Indole naphthopyran

Abstract

Provided is a photochromic indole naphthopyran compound having a skeleton structure of formula (I): wherein R 1 and R 2 Each independently has a spatial volume A, where R 1 or R 2 At least one of them has a spatial volume A, R of at least 0.6 3 and R 4 Each independently has a Hammett's σρ value, and wherein the indole naphthopyran compound has a calculated electron steric factor of at least -3.3.

Description

Technical Field

[0001] The present invention relates to photochromic compounds, such as photochromic indole naphthopyran compounds, and photochromic compositions and photochromic articles comprising such photochromic compounds. Background Art

[0002] Photochromic compounds undergo a transition from one state (or form) to another state in response to certain wavelengths of electromagnetic radiation (e.g., "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) state when exposed to actinic radiation. When the actinic radiation is removed, the photochromic compound reversibly transitions from the activated state back to the unactivated state.

[0003] Photochromic compounds can be characterized with respect to various properties, such as, but not limited to: rate of fading; change in optical density (ΔOD); change in optical density at saturation (ΔOD); sensitivity (ΔOD / minute); efficiency (chromaticity) of the photochromic compound in absorbing the radiation required to activate the photochromic compound; bleached color; and dichroic properties, such as in the case of photochromic-dichroic compounds, which can be quantified with respect to an absorbance ratio (AR) value. The change in optical density measures the change from an unactivated state to an activated state.

[0004] The indole naphthopyrans of the present invention provide improved bleached colors. For example, placing an aromatic group on the bridgehead nitrogen significantly improves the bleached color compared to prior art naphthopyrans, and specific substitutions on the aromatic rings further improve the bleached color. In addition, in the unactivated state, indole naphthopyrans generally have more color than their indeno-fused naphthopyran counterparts. By selecting specific substituents, color differences can be improved.

[0005] It is preferred that the photochromic lens be as transparent as a non-photochromic lens of the same material in the unactivated state. Typically, a non-tinted substrate has a transmittance greater than 89% and a color a* and b* values ​​less than 1, respectively. Introducing a photochromic compound on a coating or in a substrate typically results in lower transmittance and higher color a* and b* values ​​due to residual activation of the chromene. Thus, the residual color of the photochromic compound in the unactivated state may affect the overall properties of the product and be visible to eye care providers and consumers.

[0006] It would be desirable to provide a photochromic compound with enhanced bleached color to improve color and aesthetics. For example, it would be desirable to provide new photochromic indole naphthopyran compounds having such characteristics. Summary of the invention

[0007] The photochromic compound comprises a core skeleton structure represented by the following formula (I),

[0008]

[0009] Where R 1 and R 2 Each independently has a spatial volume A, and R 1 or R 2 At least one of them has a spatial volume A of at least 0.6; R 3 and R 4 Each independently has a Hammett σ p value; and the compound has a calculated electronic steric factor calculated to be at least -3.3.

[0010] 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

[0011] Figure 1 A general scheme, Scheme 1, is shown for an exemplary method for preparing the photochromic compounds of the present invention. DETAILED DESCRIPTION

[0012] As used herein, the articles "a," "an," and "the" include plural referents unless expressly and unequivocally limited to one referent.

[0013] As used herein, the term "includes" is synonymous with "comprises."

[0014] 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.

[0015] 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)-.

[0016] 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 regarded as a limitation on any analysis of values ​​under the principle of equivalents.

[0017] As used herein, molecular weight values, such as weight average molecular weight (Mw) and number average molecular weight (Mn) of polymers are determined by gel permeation chromatography using appropriate standards, such as polystyrene standards.

[0018] 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.

[0019] 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 acrylates, methacrylates, acrylamides, methacrylamides, acrylic acid and methacrylic acid. As used herein, the term "(meth)acrylic acid" means methacrylic acid and / or acrylic acid.

[0020] In some embodiments, the photochromic compounds of the present invention are also referred to herein as photochromic-dichroic compounds (e.g., when they include one or more mesogen-containing groups such as L 1 hour).

[0021] As described herein, the photochromic compounds of the present invention include, but are not limited to, photochromic compounds represented by Formula (I), Formula (Ia), and Formula (Ib), in each case optionally further including one or more by-products resulting from the synthesis of such compounds.

[0022] As used herein, the term "photochromic" and similar terms (such as "photochromic compound") means having an absorption spectrum of at least visible radiation that changes in response to 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 of at least visible radiation that changes in response to absorption of at least actinic radiation) and including at least one photochromic compound.

[0023] 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.

[0024] As used herein, the term "dichroic" means the ability to absorb one of two orthogonal plane-polarized components of at least transmitted radiation more strongly than the other.

[0025] As used herein, the term "photochromic-dichroic" and similar terms (such as "photochromic-dichroic compound") mean a compound that possesses and / or provides both photochromic properties (i.e., having an absorption spectrum of at least visible radiation that varies in response to at least actinic radiation) and dichroic properties (i.e., being able to absorb one of two orthogonal plane-polarized components of at least transmitted radiation more strongly than the other).

[0026] 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. The term "thermally reversible photochromic compound / material" as used herein 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. The term "non-thermally reversible photochromic compound / material" as used herein 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).

[0027] As used herein, the terms "first" and "second" are not intended to refer to any particular order or temporal 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, 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 and second states. 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.

[0028] 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 or 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.

[0029] As used herein, the term "ophthalmic" means pertaining to or relating to the eye and vision. Non-limiting examples of ophthalmic articles or elements include corrective and non-corrective lenses (which include single-vision or multi-vision lenses, which may be segmented or non-segmented multi-vision 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).

[0030] 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.

[0031] 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.

[0032] As used herein, the term "mirror" means a surface that specularly reflects a significant portion of incident light.

[0033] 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.

[0034] As used herein, the terms "formed over", "deposited over", "provided over", "applied over", "residing over", or "positioned over" mean formed, deposited, provided, applied, applied, residing, or positioned over, but not necessarily in direct (or adjacent) contact with an underlying element, or a surface of an underlying element. For example, a layer "positioned over" does not exclude the presence of one or more other layers, coatings, or films of the same or different composition between the positioned or formed layer and the substrate.

[0035] As used herein, references 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 (such as the core skeleton structure) of a compound (such as the indole naphthopyran photochromic compound of the present invention), and these positions are described herein according to some embodiments by numbers in the ring structure of representative chemical formulae (such as, but not limited to, Formula (I), (Ia) and / or (Ib)).

[0036] "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 explicitly shown to the contrary, one or more core skeleton structures may have one or more atoms or one or more groups (not specifically shown in the corresponding formula) bonded to one or more numbered ring positions on the core skeleton structure, which may be the same or different from each other.

[0037] 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), (Ia) and / or (Ib).

[0038] All documents or portions of documents (such as but not limited to published patents and patent applications) referred to herein and unless otherwise indicated are deemed to be "incorporated by reference in their entirety."

[0039] "Aryl" refers to an aromatic cyclic monovalent hydrocarbon radical, and the term "aromatic" refers to a cyclic conjugated hydrocarbon having a stability (due to delocalization) significantly greater than the stability of a presumed localized structure. Examples of aryl groups include C6-C 14 Aryl groups such as, but not limited to, phenyl, naphthyl, phenanthrenyl, and anthracenyl.

[0040] 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 a halogen group. The term "halogen substituted" includes "perhalogen substituted". As used herein, the term perhalogenated 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 a halogen group. For example, perhalomethyl is -CX3; perhalophenyl is -C6X5, wherein X represents one or more halo groups, such as but not limited to F, Cl or Br.

[0041] As used herein, descriptions of "straight or branched" groups (such as straight or branched alkyl groups) are understood herein to include: straight chain (or "straight chain") groups, such as straight chain C1-C 25 Alkyl; and appropriately branched groups, such as branched C3-C 25 alkyl.

