated state. However, in some cases, these photochromic compounds may exhibit an undesirable hue or color in the whitish unactivated state. This is often referred to as a "whitish cast". This whitish cast may adversely affect the aesthetics of an article, such as an optical article containing such a photochromic compound.

[0004] Photochromic ophthalmic lenses reduce glare for the lens wearer when exposed to solar (actinic) radiation that promotes rapid tinting of the lens, thereby reducing the amount of light reaching the wearer's eyes. When returning to an indoor environment, any lens tinting or tint that remains in the lens may be detrimental to the wearer from both a cosmetic and functional perspective. It is therefore desirable to provide a photochromic lens that is transparent when the lens wearer is indoors and is tinted / dyed when the wearer is outdoors, acting as a pair of sunglasses. This can be achieved by using photochromic dyes that provide high absorbance in an activated state, rapidly switching from a transparent (unactivated, indoor) state to a tinted (darkened, outdoor) state and back again. Photochromic dyes that have minimal residual color or tint when the wearer is indoors (i.e., in an unactivated state) are necessary to produce the highest quality photochromic lenses.

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

[0006] For example, the compounds described in U.S. Pat. No. 9,028,728 can exhibit a desired level of blue coloration in the activated state, but may be affected by residual color in the whitish state. This residual hue can be manifested as yellowness (b*) due to the absorption of the photochromic dye in the closed form into the high-energy visible region of the solar spectrum. The residual hue may also be the result of thermochromism of the dye, which causes the photochromic dye to maintain a lower level of the activated state when indoors and not fully recover to the unactivated state. This is usually measured as a decrease in the unactivated transmittance of the sample.

[0007] Further, known photochromic indeno-fused naphthopyran compounds having no substitution at the 7-position and a strong electron donor group on the 3,3'-aryl group can provide good white color, but may suffer from a darker activated state. The reduced activated outdoor darkness of such compounds, especially at warm temperatures, may limit photochromic lenses containing such compounds.

[0008] According to the following equation 1, ΔE ％T The transmittance percentage (%T), a* value and b* value (%T) of the unactivated photochromic layer relative to the transparent substrate to which the photochromic layer is applied are shown in Table 1. o , a*0, b*0).

[0009] ΔE ％T =[(%T-%T o ) 2 +(a*-a* o ) 2 +(b*-b* o ) 2 ] 0.5

[0010] Equation 1

[0011] In this case, in the unactivated state, ΔE ％T The lower the value, the less hue and color the sample has. The activated %T at 35°C indicates how dark the photochromic sample will become when exposed to actinic radiation under warm summer-like conditions.

[0012] The inventors have surprisingly found that indeno-fused naphthopyran compounds having alkyl substitution at position 7 can significantly reduce ΔE when combined with electron donating groups on the 3,3'-aryl groups compared to similar compounds having alkoxy groups at position 7. ％T It has also been found that the indeno-fused compounds of the present invention have improved activated darkness over structurally similar compounds which are not substituted at the 7-position. Summary of the invention

[0013] The present invention relates to an indeno-fused naphthopyran having the following core skeleton structure (I):

[0014]

[0015] in

[0016] R 1 is a substituted or unsubstituted alkyl group;

[0017] R 2 yes

[0018] i. substituted or unsubstituted amino;

[0019] ii. substituted or unsubstituted alkyl;

[0020] iii. substituted or unsubstituted alkenyl;

[0021] iv. substituted or unsubstituted alkynyl;

[0022] v. substituted or unsubstituted aryl;

[0023] vi. substituted or unsubstituted heteroaryl;

[0024] vii. substituted or unsubstituted alkoxy;

[0025] viii. substituted or unsubstituted aryloxy;

[0026] ix. substituted or unsubstituted alkylthio;

[0027] x. substituted or unsubstituted arylthio;

[0028] xi. substituted or unsubstituted amides;

[0029] xii. substituted or unsubstituted urea; or

[0030] xiii. substituted or unsubstituted carbamates; and

[0031] R 3 and R 4 At least one of them is an electron-donating group, wherein R 3 and R 4Hammett's σ p The sum of the values ​​is less than -0.40, and

[0032] When R 1 In the case of a substituted alkyl group, the carbon atom of the alkyl group is directly bonded to the carbon atom at the 7-position, and the carbon atom of the alkyl group bonded to the carbon atom at the 7-position is unsubstituted.

[0033] Compositions and articles comprising the indeno-fused naphthopyrans are also provided.

[0034] The features that characterize the present invention are particularly pointed out in the claims, which are attached to and constitute a part of this disclosure. These and other features of the present invention, its operating advantages and specific objects obtained by its use will be more fully understood from the following detailed description, in which non-limiting embodiments of the present invention are shown and described. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 A general scheme, Synthesis Part 1, is presented for an exemplary method for synthesizing intermediates used to prepare the photochromic compounds of the present invention.

[0036] Figure 2 A general scheme, Synthesis Part 2, of an exemplary method for preparing the photochromic compounds of the present invention is presented. DETAILED DESCRIPTION

[0037] As used herein, the articles "a," "an," and "the" include plural referents unless expressly and unequivocally limited to one referent otherwise.

[0038] As used herein, the term "includes" is synonymous with "comprises."

[0039] Unless otherwise indicated, all ranges or ratios disclosed herein should be understood to encompass any and all subranges or subratios contained therein. For example, a recited range or ratio of "1 to 10" should be considered to include any and all subranges between (and including) a minimum of 1 and a maximum of 10; that is, all subranges or subratios starting with a minimum of 1 or greater and ending with a maximum of 10 or less, such as, but not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.

[0040] As used herein, unless otherwise indicated, left-to-right representation of a linking group, such as a divalent linking group, includes other suitable orientations, such as but not limited to right-to-left orientation. For non-limiting illustration purposes, a divalent linking group or equivalently, the left-to-right representation of -C(O)O- includes its right-to-left representation or equivalently -O(O)C- or -OC(O)-.

[0041] Except in the operating examples, or where otherwise indicated, all numbers used in the specification and claims to indicate the amount of ingredients, reaction conditions, etc. should be understood to be modified in all cases by the term "about". "About" means plus or minus 25 percent of the value, such as plus or minus 10 percent of the value. However, it should not be considered to be limited to any analysis of these values ​​under the principle of equivalents.

[0042] As used herein, molecular weight values ​​of polymers, such as weight average molecular weight (Mw) and number average molecular weight (Mn), are determined by gel permeation chromatography using appropriate standards, such as polystyrene standards.

[0043] As used herein, the term "polymer" means homopolymers (eg, prepared from a single monomer species), copolymers (eg, prepared from at least two monomer species), and grafted polymers.

[0044] As used herein, the term "(meth)acrylate" and similar terms, such as "(meth)acrylic acid ester" means derivatives of acrylic acid and methacrylic acid, including acrylate ester, methacrylate ester, acrylamide, methacrylamide, acrylic acid and methacrylic acid. As used herein, the term "(meth)acrylic acid" means methacrylic acid and / or acrylic acid.

[0045] In some embodiments, the photochromic compounds of the present invention are also referred to herein as photochromic-dichroic compounds (eg, when they include one or more extending groups, such as L 1 ).

[0046] As described herein, the photochromic compounds of the present invention, including but not limited to photochromic compounds represented by Formula (I) and / or Formula (Ia), in each case may optionally further include one or more by-products resulting from the synthesis of such compounds.

[0047] As used herein, the term "photochromic" and similar terms (such as "photochromic compound") means having an absorption spectrum for at least visible radiation that changes in response to the absorption of at least actinic radiation. Further, as used herein, the term "photochromic material" means any substance suitable for displaying photochromic properties (such as suitable for having an absorption spectrum for at least visible radiation that changes in response to the absorption of at least actinic radiation) and including at least one photochromic compound.

[0048] As used herein, the term "actinic radiation" means electromagnetic radiation capable of inducing a response in a material, such as, but not limited to, transforming a photochromic material from one form or state to another, as discussed in further detail herein.

[0049] As used herein, the term "dichroic" means capable of absorbing one of at least two orthogonal plane-polarized components of transmitted radiation more strongly than the other.

[0050] As used herein, the term "photochromic-dichroic" and similar terms (e.g., photochromic-dichroic compound) means having and / or providing both photochromic properties (i.e., having an absorption spectrum for at least visible radiation that varies in response to at least actinic radiation) and dichroic properties (i.e., having a stronger absorption of one of two orthogonal plane-polarized components of at least transmitted radiation than the other).

