Preparations containing indole naphthopyrans

Abstract

An article is provided that changes from a first state to a second state in response to actinic radiation. The article comprises an indole naphthopyran, wherein in the first state the article exhibits a percent transmittance greater than 80%, and in the second state the article exhibits a percent transmittance between 35% and 75%, and a τ of less than 20%. SB The article may be a photochromic article 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.

Description

Technical Field

[0001] The present invention relates to articles, such as optical articles, comprising certain indolenaphthopyran compounds, particularly photochromic indolenaphthopyrans. 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., bleached or substantially colorless) first state to an activated (e.g., colored or darkened) second state when exposed to actinic radiation. When the actinic radiation is removed, the photochromic compound reversibly transitions from the second activated state back to the first, 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; and dichroic properties, such as in the case of photochromic-dichroic compounds, which can be quantified with respect to the absorption ratio (AR) value. The change in optical density measures the change from an unactivated state to an activated state.

[0004] Some photochromic compounds have a bimodal absorption curve having an absorption band "A" (hereinafter referred to as "A band") having a greater intensity than an absorption band "B" (hereinafter referred to as "B band"). The absorption of the A band generally occurs in the wavelength range of 420-500 nanometers, while the absorption of the B band occurs in the wavelength range of 500-650 nanometers in the active visible spectrum.

[0005] Yellow colored naphthopyrans have high b* values ​​in the activated (i.e. colored) state, but these compounds have inherent weaknesses in durability and often degrade at a much faster rate than the violet or blue photochromic compounds of the indeno-fused naphthopyran family. Broadband absorbing indeno-fused compounds have been used to overcome the limitations of yellow naphthopyrans, but indeno-fused naphthopyrans that are yellow (high b*) in the activated (i.e. colored) state remain elusive.

[0006] The harmful health effects of blue light, such as cataracts, macular degeneration, and disruption of circadian rhythms, have been well documented. Many fixed tint optical products have been produced to help block harmful blue light from indoor light sources (such as from fluorescent lighting) and outdoor exposure to sunlight with high levels of blue light present. Such conventional optical products typically use static yellow dyes or tints as blue light blockers. However, the static yellow color of such optical products containing these static yellow dyes is aesthetically undesirable, especially when worn indoors. In addition, when worn outdoors, such optical products do not provide increased protection against blue light present in sunlight. That is, conventional optical products that rely on static yellow dyes or tints to block blue light have a yellow color both indoors and outdoors, and provide the same level of blue light blocking both indoors and outdoors.

[0007] It would therefore be desirable to provide an article, such as an optical article, that is substantially clear and somewhat blue blocking in an indoor environment, but changes color and becomes more blue blocking when exposed to sunlight in an outdoor environment. Summary of the invention

[0008] The present invention relates to an article that changes from a first state to a second state in response to actinic radiation. The article comprises an indole naphthopyran, wherein in the first state the article exhibits a percent transmittance greater than 80%, and in the second state the article exhibits a percent transmittance between 35% and 75%, and a τ of less than 20. SB value.

[0009] 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

[0010] Figure 1 A general scheme for an exemplary method of preparing photochromic indole naphthopyran compounds useful in preparing articles of the present invention is illustrated, Scheme 1. DETAILED DESCRIPTION

[0011] As used herein, the articles "a," "an," and "the" include plural referents unless expressly and unequivocally limited to one referent.

[0012] As used herein, the term "includes" is synonymous with "comprises."

[0013] 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.

[0014] 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)-.

[0015] 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.

[0016] 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.

[0017] 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.

[0018] 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.

[0019] 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 L1 hour).

[0020] As described herein, the photochromic compounds of the present invention (including but not limited to the photochromic compounds represented by Formula (I) and Formula (Ia)) may in each case optionally further include one or more by-products resulting from the synthesis of such compounds.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] 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).

[0025] 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 switched from a first state (e.g., a "transparent state") to a second state (e.g., a "colored state") in response to actinic radiation, and returned 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 switched from a first state (e.g., a "transparent state") to a second state (e.g., a "colored state") in response to actinic radiation, and returned 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).

[0026] 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.

[0027] 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.

[0028] 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).

[0029] 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.

[0030] 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.

[0031] As used herein, the term "mirror" means a surface that specularly reflects a significant portion of incident light.

[0032] 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.

[0033] 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.