[0042] The term "alkyl" as used herein 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 groups, such as C1-C 20 Alkyl groups, such as C2-C 10 Alkyl groups, such as C1-C 12 Alkyl groups such as C1-C6 alkyl groups. Examples of alkyl groups from which the various alkyl groups of the present invention may be selected include, but are not limited to, those further listed herein. Alkyl groups may include "cycloalkyl" groups. The term "cycloalkyl" as used herein means a suitable cyclic group such as, but not limited to, C3-C 12 Cycloalkyl (including but not limited to cyclic C5-C7 alkyl, or cyclic C3-C 10Examples of cycloalkyl groups include, but are not limited to, those further listed herein. The term "cycloalkyl" as used herein also includes: bridged polycycloalkyl groups (or bridged polycyclic (polycyclic) alkyl), such as, but not limited to, bicyclo [2.2.1] heptyl (or norbornyl) and bicyclo [2.2.2] octyl; and condensed polycycloalkyl groups (or condensed polycyclic (polycyclic) alkyl), such as, but not limited to, octahydro-1H-indenyl, and decahydronaphthyl.

[0043] The term "heterocycloalkyl" as used herein 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.

[0044] 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.

[0045] As used herein, the term "fused polycyclic-aryl-alkyl" and similar terms such as fused polycyclic-alkyl-aryl, fused polycyclic-aryl-alkyl, and fused polycyclic-alkyl-aryl refer to fused polycyclic groups that include 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 fused polycyclic-aryl-alkyl include, but are not limited to, indenyl, 9H-fluorenyl, cyclopentanaphthenyl, and indacenyl.

[0046] As used herein, the term "aralkyl" includes, but is not limited to, C6-C 24 Arylalkyl, such as but not limited to C6-C 10Aralkyl refers to an alkyl group substituted by an aryl group. Examples of aralkyl groups include, but are not limited to, benzyl and phenethyl.

[0047] 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 their structural isomers). Representative heteroaryl includes but is not limited to furanyl, pyranyl, pyridyl, isoquinolinyl, and pyrimidinyl. Representative aralkyl includes but is not limited to benzyl and phenethyl.

[0048] As used herein, the term "nitrogen-containing heterocycle" includes, but is not limited to, a nitrogen-containing ring, wherein the nitrogen-containing ring is bonded via a ring nitrogen. Examples of nitrogen-containing heterocycles include, but are not limited to, cyclic amino groups such as morpholino, piperidino, and pyrrolidino; and heteroaromatic compounds such as imidazole, pyrrole, indole, and carbazole.

[0049] As used herein, the recitation of a "substituted" group is intended to refer to groups including, but not limited to, alkyl, heterocycloalkyl, aryl, and / or heteroaryl groups in which at least one hydrogen has been replaced or substituted by a group other than hydrogen, such as, but not limited to, alkoxy; halogen groups (e.g., F, Cl, I, and Br); hydroxyl; thiol groups; alkylthio; arylthio; ketone groups; aldehyde groups; ester groups; carboxylic acid groups; phosphoric acid groups; phosphate ester groups; sulfonic acid groups; sulfonate groups; nitro; cyano groups; alkyl (including aralkyl); alkenyl; alkynyl; haloalkyl; perhaloalkyl; heterocycloalkyl; aryl (including alkaryl, including hydroxy-substituted aryl, such as phenol, and including polycondensed ring aryl); heteroaryl (including polycondensed ring heteroaryl); amino groups, such as -N(R 11’ )(R 12’ ), where R 11’ and R 12’ Each is independently selected from, for example, hydrogen, alkyl, heterocycloalkyl, aryl, or heteroaryl; a carboxylate group; a siloxane group; an alkoxysilane group; a polysiloxane group; an amide group; a urethane 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; a nitrogen-containing heterocyclic compound; or a combination thereof, including those classes and examples as further described herein.

[0050] 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.

[0051] As used herein, "selected from" is synonymous with "chosen from", regardless of whether the elements are listed in combination or separately. Further, 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.

[0052] The discussion of the present invention may describe certain features as "particularly" or "preferably" within certain limitations (e.g., "preferably", "more preferably", or "even more preferably" within certain limitations). It should be understood that the present invention is not limited to these specific or preferred limitations, but encompasses the entire scope of the disclosure.

[0053] The present invention comprises, or consists essentially of, the following aspects of the invention in any combination.

[0054] According to the invention of formula I, formula Ia and / or formula Ib, the functional group R 1 and R 2 The spatial effect and R 3 and R 4 The electronic effects of the groups combine to give an acceptable color, expressed as ΔE ％T According to Equation 1, ΔE ％T The percent transmittance (%T), a* values, and b* values ​​of the unactivated photochromic layer were correlated to those of the transparent substrate (T*0, a*0, b*0).

[0055] ΔE ％T =[(%T-%T o ) 2 +(a*-a* o ) 2 +(b*-b* o ) 2 ] 0.5

[0056] Equation 1

[0057] ΔE ％T The lower the value, the less hue and color the sample has, in this case in an unactivated state. 1 and R 2 The spatial effect and R 3 and R 4 The relationship between the electronic effect of can be expressed and predicted by the electronic steric factor (ESF) according to Equation 2.

[0058] ESF=[(R 3 and R 4 Hammett's σ p The sum of the values))x10]+(R 1 and R 2 The sum of the spatial volume A values)

[0059] Equation 2

[0060] The relative strength of electron donor groups is usually expressed by the Hammett σ value, or σ p The more negative the Hammett σ value, the more color the unactivated state may exhibit. It has been found that steric volume at specific locations can overcome this undesirable coloration. The steric volume required to overcome the residual unactivated color increases with increasing electron donation intensity (i.e., the Hammett σ value becomes more negative).

[0061] From Equation 2, we can see that the electron space factor (ESF) is given by R 3 and R 4 The sum of the Hammett values ​​from the literature (multiplied by 10 to produce comparable units) and R 1 and R 2 The Hammett σ for various substituents is calculated by summing the literature steric volume A values. p A list 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. The Hammett σ values ​​for selected substituents of the present invention are given in Table 1. p Examples of values ​​include those listed in Table 1 below.

[0062] Table 1 - Hammett σ for selected substituents p value

[0063] Substituents <![CDATA[σ p Value]]> Substituents <![CDATA[σ p Value]]> -H 0 -Phenyl -0.01 <![CDATA[-CH3]]> -0.17 -NHCOOET -0.15 <![CDATA[-OCH3]]> -0.27 -F 0.062 <![CDATA[-N(CH3)2]]> -0.84 -Cl 0.23 -Morpholino -0.65 (estimated) <![CDATA[-SCH3]]> 0.0 -OCOMe 0.31 -SPh 0.07 <![CDATA[-COOC2H5]]> 0.45 -CN 0.66 -OH -0.37 <![CDATA[-CF3]]> 0.54

[0064] A list of steric bulk A values ​​for various substituents can be found in Gordon, Arnold J. Ford, Richard A., "Chemist's Companion-A Handbook of Practical Data, Techniques, and References-3.3 Conformational Free Energy Values", 1972, John Wiley & Sons, 156-157, the disclosure of which is incorporated herein by reference. The steric bulk A values ​​for selected substituents of the present invention include, for example, those listed in Table 2 below.

[0065] Table 2 - Spatial volume A values ​​of selected substituents

[0066]

[0067] Referring to Equation 1, this can be achieved by increasing R 1 and R 2 space volume or by introducing less electron donating R 3 and R 4 Groups to achieve lower ΔE ％T In many cases, it is desirable to use a stronger electron donor R 3 and R 4 The group provides a faster fading rate and changes the absorption spectrum of the activated chromene. Increasing the ESF value will reduce the ΔE ％T , and thus improve the color of the bleached state. That is, the larger the ESF value, the better the bleached color of the photochromic compound. When the ESF is greater than -3.3, the ΔE of the photochromic product using the photochromic compound ％T becomes acceptable (less than 7). The preferred ΔE of the photochromic compound ％T For example, less than 3.5, such as less than 3, such as less than 2.5, or such as less than 2.

[0068] The photochromic compounds according to the present invention may be represented by one or more core skeleton structures described below. Each available numbered ring position (e.g., 5, 6, 7, 8, 9, 10, 11, 12 and / or 17) of the core skeleton structure of formula (I) may 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.

[0069]

[0070] Regarding formula (I), R 1 and R 2Each independently has a spatial volume A, and R 1 or R 2 At least one of them has a spatial volume A of at least 0.6. R can be selected from 1 and R 2 Examples of the group include, but are not limited to, alkoxy groups such as methoxy, ethoxy, and butoxy; linear or branched alkyl groups such as methyl, ethyl, isopropyl, tert-butyl, and neopentyl; perfluoroalkyl groups such as trifluoromethyl and pentafluoroethyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; and aryl groups such as phenyl.