[0051] As used herein, and unless otherwise specified or limited, the term "photochromic material" includes thermally reversible photochromic materials and compounds and non-thermally reversible photochromic materials and compounds. As used herein, the term "thermally reversible photochromic compound / material" means a compound / material that can be converted from a first state (e.g., a "transparent state") to a second state (e.g., a "colored state") in response to actinic radiation, and return to the first state in response to thermal energy. As used herein, the term "non-thermally reversible photochromic compound / material" means a compound / material that can be converted from a first state (e.g., a "transparent state") to a second state (e.g., a "colored state") in response to actinic radiation, and return to the first state in response to actinic radiation of substantially the same wavelength as the absorption of the colored state (e.g., cessation of exposure to such actinic radiation).

[0052] As used herein, the terms "first" and "second" are not intended to refer to any particular order or sequence, but rather to two different conditions or properties, for purposes of non-limiting illustration. For purposes of non-limiting illustration, the first state and the second state of the photochromic compound may differ in at least one optical property, such as, but not limited to, the absorption of visible radiation 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 each of the first state and the second state. For example, although not limited herein, the photochromic compounds of the present invention may be transparent in the first state and colored in the second state. Alternatively, the photochromic compounds of the present invention may have a first color in the first state and a second color in the second state.

[0053] 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, the optical article, element or device 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.

[0054] As used herein, the term "ophthalmic" means pertaining to or associated with the eye and vision. Non-limiting examples of ophthalmic articles or elements include corrective and non-corrective lenses (which include single vision or multifocal lenses, which may be segmented or non-segmented multifocal lenses (such as, but not limited to, bifocal lenses, trifocal lenses, and progressive lenses)), and other elements for correcting, protecting, or enhancing (cosmetic or other) vision (which include, but are not limited to, contact lenses, intraocular lenses, magnifying lenses, and protective lenses or goggles).

[0055] As used herein, the term "display" means a visible or machine-readable representation of information in the form of words, numbers, symbols, designs, or diagrams. Non-limiting examples of display elements include screens, monitors, and security elements, such as security markings.

[0056] As used herein, the term "window" means an aperture adapted to allow radiation to be transmitted therethrough. Non-limiting examples of windows include automotive and aircraft transparencies, windshields, filters, shutters, and optical switches.

[0057] As used herein, the term "mirror" means a surface that specularly reflects a significant portion of incident light.

[0058] As used herein, the term "liquid crystal cell" refers to a structure containing liquid crystal material that is capable of being ordered. A non-limiting example of a liquid crystal cell element is a liquid crystal display.

[0059] As used herein, spatial or directional terms, such as "left", "right", "inner", "outer", "above", "below", etc., relate to the present invention as depicted in the accompanying drawings. However, it should be understood that the present invention can assume various alternative orientations, and therefore, such terms should not be considered limiting.

[0060] As used herein, the terms "formed over", "deposited over", "provided over", "applied over", "residing over", or "positioned over" mean formed, deposited, provided, applied, applied, present, or positioned on an underlying element, or on a surface of an underlying element, but not necessarily in direct (or adjacent) contact therewith. 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.

[0061] As used herein, statements relating to ring positions, such as but not limited to position x (e.g., position 3 or position 13), refer to specific positions in the ring structure (e.g., core skeleton structure) of a chemical compound (e.g., the indeno-fused-ring photochromic compound of the present invention), and are depicted herein according to some embodiments by numbers within the ring structure of representative chemical formulae such as but not limited to Formula (I) and / or (Ia).

[0062] "Core skeleton structure" means a compound comprising at least the skeleton structure depicted in the relevant formula. The core skeleton structure is provided for the purpose of identifying the numbered ring positions. However, it should be understood that, unless specifically shown to the contrary, the core skeleton structure may have one or more atoms or one or more groups (not specifically shown in the corresponding molecular formula) bonded to one or more of the numbered ring positions on the core skeleton structure, which may be the same or different from each other.

[0063] The photochromic compounds of the present invention are referred to herein with reference to the term "core skeleton structure", which may be represented by one or more formulas, such as but not limited to formula (I) and / or (Ia).

[0064] All documents or portions of documents (such as but not limited to issued patents and patent applications) mentioned herein and unless otherwise indicated, are deemed to be "incorporated by reference" in their entirety.

[0065] As used herein, the recitation of a "substituted" group refers to a group including, but not limited to, an alkyl, heterocycloalkyl, aryl, and / or heteroaryl group in which at least one hydrogen has been replaced or substituted by 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, an alkenyl, an alkynyl, a haloalkyl, a perhaloalkyl, a heterocycloalkyl, an aryl, a heteroaryl, an alkoxy group, a hydroxyl group, an alkylthio group, an arylthio group, a phosphate group, a sulfonic acid group, a sulfonate group, a ketone group, an aldehyde group, an ester group, a carboxylic acid group, a carboxylate group, a siloxane group, a Alkyl groups, alkoxysilane groups, polysiloxane groups, amide groups, amino groups, carbamate groups, carbonate groups, urea groups, polyester groups, polyether groups, polycarbonate groups, polyurethane groups, acrylate groups, methacrylate groups, arylamino groups, such as diphenylamino groups; alkylamino groups, such as dimethylamino groups; cyclic amino groups, such as morpholinyl, piperidinyl, piperazinyl, or pyrrolidinyl groups; heteroaromatic compounds, such as imidazole, pyrrole, indole or carbazole; or combinations thereof; or any other group as long as it does not adversely affect the performance properties of the compound, such as the photochromic performance properties of the compound.

[0066] "Aryl" refers to an aromatic cyclic monovalent hydrocarbon group, and the term "aromatic" refers to a cyclic conjugated hydrocarbon whose stability (due to delocalization) is significantly greater than the stability of the assumed local structure. Examples of aryl groups include C6-C 14 Aryl groups such as, but not limited to, phenyl, naphthyl, phenanthrenyl, and anthracenyl.

[0067] As used herein, the description of "halogen-substituted" and related terms (such as but not limited to haloalkyl, haloalkenyl, haloalkynyl, halogenated aryl and halogenated heteroaryl) means a group in which at least one, and at most and including all available hydrogen groups are replaced by halogen groups. The term "halogen-substituted" includes "perhalogen-substituted". As used herein, the term perhalogen-substituted group and related terms (such as but not limited to perhaloalkyl, perhaloalkenyl, perhaloalkynyl, perhaloaryl or perhalogenated heteroaryl) means a group in which all available hydrogen groups are replaced by halogen groups. For example, perhalomethyl is -CX3; perhalophenyl is -C6X5, wherein X represents one or more halogen groups, such as but not limited to F, Cl or Br.

[0068] As used herein, the description of a "straight chain or branched chain" group (such as a straight chain or branched chain alkyl) is understood herein to include: methylene or methyl; a straight chain (or "straight chain") group, such as a straight chain C1-C 25 Alkyl; and appropriately branched groups, such as branched C3-C 25 alkyl.

[0069] As used herein, the term "alkyl" refers to a linear or branched, cyclic or non-cyclic C1-C 25 Alkyl. A straight chain or branched chain alkyl may include C1-C 25 Alkyl, such as C1-C 20 Alkyl, such as C2-C 10 Alkyl, such as C1-C 12 Alkyl, such as C1-C6 alkyl. 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. Alkyl groups may include "cycloalkyl". As used herein, the term "cycloalkyl" means a suitable cyclic group, such as, but not limited to, C3-C6 alkyl. 12 Cycloalkyl (including but not limited to cyclic C5-C7 alkyl, or cyclic C3-C 10 Alkyl). Examples of cycloalkyl include, but are not limited to, those further listed herein. As used herein, the term "cycloalkyl" also includes: bridged ring polycycloalkyl group (or bridged ring polycyclic alkyl group), such as but not limited to bicyclo[2.2.1]heptyl (or norbornyl) and bicyclo[2.2.2]octyl; and condensed ring polycycloalkyl (or condensed ring polycycloalkyl (polycyclic alkyl)), such as but not limited to octahydro-1H-indenyl, and decahydronaphthyl.

[0070] As used herein, the term "heterocycloalkyl" refers to a suitable cyclic group, such as but not limited to C2-C 12 Heterocycloalkyl, such as C5-C7 heterocycloalkyl, such as C2-C 10 Heterocycloalkyl, and it has at least one heteroatom in the cyclic ring, such as but not limited to O, S, N, P, and combinations thereof. Examples of heterocycloalkyl include, but are not limited to, imidazolyl, tetrahydrofuranyl, tetrahydropyranyl, and piperidinyl. As used herein, the term "heterocycloalkyl" also includes: bridged polycyclic heterocycloalkyl, such as but not limited to 7-oxabicyclo[2.2.1]heptyl; and fused polycyclic heterocycloalkyl, such as but not limited to octahydrocyclopenta[b]pyranyl and octahydro-1H-isochromenyl.