[0034] As used herein, statements concerning ring positions (such as, but not limited to, position-x (e.g., position-3 or position-13) refer to specific positions of chemical compounds (such as the indole naphthopyran photochromic compounds of the present invention) in a ring structure (such as a core skeleton structure), and are depicted herein according to some embodiments by numbers within the ring structure of representative chemical formulas (such as, but not limited to, formula (I) and / or (Ia)).

[0035] "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.

[0036] 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).

[0037] 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."

[0038] 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 groups; ketone groups; aldehyde groups; ester groups; carboxylic acid groups; phosphoric acid groups; phosphate ester groups; sulfonic acid groups; sulfonate groups; nitro groups; 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.

[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 C 6 -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 halogen groups. The term "halo ()" includes "perhalogenated ()". 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 halogen groups. For example, a perhalomethyl group is -CX 3 ; Perhalogenated phenyl is -C 6 X 5 , wherein X represents one or more halo groups such as but not limited to F, Cl or Br.

[0041] As used herein, description of a "straight chain or branched" group (such as a straight chain or branched alkyl group) is understood herein to include: a straight chain (or "straight chain") group, such as a straight chain C 1 -C 25 Alkyl; and appropriately branched groups, such as branched C 3 -C 25 alkyl.

[0042] The term "alkyl" as used herein refers to a linear or branched, cyclic or non-cyclic C 1 -C 25 Alkyl. A straight chain or branched chain alkyl group may include C 1 -C 25 Alkyl groups, such as C 1 -C 20 Alkyl groups, such as C 2 -C 10 Alkyl groups, such as C 1 -C 12 Alkyl groups, such as C 1 -C 6 Alkyl. 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, C 3 -C 12 Cycloalkyl (including but not limited to cyclic C 5 -C 7 Alkyl or cyclic C 3 -C 10 Examples 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 C 2 -C 12 Heterocycloalkyl, such as C 5 -C 7 Heterocycloalkyl, such as C 2 -C 10Heterocycloalkyl, 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. The term "heterocycloalkyl" as used herein 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, C 3 -C 18 Heteroaryl, such as but not limited to C 3 -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 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, cyclopentanaphthyl and indacenyl.

[0046] As used herein, the term "aralkyl" includes, but is not limited to, C 6 -C 24 Arylalkyl, such as but not limited to C 6 -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.

[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, "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.

[0050] 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.

[0051] 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.

[0052] The present invention includes, or consists essentially of, the following aspects of the present invention in any combination. As previously described, the present invention relates to an article that changes from a first state to a second state in response to exposure to electromagnetic radiation (e.g., actinic radiation). In the first state, the article exhibits a percent transmittance greater than 80%, such as greater than 85%, such as greater than 88%. In the second state, the article exhibits a percent transmittance between 35% and 75%, such as between 40% and 70%, such as between 45% and 65%, and a τ of less than 20%, such as less than 15%, such as less than 10%. SB For example, in the second state, the article may exhibit a τ of 3.0% to less than 20%, such as 4.0% to less than 20%, such as 5.0% to less than 20%. SB The term "percent transmittance" means the percentage of spectral light transmitted through a transparent article as perceived by the human eye, as determined using CIE Y values ​​according to CIE 15:2004 colorimetry, using a D65 illuminant and a 10° observer. In the description and examples herein, percent transmittance may also be referred to as "%T". SB The value is the solar blue transmittance, which is the result of the average of the spectral transmittances between 380 and 500 nanometers and an appropriate weighting function. See ISO 12311:2013(E), subsection 7.4.

[0053] For example, the article of the present invention can be a photochromic article in which the first state is an unactivated, generally colorless state, such as when the article is not exposed to actinic radiation. The percent transmittance in the first state is greater than 80%. Upon exposure to actinic radiation, the photochromic article transforms to a second, activated or colored state in which the percent transmittance decreases in response to the actinic radiation. The percent transmittance in the second state decreases to a value ranging from 35% to 75%. Due to the decrease in the percent transmittance in response to actinic radiation in the second state, τ SB The value (i.e., solar blue light transmittance) is also reduced to less than 20%. Thus, the article of the present invention changes from a generally transparent first state to a colored second state with enhanced blue light blocking in response to actinic radiation. Upon removal of the actinic radiation source, the article can return to the first unactivated and transparent or colorless state.