[0071] R 3 and R 4 Each independently has a Hammett σ ranging from -0.84 to 0.23 p If R 1 and R 2 As long as the combined steric bulk A value of is sufficient to overcome the combined Hammett value to meet the electron steric factor (ESF) requirements calculated above, any substituent having a Hammett value within the stated range may be used.

[0072] The indole naphthopyran compound having formula (I) has a calculated electron steric factor of at least -3.3. For example, the indole naphthopyran compound may have a calculated electron steric factor of at least 0.

[0073] R 1 and R 2 At least one of them can be independently an alkyl group, an alkoxy group, a haloalkyl group, or a nitrogen-containing heterocycle. 1 or R 2 At least one of R may be methyl, ethyl, butyl, tert-butyl, trifluoromethyl, or methoxy. 1 and R 2 The two may be the same group. 3 and R 4 At least one of can be independently hydrogen, alkyl, alkoxy, halogenated alkyl, or nitrogen-containing heterocycle. 3 or R 4 At least one of the groups may be a methoxy group or a trifluoromethyl group.

[0074] Additionally or alternatively, the photochromic compounds of the present invention may be represented by a core skeleton structure of formula (Ia):

[0075]

[0076] Regarding formula (Ia), R 1 , R 2 , R 3 , and R 4 is as previously described for formula (I).

[0077] Further with respect to Formula (Ia), m is 0 to 4, n is 0 to 4, and independently of each m, R 5 and R is independent of each n 6 is hydroxyl; cyano; (meth)acrylate; amino or nitrogen-containing heterocyclic; mesogen-containing group L 1 ; substituted or unsubstituted alkyl; substituted or unsubstituted alkenyl; substituted or unsubstituted alkynyl; halogen group; perhalogenated group; borate or boronic acid; polyether, polyester, polycarbonate, or polyurethane; substituted or unsubstituted aryl; substituted or unsubstituted heterocycloalkyl; substituted or unsubstituted heteroaryl; substituted or unsubstituted alkoxy or substituted or unsubstituted aryloxy; substituted or unsubstituted alkylthio or substituted or unsubstituted arylthio; ketone, aldehyde, ester, carboxylic acid, carboxylate, or amide; carbonate, carbamate, or urea; or siloxane, alkoxysilane, or polysiloxane. Each alkyl substituent, each alkenyl substituent, each alkynyl substituent, each aryl substituent, each heterocycloalkyl substituent, each heteroaryl substituent, each alkoxy substituent, each aryloxy substituent, each alkylthio substituent, and each arylthio substituent is independently selected from halogen, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, perhaloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, hydroxy, alkylthio, 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, arylamine, alkylamine, cyclic amino group, heteroaromatic compound, or a combination thereof.

[0078] For example, R 1 It can be trifluoromethyl, R 2 can be trifluoromethyl or hydrogen, and R 3 and R 4 It may be hydrogen.

[0079] Further with respect to formula (Ia), each mesogen-containing group L 1 can be independently represented by the following formula (II),

[0080] Formula (II)

[0081] -[S 1 ] c -[Q 1 -[S 2 ] d ] d’ -[Q 2 -[S 3 ] e ] e’ -[Q 3 -[S4 ] f ] f’ -R

[0082] Q 1 , Q 2 , and Q 3 Each occurrence is independently a divalent group selected from the group consisting of unsubstituted aryl, substituted aryl, unsubstituted cycloalkyl, and substituted cycloalkyl. The aryl substituent and the cycloalkyl substituent may each independently be selected from the group consisting of: liquid crystal mesogen, halogen, alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkoxycarbonyl, alkylcarbonyl, alkoxycarbonyloxy, aryloxycarbonyloxy, perfluoroalkyl, and perfluoroalkoxy. Further with respect to formula (II), c, d, e, and f are each independently an integer from 0 to 3; and each S 1 , S 2 , S 3 , and S 4 Each occurrence is independently selected from a spacer unit, the spacer unit being selected from the group consisting of: (i) -C(Z)2-, -N(Z)-, -C(Z)=C(Z)-, -C(Z)=N-, wherein Z is independently selected from the group consisting of hydrogen, alkyl, or aryl at each occurrence; (ii) -Si(CH3)2-, -Si(CH3)2O-; and (iii) -O-, -C(=O)-, -C≡C-, -N=N-, -S-, -S(=O)-, -(O=)S(=O)-, -(O=)S(=O)O-, -O(O=)S(=O)O-, provided that when two spacer units containing heteroatoms are linked together, the spacer units are linked so that the heteroatoms are not directly linked to each other. Further with respect to formula (II), R is an alkyl group. Further with respect to formula (II), d', e' and f' are each independently 0, 1, 2, 3, and 4, provided that the sum of d'+e'+f' is at least 1.

[0083] Additionally or alternatively, the photochromic compounds of the present invention may be represented by a core skeleton structure of formula (Ib):

[0084]

[0085] Regarding formula (Ib), R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 is as previously described for formula (I) and / or (Ia).

[0086] Further with respect to formula (Ib), R 7Selected from the group consisting of an alkyl group, an alkoxy group, a haloalkyl group, and a nitrogen-containing heterocycle.

[0087] As used herein, the term "polysiloxane" (such as a substituent for various groups of the photochromic compound of the present invention) includes materials represented by the following formula (G):

[0088]

[0089] With respect to formula (G), in each case, the subscript t' is from 2 to 200, such as from 2 to 100, or 2 to 50, or from 2 to 25, or from 2 to 15, or from 2 to 10, or from 2 to 5, inclusive. Further with respect to the following formula (G): for each t', R 32 and R 33 are each independently selected from alkyl or aryl; and R 34 is selected from hydrogen, alkyl, or aryl. In some embodiments: for each t', R 32和 R 33 are each independently selected from methyl, ethyl, or phenyl; and R 34 is selected from hydrogen, methyl, ethyl, or phenyl.

[0090] As used herein, the term "polysiloxane" (such as a substituent for various groups of the photochromic compound of the present invention, alternatively or in addition to the material represented by formula (G)) includes a material represented by the following formula (H):

[0091]

[0092] With respect to formula (H), subscript u' is 0-2 and subscript x' is 1-3, provided that u'+x' is 3; and subscript v' is 0-2 and subscript w' is 1-3, provided that v'+w' is 3. Further with respect to formula (H), in each case, for each u', R 35 Independently, for each v' and each x', R 36 Independently, and for each w' and each x', each R 37 Independently selected from alkyl (such as but not limited to methyl or ethyl) or aryl (such as but not limited to phenyl).

[0093] For some embodiments, the photochromic compounds of the present invention, such as those described with respect to formula (I), (Ia) and / or (Ib), can be used individually or in combination with one or more other photochromic compounds. For example, the photochromic compounds of the present invention can be used in combination with one or more other photochromic compounds having an activation absorption maximum in the range of 300 nanometers to 1,000 nanometers. In addition, the 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, for example, 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).

[0094] The 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. Patent No. 5,645,767, column 12, line 66 to column 13, line 19, which describes parameters defining neutral gray and brown.

[0095] Examples of other classes 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, phenanthropyrans, quinopyrans, fluoranthopyrans, spiropyrans, benzoxazines, naphthoxazines, spiro(dihydroindole)naphthoxazines, spiro(dihydroindole)pyridobenzoxazines, spiro(dihydroindole)fluoranthopyrazines, spiro(dihydroindole)quinooxazines, fulgides, fulgimides, diarylethenes, diarylalkylethylenes, diarylalkenylethylenes, 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 at column 34, line 20 to column 35, line 13 of US 9,028,728 B2.

[0096] The indole naphthopyran compounds of the present invention can be prepared as follows according to methods known in the art. Figure 1 , General Synthesis Scheme 1, the preparation of the photochromic compounds according to the present invention is described below. Further detailed descriptions of the preparation of the photochromic compounds of the present invention are further provided in the Examples herein. Figure 1 In the various groups, such as R of the various intermediates, reactants, and / or compounds described 1 , R 2 , R 3 , R4 , R 5 , R 6 , R 芳基 , and R 烷基 , are each as described herein, and / or represent a precursor of such a group.