[0071] As used herein, the term "heteroaryl" includes, but is not limited to, C3-C 18 Heteroaryl, such as but not limited to C3-C 10 Heteroaryl (including fused polycyclic heteroaryl) and means an aryl having at least one heteroatom in an aromatic ring or in at least one aromatic ring in the case of a fused polycyclic heteroaryl. Examples of heteroaryl include, but are not limited to, furanyl, pyranyl, pyridyl, isoquinoline, and pyrimidinyl.

[0072] As used herein, the term "polycyclic-aryl-alkyl group" and similar terms, such as polycyclic-alkyl-aryl group, polycyclo-aryl-alkyl group, and polycyclo-alkyl-aryl group, refer to a fused polycyclic group comprising at least one aryl ring and at least one cycloalkyl ring fused together to form a fused ring structure. For non-limiting purposes, examples of polycyclic-aryl-alkyl groups include, but are not limited to, indenyl, 9H-fluorenyl, cyclopentanaphthenyl, and indacenyl.

[0073] As used herein, the term "aralkyl" includes, but is not limited to, C6-C 24 Arylalkyl, such as but not limited to C6-C 10 Aralkyl refers to an alkyl group substituted by an aryl group. Examples of aralkyl groups include, but are not limited to, benzyl and phenethyl.

[0074] Representative alkyl includes but is not limited to methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl. Representative alkenyl includes but is not limited to vinyl, allyl and propenyl. Representative alkynyl includes but is not limited to ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, and 2-butynyl. Representative cycloalkyl includes but is not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl substituents. Representative heterocycloalkyl includes but is not limited to imidazolyl, tetrahydrofuranyl, tetrahydropyranyl and piperidinyl. Representative aryl includes but is not limited to phenyl, naphthyl, anthracenyl, phenanthrenyl and tetraphenyl (including structural isomers thereof). Representative heteroaryl includes but is not limited to furanyl, pyranyl, pyridinyl, isoquinolinyl, and pyrimidinyl. Representative aralkyl includes but is not limited to benzyl and phenethyl.

[0075] As used herein, the term "nitrogen-containing heterocycle" is a cyclic amino group, including but not limited to a nitrogen-containing ring, wherein the nitrogen-containing ring is bonded through a ring nitrogen. Examples of nitrogen-containing heterocycles are those cyclic amino groups, including but not limited to morpholinyl, piperidinyl, piperazinyl, and pyrrolidinyl; and heteroaromatic compounds, such as imidazole, pyrrole, indole, and carbazole.

[0076] As used herein, "at least one of" is synonymous with "one or more of," whether the elements are listed in conjunction or separately. For example, the phrases "at least one of A, B, and C" and "at least one of A, B, or C" each mean any one of A, B, or C, or any combination of any two or more of A, B, or C. For example, A alone; or B alone; or C alone; or A and B; or A and C; or B and C; or all of A, B, and C.

[0077] As used herein, "selected from" or "chosen from" is synonymous with "at least one of...", whether the elements are listed in conjunction or separately. For example, the phrases "selected from A, B, and C" and "selected from A, B, or C" each mean any one of A, B, or C, or any combination of any two or more of A, B, or C. For example, A alone; or B alone; or C alone; or A and B; or A and C; or B and C; or all of A, B, and C.

[0078] The discussion of the present invention may describe certain features as "specifically" or "preferably" within certain limitations (e.g., "preferably", "more preferably" or "even more preferably" within certain limitations). It is to be understood that the present invention is not limited to these specific or preferred limitations, but encompasses the full scope of the present disclosure.

[0079] The present invention comprises, consists of, or consists essentially of the following aspects of the invention in any combination.

[0080] According to the present invention, indeno-fused naphthopyran compounds can be represented by one or more of the core skeleton structures described below. Each available numbered ring position (e.g., 5, 6, 8, 9, 10, 12, and / or 13) of the core skeleton structure with formula (I) can have a hydrogen or a group other than hydrogen covalently bonded thereto, such as a group described herein. Examples of such groups are described below.

[0081]

[0082] Referring to formula (I), R 1 is a substituted or unsubstituted alkyl group, such as C1 to C 20 substituted or unsubstituted alkyl or substituted or unsubstituted C1 to C6 alkyl. 1 When it 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. 1It may also be a substituted or unsubstituted alkyl radical, which may be interrupted by heteroatoms, provided that the carbon atom in position 7 is directly bonded to a carbon atom of the alkyl radical. 1 Can include but not limited to substituted or unsubstituted alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl or heptyl, each of which can be substituted or unsubstituted independently. Suitable substituents can include those described above. For example, each alkyl substituent can be independently selected from one or more of the following in each case: 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 its combination; Or any other group, as long as it does not adversely affect the performance characteristics of the compound, such as the photochromic performance characteristics of the compound. In addition, R1 can be unsubstituted C1 to C6 alkyl.

[0083] In addition, referring to formula (I), R 2 It may be a substituted or unsubstituted amino group, 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 an alkyl and / or aryl substituent, or a cyclic amino group, such as a substituted or unsubstituted nitrogen-containing heterocycle; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted alkylthio group; a substituted or unsubstituted arylthio group; a substituted or unsubstituted amide, including, for example, a substituted amide having an aryl or alkyl substituent; a substituted or unsubstituted urea; and a substituted or unsubstituted carbamate. For the purposes of the present invention, when R 2 is a substituted or unsubstituted amide group or a substituted or unsubstituted carbamate group, as the case may be, R 2 The amide group or the urethane group is bonded to the carbon atom at position 11 via the nitrogen atom.

[0084] R 2 may be selected from the group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, and a substituted or unsubstituted arylthio group. 2 The aryl group may be substituted or unsubstituted.

[0085] Suitable substituents may include those described above. For example, each alkyl substituent, each heterocycloalkyl substituent, each aryl substituent, and each heteroaryl substituent herein may be independently selected from one or more of the following in each case: halogen, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, perhaloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, hydroxyl, alkylthio, arylthio, phosphate; sulfonic acid group; sulfonate, ketone, aldehyde, ester, carboxylic acid, carboxylate, siloxane, alkoxysilane, polysiloxane, amide, amine, carbamate, Carbonate, urea, polyester group, polyether group, polycarbonate group, polyurethane group, acrylate group, methacrylate group, arylamino group, such as diphenylamino group; alkylamino group, such as dimethylamino group; cyclic amino group, such as nitrogen-containing heterocyclic compounds, such as morpholinyl, piperidinyl, piperazinyl or pyrrolidinyl; heteroaromatic compounds, such as imidazole, pyrrole, indole or carbazole; or a combination thereof; or any other group as long as it does not adversely affect the performance properties of the compound, such as the photochromic performance properties of the compound.

[0086] Further referring to formula (I), R 3 and R 4 At least one of them is an electron-donating group, wherein R 3 and R 4 Hammett's σ p The sum of the values ​​is less than -0.40. The relative strength of electron donor groups is often expressed by the Hammett σ value or σ p The Hammett σ of various substituents is described by p Lists of values ​​can be found in C. Hansch, A. Leo and RW 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. Hammett σ for selected exemplary substituents p The values ​​are listed in Table 1 below.

[0087] Table 1 - Hammett σ for selected substituents p value

[0088]

[0089]

[0090] For example, R 3 and R 4At least one of R3 and R4 may be a substituted or unsubstituted amino group. In addition, 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: morpholinyl, piperidinyl, substituted piperazinyl and pyrrolidinyl. Further, R 3 and R 4 may be the same or different, and may each independently be a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted amino group. 3 and R 4 At least one of the groups may be selected from the group consisting of a methoxy group, a morpholinyl group, a piperazinyl group, a substituted piperazinyl group, and a dialkyl (C1-C6) amino group.

[0091] Additionally or alternatively, the indeno-fused naphthopyran compounds of the present invention may be represented by a core skeleton structure having formula (Ia):

[0092]

[0093] Referring to formula (Ia), R 1 , R 2 , R 3 and R 4 is as previously described for formula (I).

[0094] As described above, in the absence of specific substituents, the remaining numbered ring positions (e.g., 5, 6, 8, 9, 10 and / or 12) of the core backbone structure of Formula (Ia) can have hydrogen or groups other than hydrogen covalently bonded thereto, such as, for example, groups described herein.