[0054] In addition, the articles of the present invention may have a b* value ranging from -5 to 15, such as from -5 to 10, such as from -5 to 5, in the first state. In addition, the articles of the present invention may have a b* value ranging from 0 to 15, such as from 0 to 10, such as from 0 to 5, in the first state. The b* value as used in the specification and claims herein refers to the b* value measured using a Hunter UltraScan Pro device using a D 65 illuminant and a 10° observer according to CIE 15:2004 spatial colorimetry. The b* axis represents the blue-yellow component, with blue being the negative direction and yellow being the positive direction. The b* value just described above indicates that the articles of the present invention generally have no or little yellow in the first state.

[0055] As previously mentioned, the articles of the present invention comprise an indole naphthopyran, for example a photochromic indole naphthopyran comprising a core skeleton structure represented by the following formula (I). The indole naphthopyran used in the articles of the present invention may be represented by one or more core skeleton structures described below.

[0056] Each available numbered ring position (e.g., 1, 2, 5, 8, 9, 10, 11, and / or 12) of the core skeleton structure of formula (I) may have a hydrogen or a group other than hydrogen covalently bonded thereto, e.g., a group such as described herein. Examples of such groups are described below.

[0057]

[0058] For formula (I), R 1 and R 2 are each independently hydrogen, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted ether, substituted or unsubstituted thioether, amino, nitrogen-containing heterocycle, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, -NHC(O)R a , or -OC(O)R a . R a Examples of the group that can be selected therefrom include a substituted or unsubstituted alkyl 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, or a substituted or unsubstituted arylthio group. 4 is selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heterocycloalkyl, allyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. 4 and B′ are each independently substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl. Each substituted aryl or substituted heteroaryl may be replaced by a Hammett σ greater than −0.50.p The relative strength of electron donor groups is usually measured by the Hammett σ value, or σ p Value description. Hammett's σ for various substituents p A list of values ​​can be found in: "A Survey of Hammett Substituent Constants and Resonance and Field Parameters", C. Hansch, A. Leo, and RW Taft, Chem. Rev., 1991, 91, 165-195, the disclosure of which is incorporated by reference. A Hammett σ greater than -0.50 p Non-limiting examples of suitable substituents for the value include a halogen group (i.e., fluorine or bromine), an alkyl group, a perhaloalkyl group, a phenyl group, a methyl group, a phenyl ether, an aralkyl group, an ethoxy group, a methoxy group, a p-aminophenyl group, an arylthio group, an alkylthio group, an amide, a carboxylate, an aryl group, a heteroaryl group, a hydroxyl group, a cyano group, or an ester.

[0059] R 1 Examples of groups that can be selected therefrom include, but are not limited to, substituted or unsubstituted alkoxy groups. 2 Examples of groups that can be selected therefrom include substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted ether, substituted or unsubstituted thioether, amino, or nitrogen-containing heterocycle. B and B' can each independently be a substituted aryl or a substituted heteroaryl. Each substituted aryl or substituted heteroaryl can be substituted with a Hammett σ of -0.5 to 0.8. p B and B' may each independently be a substituted or unsubstituted phenyl. Each phenyl substituent may be selected from alkoxy, halogen, alkyl, or aryloxy. 1 and R 2 Taken together they can form a ring-like structure, such as a ring structure.

[0060] Additionally or alternatively, the articles of the present invention may comprise an indole naphthopyran compound represented by a core skeleton structure of formula (Ia):

[0061]

[0062] Regarding formula (Ia), R 1 , R 2 , R 4 , B and B' are as previously described with respect to formula (I).

[0063] As described above, in the absence of specific substituents shown, the remaining numbered ring positions (e.g., 1, 2, 5, and / or 8) of the core backbone structure of Formula (Ia) can have hydrogen or groups other than hydrogen covalently bonded thereto, for example, such as the groups described herein.

[0064] Further with respect to Formula (Ia), m is 0 to 4, and for each m, R 3 are independently 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 boric 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. For example, R 3 It may be a cyano group; a halogen group; a haloalkyl group; a perhaloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group. 3 Can be in 11-position. For example, R 3 The group L may be at the 10-position and may be a mesogen-containing group 1 .

[0065] Further with respect to formula (Ia), each mesogen-containing group L 1 can be independently represented by the following formula (II),

[0066] Formula (II)

[0067] -[S 1 ] c -[Q 1 -[S 2 ] d ] d’ -[Q 2 -[S 3 ] e ] e’ -[Q 3 -[S 4 ] f ] f’ -R

[0068] Q 1 , Q 2 , and Q 3Each 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 selected from the group consisting of: (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; (ii) -Si(CH 3 ) 2 -、-Si(CH 3 ) 2 O-; 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 spacing units comprising heteroatoms are linked together, the spacing 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.