[0097] The synthesis of compounds with different substituents as depicted by the following formula III has been described in many references such as US 6,296,785 or US 7,262,295.

[0098]

[0099] Hydroxyl and carboxylic acid groups can be benzylated by reaction with benzyl chloride and a base such as sodium carbonate or potassium carbonate. The resulting carboxylic acid ester can then be converted to a carboxylic acid by an acid or base method for ester hydrolysis. The resulting product is depicted as Formula IIIa below.

[0100]

[0101] The carboxylic acid group can then be converted to an NH2 group via Curtius rearrangement conditions using diphenylphosphoryl azide, which generates an isocyanate group, which is subsequently hydrolyzed to generate an amine group, as depicted in Formula IIIb below.

[0102]

[0103] The amine group is converted to an indole by first forming a picolinamide group by a conventional amide-forming reaction such as reacting an amine with an acyl chloride, an ester, or a carboxylic acid group. The reaction of the amine with picolinyl chloride and a base such as triethylamine gives picolinamide in high yield, as depicted in formula IIIc. The picolinamide can be cyclized to an indole, as depicted in formula IIId, by using a copper catalyst as described below: Takumatso, K. et al. Org. Lett. [Organic Express] 2014, 16, 2892. See the reaction depicted below.

[0104]

[0105] The indole ring depicted in formula IIId can also be formed by reacting an amine of formula IIIb with tosyl (Ts) chloride or anhydride to form an N-Ts group, as depicted in formula IIIe. This group can be cyclized with a palladium catalyst as described in: Youn, SW Org. Lett. [Organic Letters] 2011, 13, 3738. See the reaction depicted below.

[0106]

[0107] Alternatively, the amino group of formula IIIb can be converted to an azide group by forming a diazonium salt under Sandmeyer conditions followed by displacement with an azide salt such as sodium azide, as depicted in formula IIIf. The indole group of formula IIId can then be formed by exposure to UV light in a solvent such as THF. See the reaction depicted below.

[0108]

[0109] Indole groups can be arylated by cross-coupling reactions with transition metal catalysts and aryl halides, as shown in formula IIIg. Ullmann coupling methodology with copper catalysts is a common method for this transformation. See the reaction depicted below.

[0110]

[0111] Indoles can also be arylated by nucleophilic aromatic substitution, such as by reaction with an aryl fluoride in a suitable solvent such as tetrahydrofuran or dimethylformamide, as shown in Formula IIIg.

[0112] The benzyl protecting group can be removed by palladium hydrogenation conditions or with strong acid. See the reaction depicted below, where Formula IIIg refers to any R as described herein. 4 The substituted indole, and the deprotected product is shown in Formula IIIh.

[0113]

[0114] The indole-fused naphthol depicted in Formula IIIh can then react with an aryl propargyl alcohol under acidic conditions to yield an indole-fused naphthopyran, as depicted in Formula Ia. See the reaction depicted below.

[0115]

[0116] According to the present invention, there is also provided a photochromic composition comprising at least one photochromic compound according to the present invention, such as those represented by formula (I), (Ia) and / or (Ib) as previously described herein.

[0117] The photochromic composition may include (i) an organic material, wherein the organic material is at least one of a polymeric material, an oligomeric material, or a monomeric material; and (ii) a photochromic 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 at least one method including, but not limited to, blending or bonding the photochromic compound with the organic material or a precursor of the organic material. As used herein, with respect to incorporating the photochromic compound into the organic material, the terms "blending" and "blended" mean mixing or blending the photochromic compound / material with at least a portion of the organic material, but not bonding to the organic material. Further, as used herein, with respect to incorporating the photochromic compound into the organic material, the terms "bonding" or "bonded" mean that the photochromic compound / material is connected to a portion of the organic material or its precursor, such as by one or more covalent bonds. For example, although not limited herein, the photochromic material may be connected to the organic material via a reactive substituent.

[0118] When the organic material is a polymer material, the photochromic compound can be incorporated into at least a portion of the polymer material or at least a portion of the monomer material or oligomer material that forms the polymer material. For example, one or more photochromic compounds having reactive substituents according to the present invention can be bonded to an organic material (such as a monomer, oligomer, or polymer having a group that can react with the reactive portion, or a group that can react as a comonomer in a polymerization reaction to form the organic material (e.g., in a copolymerization process).

[0119] As discussed above, in 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 obtained by partial saponification of copolymers of ethylene and vinyl acetate); cellulose acetate butyrate; poly(urethane); poly(acrylate); poly(methacrylate); epoxy compounds; aminoplast functional polymers; poly(anhydrides); poly(urea urethane); N-alkoxymethyl(meth)acrylamide functional polymers; poly(siloxanes); poly(silanes); and combinations and mixtures thereof. Further categories 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 at column 39, line 45 to column 40, line 67 of US 9,028,728 B2.

[0120] 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, an inhibitor, a solvent, a light stabilizer, a thermal stabilizer, a release agent, a rheology control agent, a leveling agent, a free radical scavenger, and / or an adhesion promoter.

[0121] The photochromic composition according to the present invention may be a photochromic coating composition. The photochromic coating composition of the present invention may include: a photochromic compound according to the present invention, such as previously described herein with respect to formula (I), (Ia), and / or (Ib), optionally a curable resin composition; and optionally a solvent. The photochromic coating composition may be in the form of liquid coatings and powder coatings as are known 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.

[0122] 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, for example, an epoxide functional polymer reactant; and a second reactant (or component), which is a crosslinker having a functional group reactive to the functional group of the first reactant 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 include one or more functional species, and each is present in an amount sufficient to provide a cured photochromic coating having a desired combination of physical properties (e.g., smoothness, optical transparency, solvent resistance, and hardness).

[0123] 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: a curable resin composition comprising an epoxide functional polymer (e.g., a (meth) acrylic polymer containing a residue of glycidyl (meth) acrylate) and an epoxide reactive crosslinker (e.g., containing active hydrogen, such as hydroxyls, thiols, and amines); and a curable resin composition comprising an active hydrogen functional polymer (e.g., a hydroxyl, thiol, and / or amine functional polymer) and a capped or blocked isocyanate functional crosslinker. "Capped or blocked isocyanate functional crosslinker" means a crosslinker having two or more blocked isocyanate groups that can be decapped or 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 unblocking of the crosslinking agent 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. 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 the following: 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.

[0124] The curable photochromic coating composition according to the present invention may optionally contain additives such as waxes for flow and wetting, flow control agents (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 trade names IRGANOX and TINUVIN. When used, these optional additives are typically present in an amount of up to 20% by weight (e.g., from 0.5% to 10% by weight), based on the total weight of the resin solids of the curable resin composition.

[0125] The photochromic composition, photochromic article and photochromic coating composition according to the present invention may further include additives known in the art that aid or assist the processing and / or performance of the composition or article. Non-limiting examples of such additives include photoinitiators, thermal initiators, inhibitors, solvents, light stabilizers (such as but not limited to UV absorbers and light stabilizers, such as hindered amine light stabilizers (HALS)), thermal stabilizers, release agents, rheology control agents, 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.

[0126] The photochromic compounds of the present invention can be used in such an amount (or ratio) that the composition, organic material or substrate (e.g., photochromic articles and photochromic coatings) into which the photochromic compounds are incorporated or otherwise attached exhibits the desired optical properties. The amount and type of photochromic material can be selected so that when the photochromic compound is in a closed-form (e.g., in a whitish or unactivated state), the composition, organic material or substrate is transparent or colorless, and when the photochromic compound (such as the photochromic indole naphthopyran of the present invention) is in an open-form (e.g., when activated by actinic radiation), the desired resulting color can be exhibited. The exact amount of photochromic material utilized 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 a variety of factors, such as, but not limited to, the absorption characteristics of the photochromic compound, the desired color and intensity of the color when activated, and the method used to incorporate or attach the photochromic material into or to the substrate. The photochromic composition according to the present invention may include the following photochromic compound according to the present invention, the photochromic compound includes a compound represented by formula (I), (Ia) or (Ib) in an amount of 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 a compound represented by formula (I), (Ia) or (Ib) 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.