[0095] Further referring to formula (Ia), R 5 and R 6 Each of is independently:

[0096] (i) hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heterocycloalkyl, allyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

[0097] (ii) alkoxy, hydroxy, alkylthio, ketone, aldehyde, ester, carboxylic acid, carboxylic acid ester, siloxane, alkoxysilane, or polysiloxane;

[0098] (iii) a group comprising polyester, polyether, polycarbonate, polyurethane, or a combination thereof; or

[0099] (iv) R 5 and R 6Together with the carbon atom at position 13 bonded thereto, it forms an aliphatic ring having 3 to 20 ring member carbon atoms, a condensed polycyclic ring having an aromatic ring or an aromatic heterocyclic ring condensed to the above aliphatic ring, a heterocyclic ring having 3 to 20 ring member atoms, or a condensed polycyclic ring having an aromatic ring or an aromatic heterocyclic ring condensed to the above heterocyclic ring.

[0100] R 5 and R 6 Each of R can be independently substituted or unsubstituted alkyl. 5 and R 6 can be independently selected from the group consisting of: C1 to C6 straight or branched chain alkyl and C5 to C 10 Suitable substituents may include those described above. For example, each alkyl substituent, each heterocycloalkyl substituent, each aryl substituent, and each heteroaryl substituent herein may be independently selected in each case from one or more of the following: halogen, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, perhaloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, hydroxyl, alkylthio, arylthio, phosphate, sulfonic acid group, sulfonate, ketone, aldehyde, ester, carboxylic acid, carboxylate, siloxane, alkoxysilane, polysiloxane, amide, amine, carbamate, carbonate, urea, polyester group, polyether group, polycarbonate group, polyurethane group, acrylate group, methacrylate group, arylamino group, such as diphenylamino; alkylamino group, such as dimethylamino; cyclic amino group, such as morpholino, piperidinyl or pyrrolidinyl; heteroaromatic compound, such as imidazole, pyrrole, indole or carbazole; or a combination thereof; or any other group, as long as it does not adversely affect the performance properties of the compound, such as the photochromic performance properties of the compound.

[0101] Referring to formula (Ia), R 1 It may be an unsubstituted C1 to C6 alkyl group; R 2 It can be substituted or unsubstituted phenyl; R 3 and R 4 Each independently may be a C1 to C4 alkoxy group or a nitrogen-containing heterocycle; and R 5 and R 6 Each independently may be a C1 to C4 alkyl group.

[0102] According to the present invention, the indeno-fused naphthopyran compound can be prepared according to methods recognized in the art. Figure 1 and 2 , according to the present invention, the general synthetic scheme for preparing the photochromic compounds, namely, Synthesis Part 1 and Synthesis Part 2 are described as follows.

[0103] Synthesis part 1

[0104] Step 1

[0105] Grignard reagents can be prepared from aryl bromides and reacted with acid chlorides to form the corresponding benzophenones.

[0106]

[0107] Step 2

[0108] Benzophenones can be subjected to a Stobbe condensation to form Stobbe acids.

[0109]

[0110] Step 3

[0111] Carboxylic acids can undergo acid-catalyzed cyclization at elevated temperatures using acetic anhydride and a cosolvent.

[0112]

[0113] Step 4

[0114] The acetoxy group can undergo acid-catalyzed methanolysis in methanol at elevated temperature to give naphthols.

[0115]

[0116] Step 5

[0117] The methyl ester is reacted with two to six equivalents of a Grignard reagent, optionally in the presence of lanthanum (III) chloride-lithium chloride salt (LaCl3-2LiCl), to form a tertiary alcohol.

[0118]

[0119] Step 6

[0120] The tertiary alcohol can then undergo acid-catalyzed dehydration followed by an intramolecular Friedel-Crafts reaction to afford the indeno-fused naphthol.Naphthol 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.

[0121]

[0122] Synthesis part 2

[0123] Bromine can be cross-coupled with arylboronic acids using standard Suzuki cross-coupling conditions. Alternatively, palladium-catalyzed cross-coupling of bromine with alkyl or aryl thiols using tris(dibenzylideneacetone)dipalladium(0) and Xantphos ligands at elevated temperatures can produce thioether substitutions. 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.

[0124] Each of the resulting naphthols can be reacted with a diarylpropargyl alcohol under known conditions to produce the desired indeno-fused naphthopyran.

[0125] Figure 1 Depicted is a procedure for synthesizing an indeno-fused naphthol intermediate compound for preparing the indeno-fused naphthopyran compound of the present invention according to the steps described above in Synthesis Section 1. Figure 2 Depicted is a procedure for providing the desired substituents at the 7- and 11-positions of the indeno-fused naphthopyran compounds of the present invention according to the steps described above in Synthesis Section 2.

[0126] According to the present invention, there is also provided a photochromic composition comprising at least one indeno-fused naphthopyran compound according to the present invention, such as those represented by formula (I) and / or (Ia), as previously described herein.

[0127] The photochromic composition may include: (i) an organic material, wherein the organic material is at least one of a polymer material, an oligomeric material, or a monomeric material; and (ii) a photochromic indeno-fused naphthopyran compound according to the present invention, which is incorporated into at least a portion of the organic material. The photochromic compound may be incorporated into a portion of the organic material by the following methods, including but not limited to at least one of blending or combining the photochromic compound with the organic material or a precursor of the organic material. As used herein with reference to the incorporation of a photochromic compound into an organic material, the terms "blending" and "blended" mean that the photochromic compound / material is mixed or blended with at least a portion of the organic material, but not combined with the organic material. Further, as used herein with reference to the incorporation of a photochromic compound into an organic material, the terms "combining" or "combined" mean that the photochromic compound / material is connected to a portion of the organic material or its precursor, such as through one or more covalent bonds. For example, although not limited herein, the photochromic material may be connected to the organic material through a reactive substituent.

[0128] When the organic material is a polymer material, the photochromic indeno-fused naphthopyran compound can be incorporated into at least a portion of the polymer material or at least a portion of a monomer material or oligomer material that forms the polymer material. For example, the photochromic indeno-fused naphthopyran compound having a reactive substituent according to the present invention can be combined with an organic material such as a monomer, oligomer or polymer, the organic material having a group with which the reactive portion can react, or the reactive portion can react as a comonomer in a polymerization reaction to form the organic material, such as a copolymerization process.

[0129] As discussed above, in the case of some embodiments, the photochromic composition according to the present invention may include an organic material selected from a polymeric material, an oligomeric material and / or a monomeric material. Examples of polymeric materials that can be used with the photochromic composition of the present invention include, but are not limited to: poly(carbonates), copolymers of ethylene and vinyl acetate; copolymers of ethylene and vinyl alcohol; copolymers of ethylene, vinyl acetate and vinyl alcohol (such as those produced by partial saponification of copolymers of ethylene and vinyl acetate); cellulose acetate butyrate; poly(urethane); poly(acrylate); poly(methacrylate); epoxy resin; aminoplast functional polymer; poly(anhydride); poly(ureaurethane); N-alkoxymethyl(meth)acrylamide functional polymer; poly(siloxane); poly(silane); and combinations and mixtures thereof. Additional types and examples of polymeric materials that can be used with the photochromic composition of the present invention include, but are not limited to, those disclosed in U.S. Pat. No. 9,028,728B2, column 39, line 45 to column 40, line 67, the enumerated portion of which is incorporated herein by reference.

[0130] Further, the indeno-fused naphthopyran photochromic compounds according to 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 (at column 2, line 39 to column 8, line 41) and 6,555,028 (at column 2, line 65 to column 12, line 56), the enumerated 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, although not limited herein, mixtures of photochromic compounds can be used to obtain certain activated colors, such as near-neutral gray or near-neutral brown. See, for example, U.S. Pat. No. 5,645,767 at column 12, line 66 to column 13, line 19 (the enumerated portions of which are incorporated herein by reference), which describes parameters defining neutral gray and brown.

[0131] Examples of other types of photochromic compounds 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, spirofluoren[1,2-b]pyrans, phenanthropyrans, quinopyrans, fluoranthopyrans, spiropyrans, benzoxazines, naphthoxazines, spiro(dihydroindole)naphthoxazines, spiro(dihydroindole)pyridobenzoxazines, spiro(dihydroindole)fluoranthopyrans, spiro(dihydroindole)quinoxazines, fulgides, fulgimides, diarylethenes, diarylalkylethylenes, diarylalkenylethylenes, thermally reversible photochromic compounds, and non-thermally reversible photochromic compounds, and mixtures thereof. Additional 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 US Pat. No. 9,028,728 B2 at column 34, line 20 to column 35, line 13, the enumerated portion of which is incorporated herein by reference.

[0132] The photochromic compositions of the present invention may include at least one of the following: a complementary photochromic material (including one or more of those other photochromic materials and compounds previously described herein), a photoinitiator, a thermal initiator, a polymerization initiator, a solvent, a light stabilizer, a thermal stabilizer, a release agent, a rheology modifier, a leveling agent, a free radical scavenger, and / or an adhesion promoter.