[0069] As used herein, the term "polysiloxane", for example, with respect to the substituents of the various groups of the photochromic compound of the present invention, includes materials represented by the following formula (G):

[0070]

[0071] 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 and R 33 are each independently selected from methyl, ethyl, or phenyl; and R34 is selected from hydrogen, methyl, ethyl, or phenyl.

[0072] 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):

[0073]

[0074] 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).

[0075] In some embodiments, the articles of the present invention may include compounds of the aforementioned formula (I) and / or (Ia), alone or in combination with one or more other photochromic compounds. For example, the articles of the present invention may include compounds of the aforementioned formula (I) and / or (Ia) together with one or more other photochromic compounds having an activation absorption maximum in the range of 300 to 1,000 nanometers. In addition, the compounds of the aforementioned formula (I) and / or (Ia) may 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, lines 39 to column 8, line 41) and 6,555,028 (at column 2, lines 65 to column 12, line 56).

[0076] In addition, the compounds of formula (I) and / or (Ia) can be used in combination with mixtures of other photochromic compounds. For example, although not limiting herein, mixtures of photochromic compounds can be used to obtain certain activated colors.

[0077] Examples of other classes of photochromic compounds that can be used in combination with compounds of formula (I) and / or (Ia) in the preparation of the articles 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)quinooxazines, fulgides, fulgimides, diarylethenes, diarylalkylethylenes, diarylalkenylethylenes, thermoreversible photochromic compounds and non-thermally reversible photochromic compounds, and mixtures thereof. Other examples of other photochromic compounds that can be used in combination with the compounds of formula (I) and / or (Ia) may include, but are not limited to, those disclosed in column 34, line 20 to column 35, line 13 of US 9,028,728 B2.

[0078] Indole naphthopyran compounds useful in the articles of the present invention may be prepared according to art-recognized methods as follows. 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 intermediates, reactants, and / or compounds depicted, various groups such as R 1 , R 2 , R 3 , R 4 , B, B', R 芳基 , and R 烷基 Each is as described herein, and / or represents a precursor of such a group.

[0079] The synthesis of compounds with different substituents as depicted in the following formula III has been described in many references such as US 6,296,785 or US 7,262,295.

[0080]

[0081] 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.

[0082]

[0083] The carboxylic acid group can then be converted to NH using diphenylphosphoryl azide via Curtius rearrangement conditions. 2The diphenylphosphoryl azide generates an isocyanate group which is subsequently hydrolyzed to generate an amine group as depicted in Formula IIIb below.

[0084]

[0085] 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.

[0086]

[0087] 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.

[0088]

[0089] 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.

[0090]

[0091] The alkylation of the indole group as depicted in formula IIIg' can be accomplished by reacting with an alkyl halide, triflate, or tosylate in the presence of a base such as sodium tert-butoxide or potassium tert-butoxide. Alternatively, the indole can be deprotonated by a strong base such as sodium hydride or n-butyllithium, and then the anion is reacted with an alkyl halide, triflate, or tosylate. See the reaction depicted below.

[0092]

[0093] The indole group can be arylated by a cross coupling reaction with a transition metal catalyst and an aryl halide as depicted in Formula IIIg". Ullmann coupling methodology with a copper catalyst is a common method for this transformation. See the reaction depicted below.

[0094]

[0095] Indoles can also be arylated by nucleophilic aromatic substitution as shown in formula IIIg" by reaction with an aryl fluoride in a suitable solvent such as tetrahydrofuran or dimethylformamide.

[0096] 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.

[0097]

[0098] 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.

[0099]

[0100] As previously described and illustrated in the examples below, compounds useful in the articles of the present invention exhibit an A-band to B-band absorption ratio greater than 3:1 and in some cases greater than 6:1, such as 3 to 7:1, such as 3 to 6.5:1, such as 3 to 6.4:1, or such as 3.45 to 6.4:1.

[0101] The article of the present invention may be a photochromic article comprising one or more indole naphthopyran compounds represented by formula (I) or (Ia). The photochromic article may 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.

[0102] 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.

[0103] 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.

[0104] 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.

[0105] Such photochromic articles, such as photochromic lenses, can be transformed from a first, unactivated state (e.g., a colorless and non-blue blocking state) to a second, activated state (e.g., a tinted and blue blocking state) when exposed to actinic radiation. Upon removal of the actinic radiation source, the article can return to the first, unactivated (and transparent or colorless) 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.

[0106] 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.