[0127] The present invention also relates to a photochromic article comprising one or more photochromic compounds according to the present invention, such as a photochromic compound represented by formula (I), (Ia) or (Ib). The photochromic article can be prepared by methods known in the art, such as by imbibition methods, in-situ casting methods, coating methods, in-mold coating methods, overmolding methods, and lamination methods.

[0128] For example, the photochromic article can be selected from ophthalmic articles, display articles, windows, mirrors, active liquid crystal cell articles, and passive liquid crystal cell articles.

[0129] For example, the photochromic article of the present invention can be an ophthalmic article, and the ophthalmic article can be selected from corrective lenses, non-corrective lenses, contact lenses, intraocular lenses, magnifying lenses, protective lenses, and goggles.

[0130] For example, the photochromic article of the present invention may be a display article, and the display article may be selected from a screen, a monitor, and a security element.

[0131] Such photochromic articles (e.g., photochromic lenses) can be transformed from a first, unactivated state (e.g., a transparent and non-blue light blocking state) to a second, activated state (e.g., a tinted and blue light blocking state) when exposed to actinic radiation. Upon removal of the actinic radiation source, the article reverts to the first, unactivated (and transparent) state. Thus, photochromic articles according to the present invention provide enhanced protection against health risks associated with blue light exposure during outdoor activities while maintaining acceptable aesthetics indoors.

[0132] 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.

[0133] Examples

[0134] The following examples are provided to illustrate the photochromic compounds of the present invention, particularly the improved bleached color of the photochromic compounds of the present invention. Section 1 provides a description of the synthesis of the photochromic compounds of the present invention. Section 2 provides an evaluation of the photochromic performance of the photochromic compounds of the present invention relative to comparative photochromic compounds.

[0135] Part 1: Synthesis of photochromic compounds

[0136] Examples 1

[0137]

[0138] Step 1

[0139] While stirring under nitrogen, benzophenone (84.0g, 461mmol) and dimethyl succinate (80.84g, 553mmol) were dissolved in toluene (1.0L). Potassium tert-amyl alcohol (1.7M in toluene, 352.5mL, 599mmol) was added dropwise at room temperature within 2 hours. After 20 hours, water (1.5L) was added to the reaction mixture and the layers were separated. The organic phase was discarded. The aqueous phase was extracted with toluene (1×200ml) and the organic phase was discarded. The aqueous phase was acidified to pH 4 with 2N hydrochloric acid solution, and then the solution became turbid. The product was separated by extracting the mixture with ethyl acetate (3×300ml). The organic layers were combined, dried with sodium sulfate and concentrated under reduced pressure. The resulting solid was washed with hexane, collected and dried under vacuum to give 132.8g (97% yield) of colorless powder.

[0140]

[0141] Step 2

[0142] The product from step 1 (132.8 g, 448.2 mmol) was combined with acetic anhydride (254.2 mL, 2.69 mol) and toluene (250 ml) and heated to reflux while stirring under nitrogen. After 16 hours, the reaction mixture was concentrated under reduced pressure and the resulting oil was precipitated in hexanes to give an off-white solid. The solid was collected and dried to give 125.5 g (88% yield).

[0143]

[0144] Step 3

[0145] Under stirring, the product (150g, 468mmol) from step 2 is suspended in methanol (400ml). In the suspension, concentrated hydrochloric acid (10ml) is added and the reaction mixture is heated to reflux for 2 hours. Once completed, the reaction mixture is cooled to room temperature and left to stand for 50 hours without stirring because the product is recrystallized. Crystals are collected and dried to give complete conversion (130g).

[0146]

[0147] Step 4

[0148] While stirring under nitrogen, the product from step 3 (130 g, 467 mmol) was dissolved in anhydrous dimethylformamide (400 ml). Potassium carbonate (130 g, 934 mmol) was suspended in the mixture, followed by the slow addition of benzyl chloride (71.0 g, 560 mmol). The reaction mixture was heated at 75 ° C for 16 hours. Once cooled, the reaction mixture was slowly poured into ice water and extracted into ethyl acetate (3 × 500 ml). The organic layers were combined, washed with brine (2 × 300 ml), dried over sodium sulfate and concentrated under reduced pressure. The resulting solid was washed with methanol, collected and dried under vacuum to give a colorless solid (155.4 g, 90% yield).

[0149]

[0150] Step 5

[0151] The product from step 4 (155.4 g, 422 mmol) was suspended in 2-propanol (300 ml) under stirring. Sodium hydroxide solution (10% w / w in water, 300 ml) was added and the reaction mixture was heated to reflux for 18 hours. Once cooled, the reaction mixture was poured into an acidic ice-water bath (pH 3-4) to form a colorless precipitate. The solid was collected and dried to give 148.9 g (99% yield).

[0152]

[0153] Step 6

[0154] While stirring under nitrogen, the product (149.1g, 421mmol) from step 5 is suspended in anhydrous toluene (800ml). Triethylamine (111g, 1.1mol) and anhydrous ethanol (100ml) are added to dissolve the suspension. Diphenylphosphoryl azide (174g, 632mmol) is added to the reaction mixture in batches, and the reaction mixture is exothermic to reflux by itself, and heat is added to reflux for a total of 2 hours. Once cooled, the reaction mixture is added to water (1.5L) and ethyl acetate (500ml) and each layer is separated. The organic layer is washed with water (3×1L), dried over sodium sulfate and concentrated under reduced pressure to give a reddish oil, which is used without further purification.

[0155]

[0156] Step 7

[0157] The resulting oil from step 6 was dispersed in tetrahydrofuran (600 ml), ethanol (400 ml) and water (1.1 L) with sodium hydroxide (86 g, 2.2 mol). The reaction mixture was heated to reflux for 5 days. Once cooled, brine (200 ml) was added to the reaction mixture, the layers were separated, and the aqueous layer was washed with ethyl acetate (3×300 ml). The organic layers were combined, dried over sodium sulfate and concentrated under reduced pressure to give a reddish semi-solid, which was used without further purification.

[0158]

[0159] Step 8

[0160] While stirring under nitrogen, the product from step 7 is absorbed in dichloromethane (1.2 L). Picolinic acid (78 g, 632 mmol) and 4-(dimethylamino)pyridine (5.2 g, 42 mmol) are added, followed by N, N'-dicyclohexylcarbodiimide (130.4 g, 632 mmol). The reaction mixture is allowed to stand at room temperature for 16 hours. The reaction mixture is filtered and concentrated under reduced pressure to give a black solid, which is washed with methanol to give intermediate 2 (160.85 g, 89% yield for 3 steps) as an off-white powder.

[0161]

[0162] Step 9

[0163] The product from step 8 (76.5 g, 178 mmol) was dissolved in anhydrous dimethylformamide (500 ml) with stirring under nitrogen, and copper (II) acetate (65.0 g, 356 mmol) and glacial acetic acid (10.7 g, 178 mmol) were added thereto. The reaction mixture was heated to 150 ° C for 20 hours to give a 70% conversion of the starting material. The reaction mixture was filtered through a diatomaceous earth pad and the pad was washed with 500 ml of ethyl acetate. The filtrate was added to a separatory funnel along with water (1.0 L) containing ethylenediamine (10 ml), and the layers were separated. The organic layer was washed with water (3×300 ml), dried over sodium sulfate and concentrated under reduced pressure to give an off-white solid. The material was subjected to a second iteration of the reaction conditions and the same separation procedure. The resulting solid was washed twice with methanol (300 ml) to give an off-white powder (49.5 g, 86% yield). The product was obtained by 1 H NMR and mass spectrometry confirmed.

[0164]

[0165] Step 10

[0166] The product from step 9 (4.0 g, 12.4 mmol) was combined with 3,5-di-tert-butylbromobenzene (6.73 g, 25.0 mmol), copper iodide (1.20 g, 6.2 mmol), potassium carbonate (3.42 g, 24.8 mmol), 1,10-phenanthroline (0.45 g, 2.5 mmol) and dibenzo-18-crown-6-ether (0.45 g, 1.20 mmol) in anhydrous dimethylformamide (30 ml) while stirring under nitrogen. The reaction mixture was heated to 150° C. for 4 hours. Once cooled, the reaction mixture was taken up in ethyl acetate (250 ml) and washed initially with water (200 ml), with ethylenediamine (10 ml), and subsequently with water (2×250 ml). The organic layer was dried over sodium sulfate and concentrated onto silica gel under reduced pressure. Chromatography (silica gel, 0-50% dichloromethane in hexanes) gave a colorless powder which was washed with methanol and dried under vacuum (5.44 g, 86% yield).