[0133] The photochromic composition according to the present invention may be a photochromic coating composition. The photochromic coating composition of the present invention may comprise: a photochromic indeno-fused naphthopyran compound according to the present invention, as described herein previously with respect to formula (I) and / or (Ia); an optionally curable resin composition; and optionally a solvent. The photochromic coating composition may be in the form of liquid coatings and powder coatings recognized in the art. The photochromic coating composition of the present invention may be a thermoplastic or thermosetting coating composition. The photochromic coating composition may be a curable or thermosetting coating composition.

[0134] The curable resin composition of the 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 polymer reactant; and a second reactant (or component) having a functional group that is a crosslinking agent, which is reactive to the functional group of the first reactant and can form a covalent bond therewith. The first and second reactants of the curable resin composition of the curable photochromic coating composition may each independently include one or more functional substances, and each is present in an amount sufficient to provide a cured photochromic coating having a desired physical property, such as a combination of smoothness, optical clarity, solvent resistance, and hardness.

[0135] 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: curable resin compositions comprising epoxide functional polymers (e.g., (meth) acrylic polymers containing (meth) glycidyl acrylate residues) and epoxide reactive crosslinkers (e.g., containing active hydrogen, such as hydroxyl, thiol and amine); and curable resin compositions comprising active hydrogen functional polymers (e.g., hydroxyl, thiol and / or amine functional polymers) and blocked (or blocked) isocyanate functional crosslinkers. "Blocked (or blocked) isocyanate functional crosslinkers" means a crosslinker having two or more blocked isocyanate groups that can be deblocked (deblocked) under curing conditions (e.g., at elevated temperatures) to form free isocyanate groups and free blocked groups. The free isocyanate groups formed by the deblocking of the crosslinker are preferably capable of reacting with the active hydrogen groups of the active hydrogen functional polymer (e.g., with the hydroxyl groups of the hydroxyl functional polymer) and forming substantially permanent covalent bonds therewith. Additional 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: paragraphs

[0176] to

[0190] of WO 2016 / 142496 A1; and paragraphs

[0005] ,

[0037] to

[0051] ,

[0056] to

[0059] , and

[0063] to

[0065] of WO 2017 / 030545 A1, the exemplary portions of which are incorporated herein by reference.

[0136] The curable photochromic coating composition according to the present invention may optionally contain additives such as waxes for flow and wetting, flow regulators (e.g., poly(2-ethylhexyl) acrylate), auxiliary resins for modifying and optimizing coating properties, antioxidants, and ultraviolet (UV) light absorbers. Examples of useful antioxidants and UV light absorbers include those commercially available from BASF under the trademarks IRGANOX and TINUVIN. These optional additives are typically present in an amount of up to 20 weight percent (e.g., from 0.5 to 10 weight percent) based on the total weight of the resin solids of the curable resin composition when used.

[0137] The photochromic composition, photochromic article and photochromic coating composition according to the present invention may further include additives recognized in the art that help or assist the processing and / or performance of the composition or article. Non-limiting examples of such additives include photoinitiators, thermal initiators, polymerization initiators, solvents, light stabilizers (such as but not limited to ultraviolet light absorbers and light stabilizers, such as hindered amine light stabilizers (HALS)), thermal stabilizers, release agents, rheology modifiers, leveling agents (such as but not limited to surfactants), free radical scavengers, adhesion promoters (such as hexanediol diacrylate and coupling agents), and combinations and mixtures thereof.

[0138] The photochromic indeno-fused naphthopyran compounds of the present invention can be used in such amounts (or ratios) that the composition, organic material, or substrate (e.g., photochromic articles and photochromic coatings) to which the photochromic indeno-fused naphthopyran compounds are incorporated or otherwise attached exhibits desired optical properties. The amount and type of photochromic material can be selected so that the composition, organic material, or substrate is transparent or colorless when the photochromic indeno-fused naphthopyran compound is in a closed form (e.g., in a whitish or unactivated state), and can exhibit a desired resulting color when the photochromic compound (e.g., the photochromic indeno-fused naphthopyran of the present invention) is in an open form (e.g., when activated by actinic radiation). The exact amount of photochromic material used in the various photochromic compositions and articles described herein is not critical, provided that a sufficient amount is used to produce the desired effect. The specific amount of photochromic material used can depend on various factors such as, but not limited to, the absorption characteristics of the photochromic compound, the desired color and color intensity upon activation, and the method used to incorporate or attach the photochromic material to the substrate.

[0139] The photochromic composition according to the present invention may contain the indeno-fused naphthopyran compound according to the present invention, including the compound represented by formula (I) and / or (Ia), in an amount ranging from 0.01 to 40 weight percent, such as from 0.05 to 15 weight percent, such as from 0.1 to 5 weight percent, based on the weight of the photochromic composition. For further non-limiting purposes, the amount of the photochromic compound / material including the compound represented by formula (I) and / or (Ia) incorporated into the organic material may range from 0.01 to 40 weight percent, such as from 0.05 to 15 weight percent, such as from 0.1 to 5 weight percent, based on the weight of the organic material.

[0140] 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). These photochromic articles can be prepared by methods recognized in the art, such as by imbibition, cast-in-place, coating, in-mold coating, overmolding, and lamination.

[0141] For example, these photochromic articles can be selected from ophthalmic articles, display articles, windows, mirrors, active liquid crystal cell articles, and passive liquid crystal cell articles.

[0142] Additionally, the photochromic articles of the present invention may be ophthalmic articles, and these ophthalmic articles may be selected from corrective lenses, non-corrective lenses, contact lenses, intraocular lenses, magnifying lenses, protective lenses, and goggles.

[0143] Further, the photochromic articles of the present invention may be display articles, and these display articles may be selected from screens, monitors, and security elements.

[0144] 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.

[0145] Examples

[0146] The following examples are provided to illustrate the preparation of the indeno-fused naphthopyran compounds of the present invention.

[0147] Example 1

[0148] Step 1

[0149] Magnesium chips (5.33 g) and iodine (catalyst) were vigorously stirred in anhydrous tetrahydrofuran (50 mL) for 30 minutes under nitrogen. The mixture was then cooled to -5 ° C in salt water and an ice bath. Then 3-bromotoluene (3.75 g) dissolved in anhydrous tetrahydrofuran (10 mL) was added dropwise to the reaction mixture. After 15 minutes, an exothermic curve was observed. Additional 3-bromotoluene (21.25 g) dissolved in anhydrous tetrahydrofuran (30 mL) was added dropwise at a rate keeping the temperature below 5 ° C. After completion, the mixture was kept for one hour and then decanted into the second reaction vessel, leaving unreacted magnesium chips. The second reaction vessel was stirred under nitrogen and placed in an ice bath. Double [2-(N, N,-dimethylaminoethyl)] ether (23.42 g) dissolved in anhydrous tetrahydrofuran (20 mL) was added dropwise within 10 minutes while keeping the temperature below 5 ° C. After completion, the mixture was kept for one hour. In 15 minutes, 4-bromobenzoyl chloride (32.08g) was then added to the reaction mixture in batches, while keeping the temperature below 5 ℃. The reaction was kept for two hours, then heated to room temperature and kept for 16 hours. The reaction mixture was poured into a mixture of 10% hydrochloric acid aqueous solution (v / v) and ice, and extracted twice with dichloromethane. The organic layer merged was washed with saturated sodium bicarbonate aqueous solution, dried over sodium sulfate, and concentrated under reduced pressure. The gained residue was purified using flash chromatography on silica gel with a mixture of 95% hexane and 5% ethyl acetate. The fraction containing the desired product was merged and concentrated under reduced pressure. The gained solid was ground in a mixture of 93% hexane and 7% ethyl acetate and then collected by filtration to obtain white solid (4-bromophenyl) (m-tolyl) ketone (27.80g, 69% yield).

[0150] Step 2

[0151] The product (27.80g) and dimethyl succinate (20.67g) from step 1 are combined and stirred vigorously in toluene (556mL), and are placed in an ice bath. Potassium tert-amyl alcohol solution (1.7M in toluene, 101mL) is added dropwise in 30 minutes. After another two hours, the reaction mixture is poured into ice water. Concentrated hydrochloric acid is added to water layer and ice until pH reaches 1. The water layer is then extracted with dichloromethane twice. The organic layer washed with salt water combined, dried over sodium sulfate, and concentrated under reduced pressure to obtain amber oil (E) -4- (4- bromophenyl) -3- (methoxycarbonyl) -4- (m-tolyl) but-3-enoic acid (39.3g, 100% yield).