[0107] Examples

[0108] The preparation of indole naphthopyran compounds useful for preparing the articles of the present invention is described below with reference to Examples 1 to 11 below and Examples 1A and 2A. Unless otherwise indicated, the structures of the compounds were confirmed by mass spectroscopy.

[0109] Part 1: Synthesis of compounds

[0110] Example 1

[0111]

[0112] Step 1

[0113] Methyl 4-acetoxy-6,7-dimethoxy-1-(4-(trifluoromethyl)phenyl)-2-naphthoate (50 g, 131 mmol) was dispersed in methanol (200 ml) with stirring. Concentrated hydrochloric acid (8 ml) was added and the reaction mixture was heated to reflux for 4 hours. Once cooled, the reaction mixture was concentrated to half of the original volume and the product was precipitated by standing. The product was collected and dried under vacuum to give 41 g (90% yield) of a colorless powder.

[0114]

[0115] Step 2

[0116] While stirring under nitrogen, the product from step 1 (41 g, 101 mmol) was dissolved in anhydrous dimethylformamide (200 ml) and potassium carbonate (28.0 g, 202 mmol) was added, followed by benzyl chloride (15.3 g, 121 mmol). The reaction mixture was heated to 70 ° C for 5 hours and stirred overnight at room temperature. A precipitate was formed and the reaction mixture was poured into ice water (1.0 L) under stirring. The precipitate was collected and dried under vacuum to give a colorless solid of 49.44 g (99% yield).

[0117]

[0118] Step 3

[0119] The product from step 2 (49.4 g, 99.5 mmol) was suspended in 2-propanol (150 ml) under stirring. Sodium hydroxide solution (10% w / w in water, 150 ml) was added and the reaction mixture was heated to reflux for 16 hours. Once cooled, the reaction mixture was poured into ice water (1.0 L) to form a colorless precipitate. The powder was collected and dried under vacuum to give 46.71 g (97% yield).

[0120]

[0121] Step 4

[0122] The product from step 3 (46.7 g, 96.8 mmol) was suspended in anhydrous toluene (300 ml) while stirring under nitrogen. Triethylamine (25.5 g, 252 mmol) and anhydrous ethanol (25 ml) were added to dissolve the suspension. Diphenylphosphoryl azide (40 g, 145 mmol) was added in portions and the reaction was heated to reflux for 3 hours. Once cooled, the reaction mixture was drawn into 200 ml of ethyl acetate, washed with water (4 x 300 ml), dried over sodium sulfate and concentrated under reduced pressure to give an off-white solid (50 g, 98% yield).

[0123]

[0124] Step 5

[0125] The product from step 4 (50.0 g, 95.1 mmol) was dispersed in a solution of ethanol (200 ml) and water (220 ml) with sodium hydroxide (19.2 g, 48.0 mmol) under stirring. The reaction mixture was heated to reflux for 4 hours. Once cooled, the reaction mixture was poured into ice water (1.0 L) and a colorless precipitate was formed. The powder was collected and dried under vacuum to give 41.81 g (97% yield).

[0126]

[0127] Step 6

[0128] While stirring under nitrogen, the product from step 5 (41.81 g, 92.2 mmol) is inhaled into dichloromethane (250 ml). Picolinic acid (17.0 g, 138.3 mmol) and 4-(dimethylamino)pyridine (1.13 g, 9.20 mmol) are added, followed by N, N'-dicyclohexylcarbodiimide (22.8 g, 110.6 mmol). The reaction mixture is allowed to stir at room temperature for 4 hours. The reaction mixture is filtered and concentrated under reduced pressure to give a reddish solid. The material is washed with methanol, collected and dried under vacuum to give 50.9 g (99% yield) of off-white powder.

[0129]

[0130] Step 7

[0131] The product from step 6 (50.9 g, 91.1 mmol) was dissolved in anhydrous dimethylformamide (100 ml) and copper (II) acetate (33.1 g, 182.2 mmol) and glacial acetic acid (5.47 g, 91.1 mmol) were added to this while stirring under nitrogen. The reaction mixture was heated to 150° C. for 20 hours to give a 66% conversion of the starting material to the product as determined by high performance liquid chromatography. The reaction mixture was filtered through a pad of diatomaceous earth 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 (37.44 g, 91% yield). The product indole core 5-(benzyloxy)-2,3-dimethoxy-9-(trifluoromethyl)-7H-benzo[c]carbazole was 1 H NMR and mass spectrometry confirmation.