[0167]

[0168] Step 11

[0169] The product from step 10 (2.0 g, 3.91 mmol) was combined with ammonium formate (2.52 g, 40.0 mmol) and palladium on carbon (Degussa model E1003 U / W, 0.14 g, 1.2 mmol) in dimethylformamide (30 ml) while stirring under nitrogen. The reaction mixture was heated to 80° C. for 3 hours. Once cooled, the reaction mixture was filtered through a pad of celite and the pad was washed with ethyl acetate (250 ml). The filtrate was washed with water (3×300 ml), dried over sodium sulfate and concentrated under reduced pressure to give a brown glass which was used without further purification. (If precipitated from dichloromethane into hexanes, a powder may be obtained.)

[0170]

[0171] Step 12

[0172] While stirring under nitrogen, the product from step 11 (0.80g, 1.90mmol) is combined with 1,1-bis(4-methoxyphenyl)prop-2-yn-1-ol (0.55g, 2.3mmol) in toluene (25ml) and heated to reflux. Add p-toluenesulfonic acid (5-10mg) and heat the reaction mixture to reflux for 1 hour. Once cooled, the reaction mixture is concentrated onto silica gel under reduced pressure. Chromatography (silica gel, 0-70% dichloromethane in hexane) produces a dark solid. The product is recrystallized twice from tetrahydrofuran, methyl tert-butyl ether and methanol to give Example 11 (1.14g, 89% yield) as a light yellow powder, and confirmed by mass spectrometry.

[0173] Example 2-21 and Comparative Example 1-11

[0174] Additional photochromic dyes were prepared according to Example 1 and are summarized in Table 3. For each example, the appropriate substituted phenyl bromide was used in place of 3,5-di-tert-butyl bromobenzene in Step 10 of Example 1, as indicated in the N-coupling component column in Table 3. The appropriate substituted 1,1-diphenylprop-2-yn-1-ol ("propargyl alcohol") was used in Step 12 of Example 1, as indicated in the Propargyl alcohol column of Table 3. Comparative Examples 4, 8, and 11 were prepared by alkylating the product of Step 9 of Example 1 using sodium hydride and methyl iodide in anhydrous dimethylformamide. All products were confirmed by mass spectrometry.

[0175] Table 3

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182] 1 The yield corresponds to the isolated intermediate (Formula IIIg) prior to deprotection and propargyl alcohol addition. 2 The yield corresponds to the isolated dye compound (Formula Ia).

[0183] Examples 22-24 and CE12

[0184] Additional photochromic dyes were prepared according to Example 1, except that 4,4'-dimethylbenzophenone was used instead of benzophenone in Example 1, Step 1, and are summarized in Table 4. For each example, the appropriate substituted phenyl bromide is indicated in the N-coupling component column in Table 4. The appropriate substituted 1,1-diphenylprop-2-yn-1-ol ("propargyl alcohol") was also used as indicated in the propargyl alcohol column in Table 4. All products were confirmed by mass spectrometry.

[0185] Table 4

[0186]

[0187]

[0188] Instance 25 and CE13

[0189] Additional photochromic dyes were prepared according to Example 1, except that 4-methoxybenzophenone was used instead of benzophenone in Example 1, Step 1, and are summarized in Table 5. For each example, the appropriate substituted phenyl bromide is indicated in the N-coupling component column in Table 5. The appropriate substituted 1,1-diphenylprop-2-yn-1-ol ("propargyl alcohol") was also used as indicated in the propargyl alcohol column in Table 5. All products were characterized by mass spectroscopy.

[0190] Table 5

[0191]

[0192] Examples 26-27 and CE14

[0193] Additional photochromic dyes were prepared according to Example 1, except that (3,4-dimethoxyphenyl)(4-(trifluoromethyl)phenyl)methanone was used instead of benzophenone in Example 1, Step 1, and are summarized in Table 6. For each example, the appropriate substituted phenyl bromide is indicated in the N-coupling component column in Table 6. The appropriate substituted 1,1-diphenylprop-2-yn-1-ol ("propargyl alcohol") was also used as indicated in the propargyl alcohol column in Table 6. All products were characterized by mass spectroscopy.

[0194] Table 6

[0195]

[0196] Part 2: Evaluation of Photochromic Dyes

[0197] Each of the photochromic dyes from Examples 1 to 27 and each of Comparative Examples CE1 to CE14 was incorporated into a polyurethane coating system at the same mol % and applied at the same coating thickness to a polyurethane coating system consisting of 2" x 2" test chips made of PTFE monomer (PPG Industries, Inc.). All coated test pieces were cured at 125°C for 1 hour.

[0198] Each coated test piece was conditioned by first exposing to 365-nanometer ultraviolet light at a distance of about 14 centimeters for 10 minutes to activate the photochromic material within the coating. The UVA (315 nm to 380 nm) irradiance at the sheet was measured with a model Li-1800 spectroradiometer and found to be 22.2 watts per square meter. Each test sheet 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 sheet and is found to be 21.9 Klux. The coated test sheet 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 coated test sheet at 390 nanometers is measured before measuring on the optical bench.

[0199] The percent transmittance (%T) of Examples 1 to 27 and each of Comparative Examples CE1 to CE14 was determined using CIE Y values ​​according to CIE 15:2004 colorimetry, using D 65 illuminant and 10° observer. The a* and b* values ​​as used in the specification and claims herein refer to the 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.

[0200] The BMP optical bench is equipped with two 150-watt Model #66057 Xenon Arc Lamp. Direct the light path from Lamp 1 through the 3 mm KG-2 bandpass filter and appropriate neutral density filters, which contribute to the required UV and partial visible light irradiance levels. Direct the light path from lamp 2 through a 3 mm 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 inch x 2 inch 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 (i.e., BMPSoft version 2.1) was used on the BMP to control timing, irradiance, chamber and sample temperature, shutters, filter selection, and response measurement. A spectrophotometer (Model MCS 501) and fiber optic cables were used to transmit light through the coated test chips for response and color measurements. Photopic response measurements were collected on each coated test chip. The power output of the optical bench (i.e., the dose of light to which the coated test chip was exposed) was adjusted to 6.7 W / m2. 2 ) UVA, from 315nm-380nm integration and 50Klux illumination, from 380nm-780nm integration. The power set point is measured using an irradiance probe and a calibrated Zeiss spectrophotometer. The coated test chip sample pool is equipped with a quartz window and an automatic centering sample holder. The temperature in the sample pool is controlled at 23 ° C by the software of the FX-10 model environmental simulator with an improved Facis. The same Zeiss spectrophotometer and fiber optic cable are used to transmit light from a tungsten halogen lamp and pass through the sample to measure the dynamic photochromic response and color measurement of the sample. The collimated monitoring beam from the fiber optic cable is maintained perpendicular to the test sample while passing through the sample and directed to the receiving fiber optic cable assembly attached to the spectrophotometer. The exact placement point of the sample in the sample pool 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 from the vertical line at the sample placement point is =30°.

[0201] The response measurement is determined by establishing an initial unactivated transmittance, opening the shutter from the xenon lamp, and measuring the transmittance through activation at selected time intervals, based on the change in optical density (ΔOD) from the unactivated or whitish state to the activated or colored state. The optical density change is determined according to the following formula: ΔOD = log (10) (% Tb / % Ta), where % Tb is the percent transmittance in the whitish state and % Ta is the percent transmittance in the activated state. The ΔOD at saturation is after 15 minutes of 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 fifteen-minute ΔOD at 73.4°F (23°C) after the activating light source is removed.

[0202] Calculate ΔE according to the following equation ％T and ESF.