[0152] Step 3

[0153] The product (39.3 g) from step 2 and acetic anhydride (41.2 g) were stirred in xylene (118 mL). The solution was heated to 90 ° C for 2 hours under a nitrogen atmosphere. The temperature was then increased to 140 ° C for 1 hour. The solution was cooled to room temperature and concentrated under reduced pressure to obtain 4-acetoxy-1-(4-bromophenyl)-7-methyl-2-naphthoic acid methyl esters (37.5 g, 90% yield) as an amber oil.

[0154] Step 4

[0155] The product (37.5g) from step 3 is dissolved in methanol (563mL) and concentrated hydrochloric acid (3.75mL) is added thereto. The solution is heated to 65°C under nitrogen for 4 hours, then cooled to room temperature and slowly poured into a mixture of saturated sodium bicarbonate aqueous solution and ice while stirring vigorously. The mixture is extracted twice with dichloromethane. The combined organic layer is washed with salt water, dried over sodium sulfate, and concentrated under reduced pressure. The obtained residue is eluted with methylene chloride on silica gel for chromatographic separation. The purer fractions determined by HPLC area % are combined and concentrated under reduced pressure. The obtained oily matter is recrystallized in a mixture of 90% hexane and 10% ethyl acetate to produce 1-(4-bromophenyl)-4-hydroxy-7-methyl-2-naphthoic acid methyl esters (6.5g, 19% yield) as a white crystalline solid.

[0156] Step 5

[0157] Lanthanum chloride (7.93g) and lithium chloride (4.11g) are stirred in anhydrous tetrahydrofuran (90mL) under nitrogen.Mixture is heated to 55 ℃ and continues 16 hours and then is cooled to room temperature.The product (6.00g) from step 4 is added in the reaction mixture, and then the container is cooled to-15 ℃.In 50 minutes, the solution of propylmagnesium chloride (2.0M in diethyl ether, 49mL) is added dropwise in the reaction, while keeping the temperature between-15 ℃ and-10 ℃.After keeping 2 hours at this temperature, reaction mixture is poured in the mixture of 10% hydrochloric acid aqueous solution (v / v) and ice, and extracted twice with ethyl acetate.The organic layer merged is washed with salt water and dried over sodium sulfate, then by a small section of silica gel plug while washing with ethyl acetate. The mother liquor was concentrated under reduced pressure to give 4-(4-bromophenyl)-3-(4-hydroxyhept-4-yl)-6-methylnaphthalen-1-ol (6.0 g, 87% yield) as an amber oil.

[0158] Step 6

[0159] The product (6.91 g) and p-toluenesulfonic acid monohydrate (0.03 g) from step 5 are dissolved in toluene (104 mL) and heated to 110 ° C for 3 hours under nitrogen using a Dean-Stark trap. The solution is then cooled to 60 ° C. Bismuth trifluoromethanesulfonate (0.11 g) is added and the solution is heated to 90 ° C for 45 minutes, then cooled to room temperature and filtered through a silica plug while washing with dichloromethane. The mother liquor is concentrated under reduced pressure and then recrystallized in hexane to produce 9- bromo-2-methyl-7,7-dipropyl-7H-benzo[c]fluorene-5-ol (5.3 g, 80% yield) as a white solid.

[0160] Step 7

[0161] The product from step 6 (1.67g), 1-(3-fluoro-4-methoxyphenyl)-1-(4-morpholinylphenyl)prop-2-yn-1-ol (2.79g) and 4-dodecylbenzenesulfonic acid (0.13g) were stirred in 1,2-dichloroethane (33mL) and heated to 83 °C for 6 hours under a nitrogen atmosphere. It was then cooled to room temperature and filtered through a silica gel plug, washed with dichloromethane. The mother liquor was concentrated under reduced pressure to produce 11-bromo-3-(3-fluoro-4-methoxyphenyl)-7-methyl-3-(4-morpholinylphenyl)-13,13-dipropyl-3H,13H-indeno[2',3',3,4]naphtho[1,2-b]pyran (2.80g, 94% yield) as a dark oil.

[0162] Step 8

[0163] The product (0.90g), phenylboronic acid (0.18g) and potassium carbonate (0.37g) from step 7 are stirred in a mixture of N, N-dimethylacetamide (4mL), deionized water (1.5mL) and ethanol (1.5mL). The mixture is purged with nitrogen for 20 minutes and maintained under nitrogen. Tetrakis (triphenylphosphine) palladium (0) (0.07g) is added and the mixture is heated to 85°C for 2 hours, then cooled to room temperature and poured into a mixture of 10% aqueous hydrochloric acid solution (v / v) and ice. It is then extracted with ethyl acetate twice. The combined organic layer is washed twice with brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained residue is purified using flash chromatography on silica gel with a mixture of 75% hexane and 25% ethyl acetate. The fractions containing the desired product are combined and concentrated under reduced pressure. The obtained residue is ground in methanol and then collected by vacuum filtration to produce a light blue solid (0.69g, 77% yield). 1 H NMR is consistent with the following structure.

[0164]

[0165] Example 2

[0166] Step 1

[0167] The product of Step 6 of Example 1 (1.00 g) was subjected to the same conditions as in Steps 7 and 8 of Example 1, except that an equimolar amount of 1-(4-methoxyphenyl)-1-(4-(4-((trifluoromethyl)sulfonyl)piperazin-1-yl)phenyl)prop-2-yn-1-ol was used instead of 1-(3-fluoro-4-methoxyphenyl)-1-(4-morpholinylphenyl)prop-2-yn-1-ol in Step 7. A white solid was obtained (0.50 g, 45% yield). 1 H NMR is consistent with the following structure.

[0168]

[0169] Example 3

[0170] Step 1

[0171] The product of Example 1, Step 6, was subjected to the conditions of Example 1, Step 8, substituting an equimolar amount of (4-trifluoromethyl)phenylboronic acid for phenylboronic acid. Purification by flash chromatography on silica gel gave 2-methyl-7,7-dipropyl-9-(4-(trifluoromethyl)phenyl)-7H-benzo[c]fluoren-5-ol as a white solid (0.96 g, 83% yield).

[0172] Step 2

[0173] The product from step 1 (0.45 g), 1-(3-fluoro-4-methoxyphenyl)-1-(4-morpholinylphenyl)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 for 6 hours under nitrogen, 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 flash chromatography on silica gel eluting with a mixture of 80% hexane and 20% ethyl acetate. The resulting residue was recrystallized in hexane to produce a white solid (0.13 g, 17% yield). 1 H NMR is consistent with the following structure.

[0174]

[0175] Example 4

[0176] Step 1

[0177] The product of Example 1, Step 6 (3.26 g) was subjected to the same conditions as Example 1, Step 8, except that an equal molar amount of 4-methoxyphenylboronic acid was used instead of phenylboronic acid to produce solid 9-(4-methoxyphenyl)-2-methyl-7,7-dipropyl-7H-benzo[c]fluoren-5-ol (2.44 g, 70% yield).

[0178] Step 2

[0179] The product from Step 1 (5.00 g) was subjected to the same conditions as in Example 3, Step 2, substituting 1-(3-fluoro-4-methoxyphenyl)-1-(4-morpholinylphenyl)prop-2-yn-1-ol for 1-(3-fluoro-4-methoxyphenyl)-1-(4-morpholinylphenyl)prop-2-yn-1-ol in an equimolar amount. 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 H NMR is consistent with the following structure.

[0180]

[0181] Example 5

[0182] Step 1

[0183] The product of Example 1, Step 6 (3.00 g) was subjected to the same conditions as Example 1, Step 8, except that an equimolar amount of (2,4-dimethoxyphenyl)boronic acid was used instead of phenylboronic acid to produce solid 9-(2,4-dimethoxyphenyl)-2-methyl-7,7-dipropyl-7H-benzo[c]fluoren-5-ol (2.72 g, 80% yield).

[0184] Step 2

[0185] The product from Step 1 (0.90 g) was subjected to the same conditions as in Example 1, Step 7, except that an equimolar amount of 1-(4-methoxyphenyl)-1-(4-morpholinophenyl)prop-2-yn-1-ol was used instead of 1-(3-fluoro-4-methoxyphenyl)-1-(4-morpholinophenyl)prop-2-yn-1-ol to give a white solid (0.76 g, 51% yield). 1 H NMR is consistent with the following structure.

[0186]

[0187] Example 6

[0188] Step 1

[0189] The product of Example 1, Step 6, was subjected to the same conditions as Example 1, Step 8 to produce a white solid, wherein 1 H NMR was consistent with 2-methyl-9-phenyl-7,7-dipropyl-7H-benzo[c]fluoren-5-ol.