[0132]

[0133] Step 8

[0134] While stirring under nitrogen, the indole core (5.0 g, 11.1 mmol) from step 7 was dissolved in anhydrous dimethylformamide (40 ml) and sodium hydride (0.8 g, 33.2 mmol) was slowly added. After 15 minutes, iodobutane (2.25 g, 12.2 mmol) was added and the reaction mixture was stirred at room temperature for 30 minutes. The reaction mixture was absorbed in ethyl acetate (200 ml) and washed with water (3 × 200 ml). The organic layer was dried over sodium sulfate and concentrated onto silica gel under reduced pressure. Chromatography (silica gel, 0%-50% dichloromethane in hexane) was performed to obtain the product (3.4 g, 60% yield) as a colorless solid.

[0135]

[0136] Step 9

[0137] The product from step 8 (1.50 g, 3.0 mmol) was combined with ammonium formate (0.75 g, 11.84 mmol) and palladium on carbon (Aldrich #768243, 5% on wet support, Degussa type E1003 U / W) in dimethylformamide (20 ml) while stirring under nitrogen. The reaction mixture was heated to 85° C. for 2 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 an off-white solid which was used without further purification.

[0138]

[0139] Step 10

[0140] While stirring under nitrogen, the product from step 9 (0.62 g, 1.48 mmol) was combined with 1,1-diphenylprop-2-yn-1-ol (0.37 g, 1.78 mmol) in toluene (25 ml) and heated to 75 ° C. p-Toluenesulfonic acid (5-10 mg) was added and the reaction mixture was heated to reflux for 2 hours. Once cooled, the reaction mixture was taken up in ethyl acetate (25 ml), washed with saturated sodium bicarbonate solution (25 ml) and water (2×50 ml). The organic layer was dried over sodium sulfate and concentrated under reduced pressure to give a dark oil. The product was recrystallized twice from methyl tert-butyl ether, tetrahydrofuran and methanol to give a pale yellow powder of Example 1 (0.48 g, 54% yield) and confirmed by mass spectrometry.

[0141] Example 2

[0142]

[0143] Step 1

[0144] The indole core prepared in step 7 of Example 1 (3.0 g, 6.64 mmol) was combined with bromobenzene (4.2 g, 26.6 mmol), cuprous iodide (0.63 g, 3.32 mmol), potassium carbonate (1.82 g, 13.2 mmol), 1,10-phenanthroline (0.24 g, 1.30 mmol) and dibenzo-18-crown-6-ether (0.24 g, 0.70 mmol) in anhydrous dimethylformamide (30 ml) while stirring under nitrogen. The reaction mixture was heated to 150° C. for 5 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 under reduced pressure to give a brown solid. The product was recrystallized twice from methyl tert-butyl ether, tetrahydrofuran and methanol to give an off-white powder (3.20 g, 91% yield).

[0145]

[0146] Step 2

[0147] The product from Step 1 (1.20 g, 2.27 mmol) was treated according to the conditions of Example 1, Step 9 to give an off-white solid which was used without further purification.

[0148]

[0149] Step 3

[0150] The product from Step 2 was treated under the conditions of Example 1, Step 10 to give a yellow powder (1.12 g, 79% yield) which was confirmed by mass spectrometry.

[0151] Example 3-6

[0152] Additional photochromic dyes were prepared according to Example 2 and are summarized in Table 1. For each example, the appropriate substituted bromobenzene was used in place of the bromobenzene in Step 1 of Example 2 as indicated in the N-coupling component column in Table 1. Likewise, the appropriate substituted 1,1-diphenylprop-2-yn-1-ol ("propargyl alcohol") was used in Step 3 of Example 2 as indicated in the Propargyl Alcohol column in Table 1. The structure was confirmed by mass spectroscopy.

[0153] Example 7

[0154]

[0155] Example 7 was prepared in the same manner as Example 1, except that 4-acetoxy-6,7-dimethoxy-1-(4-(trifluoromethyl)phenyl)-2-naphthoic acid methyl ester of Example 1, step 1 was replaced with 4-acetoxy-6,7-dimethoxy-1-phenyl-2-naphthoic acid methyl ester and 1,1-diphenylprop-2-yn-1-ol of Example 1, and step 10 was replaced with 1-(4-methoxyphenyl)-1-phenylprop-2-yn-1-ol. The results are summarized in Table 1, and the different cores are shown in the column of the indole core.