[0203] ΔE ％T =[(%T-%T o ) 2 +(a*-a* o ) 2 +(b*-b* o ) 2 ] 0.5

[0204] Equation 1

[0205] ESF=[(R 3 and R 4 Hammett's σ p The sum of the values))x10]+(R 1 and R 2 The sum of the spatial volume A values)

[0206] Equation 2

[0207] The measured values ​​of a*, b*, and percent transmittance of the transparent substrate were as follows: a*0 was -0.07, b*0 was 0.3, and %T0 was 92.3. These values ​​were determined as reported above.

[0208] Table 7 shows the 3 and R 4 Color properties and kinetic data for compounds that are methoxy, including Examples 1 to 7 and Comparative Examples CE1 to CE5. The structures of Examples 1 to 7 and CE1 to CE5 can be found in Table 3.

[0209] Table 7

[0210]

[0211]

[0212] The results in Table 7 clearly show that the compounds of the present invention provide a lower ΔE compared to similar compounds having ESF values ​​outside the range of the present invention. ％T For example, compared with the lack of R with significant steric volume 1 or R 2 Compared with the indole naphthopyran compounds with substituted groups (such as comparative examples CE1 to CE4 and CE5), the indole naphthopyran compounds of the present invention have lower ΔE ％T value to obtain an ESF value of at least -3.3. The desired ΔE ％T The value is achieved by having the desired percent transmittance, a* value, and b* value. Comparative Example CE5 has a lower percent transmittance value (78.6%) and higher a* and b* values, which results in a high ΔE of 14.12. ％T In contrast, Example 1 has a higher percent transmittance value of 89.8%, and a* and b* values ​​closer to zero, yielding a desirable ΔE of 3.23. ％T The indole naphthopyran compounds of the present invention also exhibit lower ΔE values ​​than indole naphthopyran compounds having alkyl substitution on the indole nitrogen rather than aryl substitution on the indole nitrogen (such as CE4). ％T The ΔOD values ​​and the fade T1 / 2 values ​​are included in Table 7 and reported below to indicate that the compounds of the present invention are thermally reversible photochromic compounds.

[0213] Table 8 shows the 3 Color properties and kinetic data for compounds that are morpholino, including Examples 8 to 12 and Comparative Examples CE6 to CE8. The structures of Examples 8 to 12 and CE6 to CE8 can be found in Table 3.

[0214] Table 8

[0215]

[0216]

[0217] The results in Table 8 clearly show that the compounds of the present invention provide a lower ΔE compared to similar compounds having ESF values ​​outside the range of the present invention. ％T The values ​​indicated an improvement in the decolorization color. 3 The strong electron-donating nature of the substituent requires a significant steric bulk of R 1 and / or R 2 groups to achieve the desired ESF value and color properties. For example, R 1 or R 2 Compared with the indole naphthopyran compounds with substituted groups (such as comparative examples CE6 and CE7), the indole naphthopyran compounds of the present invention have lower ΔE ％T The indole naphthopyran compounds of the present invention also exhibit lower ΔE values ​​than indole naphthopyran compounds having alkyl substitutions on the indole nitrogen rather than aryl substitutions on the indole nitrogen (such as CE8). ％T value.

[0218] Table 9 shows the 3 and R 4 Color properties and kinetic data for compounds of 1,2-dihydrogen 2-nitropropene, including Examples 13 to 21 and Comparative Examples CE9 to CE11. The structures of Examples 13 to 21 and CE9 to CE11 can be found in Table 3.

[0219] Table 9

[0220]

[0221] The results in Table 9 clearly show that the absence of at least one R having a steric volume A of at least 0.6 1 or R 2 Compared with similar compounds of the group, the compounds of the present invention provide a lower ΔE ％T The value indicates the improved decolorization color. For example, with R 1 and R 2Compared with the indole naphthopyran compounds containing hydrogen (such as comparative examples CE9 and CE10), the indole naphthopyran compounds of the present invention have lower ΔE ％T The indole naphthopyran compounds of the present invention also exhibit lower ΔE values ​​than indole naphthopyran compounds having alkyl substitution on the indole nitrogen rather than aryl substitution on the indole nitrogen (such as CE11). ％T value.

[0222] Table 10 shows the 5 and R 6 Color properties and kinetic data of compounds of the substituted groups, including Examples 22 to 27 and Comparative Examples CE12 to CE14. The structures of Examples 22 to 24 and CE 12 can be found in Table 4. The structures of Example 25 and CE 13 can be found in Table 5. The structures of Examples 26 and 27 and CE 14 can be found in Table 6.

[0223] Table 10

[0224]

[0225] The results in Table 10 clearly show that the absence of at least one R having a steric volume A of at least 0.6 1 or R 2 Compared with similar compounds of the group, the compounds of the present invention provide a lower ΔE ％T The value indicates the improved decolorization color. For example, with R 1 and R 2 Compared with the indole naphthopyran compounds containing hydrogen (such as comparative examples CE12 to CE14), the indole naphthopyran compounds of the present invention have lower ΔE ％T value.

[0226] The present invention may be further characterized by one or more of the following non-limiting clauses.

[0227] Item 1. An indole naphthopyran compound comprising a core skeleton structure represented by formula (Ib),

[0228]

[0229] in,

[0230] R 1 and R 2 Each independently has a spatial volume A,

[0231] Where R 1 or R 2 At least one of them has a spatial volume A of at least 0.6,

[0232] R3 and R 4 Each has independently Hammett σ p value,

[0233] wherein the indole naphthopyran compound has a calculated electron steric factor of at least -3.3;

[0234] m is 0 to 4;

[0235] n is 0 to 4; and

[0236] R 5 , R 6 and R 7 are each independently hydrogen or a group other than hydrogen.

[0237] Item 2. The indole naphthopyran compound according to Item 1, wherein the indole naphthopyran compound has a calculated electron steric factor of at least 0.

[0238] Item 3. The indole naphthopyran compound according to Item 1 or 2, wherein R 1 and R 2 At least one of them is independently an alkyl group, an alkoxy group, a halogenated alkyl group, or a nitrogen-containing heterocycle.

[0239] Item 4. The indole naphthopyran compound according to any one of Items 1 to 3, wherein R 3 and R 4 At least one of them is independently hydrogen, alkyl, alkoxy, halogenated alkyl, or nitrogen-containing heterocycle.

[0240] Item 5. The indole naphthopyran compound according to any one of Items 1 to 4, wherein R 1 or R 2 At least one of the groups is methyl, ethyl, butyl, tert-butyl, trifluoromethyl, or methoxy.

[0241] Item 6. The indole naphthopyran compound according to any one of Items 1 to 5, wherein R 1 and R 2 Both are the same group.

[0242] Clause 7. The indole naphthopyran compound according to any one of Clauses 1 to 6, wherein R 3 or R 4 At least one of them is methoxy or trifluoromethyl.

[0243] Clause 8. The indole naphthopyran compound according to any one of clauses 1 to 7, wherein

[0244] in,

[0245] m is 0 to 4, n is 0 to 4; and

[0246] Independent of each m's R 5 and R is independent of each n 6 yes

[0247] i. Hydroxyl group;

[0248] ii. cyano;

[0249] iii. (meth)acrylate;

[0250] iv. amino or nitrogen-containing heterocyclic ring;

[0251] v. Mesogen-containing group L 1 ;

[0252] vi. substituted or unsubstituted alkyl;

[0253] vii. substituted or unsubstituted alkenyl;

[0254] viii. substituted or unsubstituted alkynyl;

[0255] ix. halogen group;

[0256] x. fully halogenated groups;

[0257] xi. borate ester or boric acid;

[0258] xii. polyether, polyester, polycarbonate, or polyurethane;

[0259] xiii. substituted or unsubstituted aryl;

[0260] xiv. substituted or unsubstituted heterocycloalkyl;

[0261] xv. substituted or unsubstituted heteroaryl;

[0262] xvi. substituted or unsubstituted alkoxy or substituted or unsubstituted aryloxy;

[0263] xvii. substituted or unsubstituted alkylthio or substituted or unsubstituted arylthio;

[0264] xviii. ketone, aldehyde, ester, carboxylic acid, carboxylic acid ester, or amide;

[0265] xix. carbonate, carbamate, or urea; or

[0266] xx. Siloxane, alkoxysilane, or polysiloxane.