[0190] Step 2

[0191] The product from Step 1 (0.40 g) was subjected to the same conditions as Example 3, Step 2, except that an equimolar amount of 1-(4-methoxyphenyl)-1-(4-morpholinophenyl)prop-2-yn-1-ol was used instead of 1-(3-fluoro-4-methoxyphenyl)-1-(4-morpholinophenyl)prop-2-yn-1-ol to give a white solid (0.37 g, 53% yield). 1 H NMR is consistent with the following structure.

[0192]

[0193] Example 7

[0194] Step 1

[0195] The product (5.00g) of Example 1 step 6 and N, N-diisopropylethylamine (4.74g) are stirred in toluene (30mL). The mixture is purged with nitrogen for 20 minutes and then placed under nitrogen cover. Tris (dibenzylideneacetone) dipalladium (0) (0.78g) and 4,5-bis (diphenylphosphino) -9,9- dimethylxanthene (1.06g) are added to the reaction mixture. Next, 2,6- dimethylthiophenol (3.38g) is added dropwise to the mixture. The reaction mixture is rapidly heated to 110 ° C and maintained at this temperature for 17 hours. It is then cooled to room temperature and filtered through a silica gel plug, washed with a mixture of 75% hexane and 25% ethyl acetate. The mother liquor is concentrated under reduced pressure. The resulting residue is purified using flash chromatography on silica gel eluted with a mixture of 80% hexane and 20% ethyl acetate. Fractions containing the desired product were combined and concentrated under reduced pressure to give 9-((2,6-dimethylphenyl)thio)-2-methyl-7,7-dipropyl-7H-benzo[c]fluoren-5-ol as an oil.

[0196] Step 2

[0197] The product of Step 1 was subjected to the same conditions as Example 5, Step 2, and precipitated from methanol to produce a solid. 1 HNMR is consistent with the following structure.

[0198]

[0199] Example 8

[0200] Step 1

[0201] The product (5.00g), morpholine (2.13g) and potassium tert-butoxide (2.74g) from step 6 of example 1 are stirred in 1,2-dimethoxyethane (40mL), purged with nitrogen for 20 minutes, and maintained under a nitrogen atmosphere. Then bis(tri-tert-butylphosphine)palladium (0) (0.44g) is added, and the mixture is heated to 85°C for 16 hours. Then the mixture is cooled to room temperature, and water (100mL), citric acid (15g) and toluene (100mL) are added. The gained organic layer is filtered through a magnesium sulfate plug and concentrated under reduced pressure. The gained residue is purified by flash chromatography on silica gel with a mixture of hexane 70% and ethyl acetate 30%. The fractions containing the desired product are combined and concentrated under reduced pressure to obtain white solid 2-methyl-9-morpholinyl-7,7-dipropyl-7H-benzo [c] fluorene-5-ol.

[0202] Step 2

[0203] The product from Step 1 (3.56 g) was subjected to the same conditions as Example 5, Step 2 to give a solid. 1 H NMR is consistent with the following structure.

[0204]

[0205] Example 9

[0206] Step 1

[0207] 2-bromo-9-methoxy-7,7-dipropyl-7H-benzo[c]fluorene-5-ol] (5.0 g) was stirred in toluene (20 mL / g). The mixture was purged with nitrogen for 20 minutes and kept under nitrogen. 1,1-bis(diphenylphosphino)ferrocenedichloropalladium (II) (0.20 g) and tri(dibenzylideneacetone)dipalladium (0) (0.11 g) were added to the mixture. A solution of 1.4 M 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, then entered into ice water and acidified with dilute hydrochloric acid until pH was 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 silica gel plug, washed with dichloromethane. The mother liquor was concentrated under reduced pressure to a white solid 9-methoxy-2-methyl-7,7-dipropyl-7H-benzo[c]fluoren-5-ol (4.1 g, 97% yield).

[0208] Step 2

[0209] The product from Step 1 was subjected to the same conditions as Example 5, Step 2 to produce a solid. 1 H NMR is consistent with the following structure.

[0210]

[0211] Example 10

[0212] Step 1

[0213] The product of Step 6 of Example 1 (2.00 g) was subjected to the same conditions as in Step 7 of Example 1, except that 1-(3-fluoro-4-methoxyphenyl)-1-(4-morpholinophenyl)prop-2-yn-1-ol was replaced with an equal molar amount of 1-(4-butoxyphenyl)-1-(4-morpholinophenyl)prop-2-yn-1-ol to give a dark oily substance, 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).

[0214] Step 2

[0215] The product (3.64g) of step 1, 2-pyrrolidone (2.05g) and tripotassium phosphate (3.06g) are stirred in 1,4-dioxane (55mL). The mixture is purged with nitrogen for 20 minutes and then placed under a nitrogen atmosphere. 2-di-tert-butylphosphino-2',4',6'-triisopropylbiphenyl (0.51g) and tris(dibenzylideneacetone)dipalladium (0) (0.44g) are added and the mixture is then heated to 90°C for 2 hours. The mixture is then cooled to room temperature and poured into a mixture of dilute hydrochloric acid aqueous solution and ice. It is then extracted twice with ethyl acetate. The combined organic layer is then washed with a saturated sodium bicarbonate aqueous solution, dried over sodium sulfate, and concentrated to dryness under reduced pressure. The resulting residue is purified by flash chromatography on silica gel eluting with a mixture of 35% ethyl acetate and 65% hexane. The fractions containing the desired product are combined and concentrated to dryness under reduced pressure. The resulting residue was recrystallized in a mixture of 25% ethyl acetate and 75% methanol.The light blue crystalline solid was isolated by filtration under vacuum to give (2.00 g, 55% yield). 1 H NMR is consistent with the following structure.

[0216]

[0217] Example 11

[0218] Step 1

[0219] The same conditions as in Step 1 of Example 1 were used, except that 1-bromo-3-(tert-butyl)benzene was used instead of 3-bromotoluene to give (4-bromophenyl)(3-(tert-butyl)phenyl)methanone (18.99 g, 74% yield) as a white solid.

[0220] Step 2

[0221] The product from Step 1 (18.90 g) was treated to the conditions of Example 1, Step 2 to produce (E)-4-(4-bromophenyl)-4-(3-(tert-butyl)phenyl)-3-(methoxycarbonyl)but-3-enoic acid (22.1 g, 86% yield) as an amber oil.

[0222] Step 3

[0223] The product from Step 2 (22.05 g) was treated to the conditions of Example 1, Step 3 to produce methyl 4-acetoxy-1-(4-bromophenyl)-7-(tert-butyl)-2-naphthoate (18.25 g, 78% yield) as an amber oil.

[0224] Step 4

[0225] The product from Step 3 (37.5 g) was treated to 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.

[0226] Step 5

[0227] The product from Step 4 (3.31 g) was treated to the same conditions as Example 1, Step 5 to produce 4-(4-bromophenyl)-6-(tert-butyl)-3-(4-hydroxyhept-4-yl)naphthalen-1-ol (3.62 g, 96% yield) as an amber oil.

[0228] Step 6

[0229] The product from Step 5 (3.60 g) was treated to 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).

[0230] Step 7

[0231] The product from Step 6 (0.80 g) was subjected to the same conditions as Example 3, Step 1, except that an equimolar amount of (2,4-dimethoxyphenyl)boronic acid was used instead of (4-trifluoromethyl)phenylboronic acid to produce a white solid 2-(tert-butyl)-9-(2,4-dimethoxyphenyl)-7,7-dipropyl-7H-benzo[c]fluoren-5-ol (0.81 g, 90% yield).

[0232] Step 8

[0233] The product from Step 7 (0.81 g) was subjected to the same conditions as Example 4, Step 2, except that an equal molar amount of 1-(4-methoxyphenyl)-1-(4-morpholinophenyl)prop-2-yn-1-ol was used instead of 1-(4-butoxyphenyl)-1-(4-morpholinophenyl)prop-2-yn-1-ol to give a solid (55 g, 42% yield). 1 H NMR is consistent with the following structure.

[0234]

[0235] Part 2: Results

[0236] Each of the photochromic dyes from Examples 1 to 11 and each of Comparative Examples CE1 to CE10 was incorporated into a polyurethane coating system (as described in Examples 1-3 of U.S. Pat. No. 8,608,988) at the same mol % and in the same proportion as that of the photochromic dyes from Examples 1 to 11 and each of Comparative Examples CE1 to CE10. The same coating thickness was applied to 2" x 2" test chips made of monomer (PPG Industries, Inc.). All coated test chips were cured at 125°C for 1 hour.