[0156] Example 8

[0157]

[0158] Step 1

[0159] The starting intermediates were prepared according to the conditions of Examples 1 and 2, except that 4-acetoxy-6,7-dimethoxy-1-(4-(trifluoromethyl)phenyl)-2-naphthoic acid methyl ester was used instead of 4-acetoxy-7-((2,6-dimethylphenyl)thio)-6-methoxy-1-phenyl-2-naphthoic acid methyl ester, and are summarized in Table 1.

[0160]

[0161] Step 2

[0162] While stirring under nitrogen, the product of step 1 (1.46g, 2.58mmol) was combined with p-toluenesulfonic acid (0.45g, 2.58mmol) in toluene (30ml) and heated to 85°C for 1 hour. Once cooled, the reaction mixture was washed with water (2×75ml), dried with sodium sulfate and concentrated under reduced pressure to give a yellow solid (a 1:2 mixture of product and by-product). The solid was suspended in toluene (20ml) and 1,1-diphenylprop-2-yn-1-ol (0.36g, 1.73mmol) was added. The reaction mixture was heated to reflux and p-toluenesulfonic acid (5mg-10mg) was added. After the reaction mixture was heated at reflux for 1 hour, the reaction mixture was cooled and concentrated onto silica gel under reduced pressure. Chromatography (silica gel, 0%-50% dichloromethane in hexane) was performed to obtain a yellow solid. Recrystallization from methyl tert-butyl ether, tetrahydrofuran and methanol gave a light yellow powder (0.23 g, 44% yield based on the mixture) which was confirmed by mass spectrometry.

[0163] Example 9

[0164]

[0165] Example 9 was prepared according to the conditions of Examples 1 and 2, except that 4-acetoxy-6,7-dimethoxy-1-(4-(trifluoromethyl)phenyl)-2-naphthoic acid methyl ester was replaced with 4-acetoxy-6-methoxy-1-phenyl-2-naphthoic acid methyl ester, and is summarized in Table 1.

[0166] Example 10

[0167]

[0168] Example 10 was prepared according to the conditions of Example 1, except that 4-acetoxy-6,7-dimethoxy-1-(4-(trifluoromethyl)phenyl)-2-naphthoic acid methyl ester was replaced with 4-acetoxy-6-methyl-1-(p-tolyl)-2-naphthoic acid methyl ester, and is summarized in Table 1.

[0169] Example 11

[0170]

[0171] Example 11 was prepared according to the conditions of Example 1, except that 4-acetoxy-6,7-dimethoxy-1-(4-(trifluoromethyl)phenyl)-2-naphthoic acid methyl ester was replaced with 4-acetoxy-1-phenyl-2-naphthoic acid methyl ester, and is summarized in Table 1.

[0172] Examples 1A and 2A were prepared as described below and are summarized below in Table 2. Unless otherwise stated, the structures of the products obtained were confirmed by mass spectrometry.

[0173] Example 1A

[0174]

[0175] Step 1

[0176] While stirring under nitrogen, Example 2, the product of step 2 (1.27g, 2.90mmol) and 1-(4-butoxyphenol)-1-phenylprop-2-yn-1-ol (0.37g, 1.78mmol) are combined in toluene (25ml) and heated to 75°C, p-toluenesulfonic acid (5-10mg) is added and the reaction mixture is heated to reflux for 3 hours. Once cooled, the reaction mixture is absorbed in ethyl acetate (200ml), washed with saturated sodium bicarbonate solution (100ml) and water (2x 100ml). The organic layer is dried over sodium sulfate and concentrated onto silica gel under reduced pressure. Chromatography (silica gel, 0-70% ethyl acetate in hexane) is carried out to obtain an off-white powder. The product is recrystallized twice from methyl tert-butyl ether, tetrahydrofuran and methanol to obtain a colorless powder (1.21g, 60% yield) and is passed through1 H NMR spectroscopy and mass spectrometry confirmed.

[0177]

[0178] Step 2

[0179] While stirring under nitrogen, dimethyl piperidine (0.33g, 2.90mmol) is added to anhydrous tetrahydrofuran (35ml). n-Butyl lithium (2.5M in hexane, 1.2ml) is slowly added and the mixture is stirred at room temperature for 5 minutes. The product of step 1 (0.5g, 0.71mmol) is added and the reaction mixture is stirred for additional 4 hours. The reaction mixture is poured into water (250ml) and extracted with ethyl acetate (2×50ml). The organic layer is dried with sodium sulfate and concentrated onto silica gel. Chromatography (silica gel, 0 to 50% dichloromethane in hexane) is performed to obtain the product (0.096g, 20% yield) as an off-white solid, which is confirmed by mass spectrometry.