[0267] Item 9. An indole naphthopyran compound as described in Item 8, wherein each alkyl substituent, each alkenyl substituent, each alkynyl substituent, each aryl substituent, each heterocycloalkyl substituent, each heteroaryl substituent, each alkoxy substituent, each aryloxy substituent, each alkylthio substituent, and each arylthio substituent are independently selected from halogen, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, perhaloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, hydroxyl, alkylthio, 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, arylamine, alkylamine, cyclic amino group, heteroaromatic compound, or a combination thereof.

[0268] Item 10. The indole naphthopyran compound according to Item 8 or 9, wherein each of the mesogen-containing groups L 1 are independently represented by the following formula (II),

[0269] Formula (II)

[0270] -[S 1 ] c -[Q 1 -[S 2 ] d ] d’ -[Q 2 -[S 3 ] e ] e’ -[Q 3 -[S 4 ] f ] f’ -R

[0271] in,

[0272] (a)Q 1 , Q 2 , and Q 3 is independently at each occurrence a divalent group selected from the group consisting of unsubstituted aryl, substituted aryl, unsubstituted cycloalkyl, and substituted cycloalkyl;

[0273] wherein the aryl substituent and the cycloalkyl substituent are each independently selected from the group consisting of liquid crystal mesogens, halogens, alkyls, alkoxys, alkylaminos, dialkylaminos, alkylthios, alkoxycarbonyls, alkylcarbonyls, alkoxycarbonyloxys, aryloxycarbonyloxys, perfluoroalkyls, and perfluoroalkoxys;

[0274] (b) c, d, e, and f are each independently an integer from 0 to 3; and each S 1 , S2 , S 3 , and S 4 Each occurrence is independently selected from a Spacer unit selected from the group consisting of:

[0275] (i.) -C(Z)2-, -N(Z)-, -C(Z)=C(Z)-, -C(Z)=N-, wherein each occurrence of Z is independently selected from the group consisting of hydrogen, alkyl, or aryl;

[0276] (ii) -Si(CH3)2-, -Si(CH3)2O-; and

[0277] (iii) -O-, -C(=O)-, -C≡C-, -N=N-, -S-, -S(=O)-, -(O=)S(=O)-, -(O=)S(=O)O-, -O(O=)S(=O)O-

[0278] Provided that when two heteroatom-containing Spacer units are linked together, the Spacer units are linked so that the heteroatoms are not directly linked to each other;

[0279] (c) R is alkyl; and

[0280] (d) d', e' and f' are each independently 0, 1, 2, 3, and 4, provided that the sum of d'+e'+f' is at least 1.

[0281] Item 11. The indole naphthopyran compound according to any one of Items 8 to 10, wherein

[0282] Where R 7 Selected from the group consisting of an alkyl group, an alkoxy group, a haloalkyl group, and a nitrogen-containing heterocycle.

[0283] Item 12. The indole naphthopyran compound according to Item 1, wherein R 1 is trifluoromethyl, R 2 is trifluoromethyl or hydrogen, R 3 is hydrogen, and R 4 It's hydrogen.

[0284] Item 13. An indole naphthopyran compound as described in any one of Items 1 to 12, wherein the formula (Ib) contains at least one additional substituent, which is the same or different, located at at least one available position on the core skeleton structure among positions 5, 6, 7, 8, 9, 10, 11 or 12 described therein.

[0285] Item 14. The indole naphthopyran compound as described in Item 13, wherein the at least one additional substituent is independently selected from an alkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, a thiol group, an alkylthio group, an arylthio group, a keto group, an aldehyde group, an ester group, a carboxylic acid group, a phosphate group, a phosphate ester group, a sulfonic acid group, a sulfonate group, a nitro group, a cyano group, an aralkyl group, an alkenyl group, an alkynyl group, a haloalkyl group, a perhaloalkyl group, an alkaryl group, a hydroxy-substituted aryl group, an alkoxy-substituted aryl group, a heterocycloalkyl-substituted aryl group, a halogen-substituted aryl group, a multi-fused-ring aryl group, a multi-fused-ring heteroaryl group, an amine group, a carboxylate group, a siloxane group, an alkoxysilane group, a polysiloxane group, an amide 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, a cyclic amino group, a heteroaromatic group, or a combination thereof.

[0286] Item 15. A photochromic composition comprising the indole naphthopyran compound of any one of Items 1 to 14.

[0287] Clause 16. A photochromic article comprising the indole naphthopyran compound of any one of Clauses 1 to 14, wherein the photochromic article is selected from the group consisting of an ophthalmic article, a display article, a window, a mirror, an active liquid crystal cell article, and a passive liquid crystal cell article; or

[0288] wherein the photochromic article is an ophthalmic article selected from the group consisting of corrective lenses, non-corrective lenses, contact lenses, intraocular lenses, magnifying lenses, protective lenses, and goggles; or

[0289] Wherein the photochromic article is a display article selected from the group consisting of: a screen, a monitor, and a security element.

[0290] Item 17. Use of the indole naphthopyran compound according to any one of Items 1 to 14 for preparing a photochromic article.

[0291] The present invention has been described with reference to specific details of particular embodiments thereof. It is not intended that these details be considered limitations on the scope of the invention except to the extent they are included in the appended claims.

Claims

1. An indole naphthopyran compound comprising a core skeleton structure represented by formula (Ia), in, R 1 and R 2 Each independently has a spatial A value, where R 1 and R 2 At least one of them is independently a linear or branched C1-C 12 Alkyl, linear or branched C1-C 12 Alkoxy, or straight or branched C1-C 12 Perfluoroalkyl, Where R 1 or R 2 at least one of has a spatial A value of at least 0.6, R 3 and R 4 Each has independently Hammett σ p Value, where R 3 and R 4 At least one of them is independently hydrogen, a linear or branched C1-C 12 Alkyl, linear or branched C1-C 12 alkoxy, fluorine, or a nitrogen-containing heterocycle, wherein the nitrogen-containing heterocycle is selected from morpholino, piperidino and pyrrolidino, wherein the indole naphthopyran compound has a calculated electron steric factor (ESF) of at least -3.3, wherein the electron steric factor is calculated according to the following equation: ESF = [(R 3 and R 4 Hammett's σ p sum of values) x 10] + (R 1 and R 2 The sum of the spatial A values) m is 0 to 4, n is 0 to 4; and Independent of each m's R 5 and R is independent of each n 6 yes: Straight or branched C1-C 12 alkyl, Straight or branched C1-C 12 Perfluoroalkyl, or Straight or branched C1-C 12 Alkoxy.

2. The indole naphthopyran compound according to claim 1, wherein The indole naphthopyran compound has a calculated electron steric factor of at least zero.

3. The indole naphthopyran compound according to claim 1, wherein R 1 or R 2 At least one of the groups is methyl, ethyl, butyl, tert-butyl, trifluoromethyl, or methoxy.

4. The indole naphthopyran compound according to claim 1, wherein R 1 and R 2 Both are the same group.

5. The indole naphthopyran compound according to claim 1, wherein R 3 or R 4 At least one of the is methoxy or morpholino.

6. The indole naphthopyran compound according to claim 1, comprising a core skeleton structure represented by formula (Ib): Where R 7 Selected from the group consisting of: straight or branched C1-C 12 Alkyl, linear or branched C1-C 12 Alkoxy, linear or branched C1-C 12 haloalkyl, and a nitrogen-containing heterocyclic ring, wherein the nitrogen-containing heterocyclic ring is selected from morpholino, piperidino and pyrrolidino.

7. The indole naphthopyran compound according to claim 1, wherein R 1 is trifluoromethyl, R 2 is trifluoromethyl or hydrogen, R 3 is hydrogen, and R 4 It's hydrogen. 8 . A photochromic composition comprising the indole naphthopyran compound according to claim 1 .

9. A photochromic article comprising the indole naphthopyran compound according to any one of claims 1 to 7, wherein the photochromic article is selected from ophthalmic articles, display articles, windows, mirrors, active liquid crystal cell articles, or passive liquid crystal cell articles.

10. The photochromic article of claim 9, 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.

11. The photochromic article of claim 9, wherein the photochromic article is selected from a display article, and the display article is selected from a screen, a monitor, and a security element.

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