[0237] Each coated test chip (hereinafter referred to as a "test sample") was conditioned by first exposing to 365 nm UV light for 10 minutes at a distance of about 14 cm to activate the photochromic material within the coating. A model Li-1800 spectroradiometer measured the UVA (315 to 380 nm) irradiance at the test sample and found it 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 about 36 cm for 10 minutes to bleach (deactivate) the photochromic material. The spectroradiometer measures the illuminance at the test sample and finds it to be 21.9 Klux. The test sample is then kept in a dark environment at room temperature (i.e., from 70°F to 75°F, or 21°C to 24°C) for at least 1 hour before testing on the optical bench. The UV absorbance of the test sample at 390 nanometers is measured before measuring on the optical bench.

[0238] The percent transmission of Examples 1 to 11 and each of Comparative Examples CE1 to CE10 was determined using CIE Y values ​​according to CIE 15:2004 colorimetry using D 65 illuminant and 10° observer. As used herein in the specification and claims, a* and b* values ​​refer to a* and b* values ​​measured using a Hunter UltraScan Pro device according to CIE 15:2004 spatial colorimetry using D 65 illuminant and 10° observer. %T, a* and b* values ​​are values ​​for samples containing photochromic dyes, and %T o 、a* o and b* o The values ​​are from samples prepared without photochromic dye in the polyurethane coating. ΔE was calculated according to the following equation ％T .

[0239] ΔE ％T =[(%T-%T o ) 2 +(a*-a* o ) 2 +(b*-b* o ) 2 ] 0.5

[0240] The BMP optical bench is equipped with two 150-watt Model #66057 Xenon Arc Lamp. The light path from lamp 1 is directed through a 3mm KG-2 bandpass filters and appropriate neutral density filters, which contribute to the required UV and partial visible light irradiance levels. The light path from lamp 2 is directed through a 3mm KG-2 bandpass filter, A short band 400 nm cutoff filter and appropriate neutral density filters were used to provide supplemental visible light illumination. A 2" x 2" 50% polka dot beam splitter at 45° to each lamp was used to mix the two beams. The intensity of the irradiance was adjusted using a combination of neutral density filters and xenon arc lamp voltage control. Proprietary software, BMPSoft version 2.1e, was used on the BMP to control timing, irradiance, chamber and sample temperature, shutters, filter selection, and response measurement. A 100 mm x 200 mm (1.3 in) x 100 mm (2.3 in) fiber optic cable was used to transmit light through the test sample. Response and color measurements were made using a spectrophotometer (Model MCS 501). Photopic response measurements were collected on each test sample. The power output of the optical bench (i.e., the dose of light to which the test sample was exposed) was adjusted to 6.7 W / m2. 2) UVA, from 315-380nm integration, and 50Klux illumination, from 380-780nm integration. Use irradiance probe and calibrated Zeiss (Zeiss) spectrophotometer to measure this power set point. The sample cell is equipped with a quartz window and an automatic centering sample holder. The temperature in the sample cell is controlled at 23 ° C by software using an improved Facis, model FX-10 environmental simulator. The measurement of the dynamic photochromic response of the test sample and the color measurement are carried out using the same Zeiss spectrophotometer, which has a fiber optic cable for transmitting light from a halogen tungsten lamp and passing through the test sample. The collimated monitoring beam from the fiber optic cable is maintained perpendicular to the test sample, while passing through the sample and being guided to the receiving fiber optic cable assembly attached to the spectrophotometer. The exact placement point of the sample in the sample cell is where the activation xenon arc beam and the monitoring beam intersect to form two concentric circles of light. The incident angle of the xenon arc beam at the sample placement point is =30 ° relative to the vertical line.

[0241] The response measurement, expressed as the change in optical density (ΔOD) from the unactivated or whitish state to the activated or colored state, is determined by establishing an initial unactivated transmittance, opening the shutter of the xenon lamp and measuring the transmittance through activation at selected time intervals. The ΔOD at saturation is measured 15 minutes after activation and the fade half-life ("T1 / 2") value is the time interval (in seconds) for the ΔOD of the activated form of the photochromic material in the coating to reach half of the ΔOD at fifteen minutes after the activating light source is removed at 73.4°F (23°C).

[0242] Table A

[0243]

[0244]

[0245]

[0246]

[0247] The results shown in Table A above clearly show that by using the photochromic indeno-fused naphthopyran compounds of the present invention, ΔE ％T Whitening is improved. These lower ΔE ％TThe values ​​correspond to photochromic articles with alkyl substituents at the 7 position, which have good indoor clarity due to improved visual sensitivity in low light conditions and desirable aesthetics. The alkyl group at the 7 position also shows an improvement in activated darkness compared to compounds without substitution at the 7 position. This is necessary to provide comfort and protection when wearing the lens outdoors. The unexpected combination of excellent white emission and darkening properties makes the indeno-fused naphthopyran compounds of the present invention with alkyl substituents at the 7 position an ideal candidate for use in photochromic lenses.

[0248] The invention has been described with reference to specific details of particular embodiments of the invention. It is not intended that these details be considered limitations on the scope of the invention unless and to the extent they are included in the appended claims.

Claims

1. An indeno-fused naphthopyran having the following core skeleton structure (I): in: R 1 is a substituted or unsubstituted alkyl group; R 2 is a substituted or unsubstituted amino group; a substituted or unsubstituted alkyl group; substituted or unsubstituted alkenyl; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted alkylthio group; a substituted or unsubstituted arylthio group; Substituted or unsubstituted amides; Substituted or unsubstituted urea; or Substituted or unsubstituted carbamates; and R 3 and R 4 At least one of them is an electron-donating group, wherein R 3 and R 4 Hammett's σ p The sum of the values ​​is less than -0.40, When R 1 In the case of 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. The indeno-fused naphthopyran according to claim 1, wherein R 1 C1 to C 20 Substituted or unsubstituted alkyl.

3. The indeno-fused naphthopyran according to claim 1 or claim 2, wherein: R 1 It is an unsubstituted C1 to C6 alkyl group.

4. The indeno-fused naphthopyran according to any one of claims 1 to 3, wherein R 2 Selected from the group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group and a substituted or unsubstituted arylthio group.

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

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

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

8. The indeno-fused naphthopyran according to claim 7, wherein R 3 and R 4 At least one of the groups is a cyclic amino group which is a nitrogen-containing heterocyclic ring selected from the group consisting of a morpholinyl group, a piperidinyl group, a substituted piperazinyl group, and a pyrrolidinyl group.

9. The indeno-fused naphthopyran according to any one of claims 1 to 5, wherein R 3 and R 4 are the same or different and are each independently a substituted or unsubstituted alkoxy group or a substituted or unsubstituted amino group.

10. The indeno-fused naphthopyran according to any one of claims 1 to 9, wherein R 3 and R 4 At least one of the following is selected from the group consisting of a methoxy group, a morpholinyl group, a piperazinyl group, a substituted piperazinyl group, and a dialkyl (C1 to C6) amino group.

11. The indeno-naphthopyran according to any one of claims 1 to 10, which has the following core skeleton structure (Ia); in: R 1 , R 2 , R 3 and R 4 Each is as described above with respect to the core skeleton structure (I); and R 5 and R 6 Each independently is: (i) hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heterocycloalkyl, allyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; (ii) alkoxy, hydroxy, alkylthio, ketone, aldehyde, ester, carboxylic acid, carboxylic acid ester, siloxane, alkoxysilane, or polysiloxane; (iii) a group comprising polyester, polyether, polycarbonate, polyurethane or a combination thereof; or (iv) R 5 and R 6 Together with the carbon atom at position 13 bonded thereto, it forms an aliphatic ring having 3 to 20 ring member carbon atoms, a condensed polycyclic ring having an aromatic ring or an aromatic heterocyclic ring condensed to the above aliphatic ring, a heterocyclic ring having 3 to 20 ring member atoms, or a condensed polycyclic ring having an aromatic ring or an aromatic heterocyclic ring condensed to the above heterocyclic ring.

12. The indeno-fused naphthopyran according to claim 11, wherein R 5 and R 6 Each is independently a substituted or unsubstituted alkyl group.

13. The indeno-fused naphthopyran according to claim 11, wherein R 1 is an unsubstituted C1 to C6 alkyl group; R 2 is a substituted or unsubstituted phenyl group; R 3 and R 4 are each independently a C1 to C4 alkoxy group or a nitrogen-containing heterocycle; and R 5 and R 6 Each is independently a C1 to C4 alkyl group.

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 according to any one of claims 1 to 13, wherein the photochromic article is selected from ophthalmic articles, display articles, windows, mirrors, active liquid crystal cell articles, or passive liquid crystal cell articles; or wherein the photochromic article is selected from ophthalmic articles, and the ophthalmic article is selected from corrective lenses, non-corrective lenses, contact lenses, intraocular lenses, magnifying lenses, protective lenses, or goggles; or The photochromic article is selected from display articles, and the display article is selected from screens, monitors, or security elements.

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