[0180] Example 2A

[0181]

[0182] Step 1

[0183] The indole core from Example 7, 5-(benzyloxy)-2,3-dimethoxy-7H-benzo[c]carbazole, was treated to the conditions of Example 1, Step 8 using 1-bromo-2-ethylhexane instead of iodobutyl.

[0184]

[0185] Step 2

[0186] While stirring under nitrogen, methyl Grignard solution (1.4M, 29.0ml) was slowly added to dimethyl piperidine (4.93g, 40.0mmol) by syringe, and the reaction mixture was allowed to stir for 10 minutes. The product from step 1 (4.95g, 10.0mmol) was dissolved in anhydrous tetrahydrofuran (30ml) and added dropwise to the Grignard / dimethyl piperidine mixture over 10 minutes. Once added, the reaction mixture was refluxed for 3 hours. Upon cooling, the reaction mixture was poured into 1M HCl solution (75ml), and the water layer was extracted with ethyl acetate (3×150ml). The organic layers were combined, dried over sodium sulfate and concentrated to silica under reduced pressure. Chromatography (silica gel, 0-100% dichloromethane in hexane) was performed to obtain a semi-solid (2.17g, 44% yield).

[0187]

[0188] Step 3

[0189] The product of Step 2 (2.17 g, 4.50 mmol) was treated according to the conditions of Example 1, Step 9 to give a foam which was used without further purification.

[0190]

[0191] Step 4

[0192] While stirring under nitrogen, the product of step 3 is merged with 1,1-bis(4-fluorophenyl)prop-2-yn-1-ol and dissolved in toluene (40ml). The mixture is heated to reflux and p-toluenesulfonic acid (10mg) is added. The reaction mixture is heated under reflux for 5 hours until the conversion rate of the reaction is determined to be 60% by high performance liquid chromatography, and once cooled, concentrated onto silica gel. Chromatography (silica gel, 5%-50% ethyl acetate in hexane) is carried out to obtain brown / green glass (0.85g, 30% yield).

[0193]

[0194] Step 5

[0195] While stirring under nitrogen, the product of step 4 (0.85g, 1.38mmol) was dissolved in anhydrous dichloromethane (25ml). Anhydrous pyridine (0.5ml, 5.52mmol) was added and the reaction mixture was cooled in an ice bath. Trifluoromethanesulfonic anhydride (0.51g, 1.80mmol) was added dropwise. After 30 minutes, the reaction mixture was poured into water and the layers were separated. The water layer was washed with dichloromethane (2×30ml). The organic layers were combined, dried over sodium sulfate and concentrated under reduced pressure to give a brown / green glass (1.0g, 97% yield).

[0196]

[0197] Step 6

[0198] The product from step 5 (1.0 g, 1.33 mmol) was combined with benzamide (0.25 g, 2.0 mmol), cesium carbonate (1.80 g, 5.52 mmol) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos) in toluene and ethanol solution (30 ml, 9:1 v / v) and bubbled under nitrogen for 10 minutes. Tris(dibenzylideneacetone)dipalladium(0) (0.12 g, 0.13 mmol) was added and the reaction mixture was heated to reflux for 2 hours. The reaction mixture was absorbed in ethyl acetate (100 ml), washed with water (2 × 100 ml), dried with sodium sulfate and concentrated onto silica gel. The method (silica gel, 0%-30% ethyl acetate in hexane) gave a brown solid. Recrystallization from methanol gave a light yellow powder of 0.38 g (40% yield).

[0199]

[0200]

[0201]

[0202]

[0203]

[0204] Part 2: Testing

[0205] As described in Examples 1-3 of U.S. Patent No. 8,608,988, each of the photochromic dyes from Examples 1 to 11 and 1A and 2A, and each of Comparative Examples CE1 to CE4, 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.

[0206] Each coated test chip (hereinafter referred to as a "test sample") was conditioned by first exposing to 365 nm UV light at a distance of about 14 cm for 10 minutes to activate the photochromic material within the coating. A Model Li-1800 spectroradiometer measured the UVA (315 to 380 nm) irradiance at the test samples and found to be 22.2 watts per square meter. Each test sample was then placed under a 500-watt high-intensity halogen lamp at a distance of about 36 centimeters for 10 minutes to decolorize (deactivate) the photochromic material. The spectroradiometer measures the illuminance at the test sample and is found 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 table. The UV absorbance of the test sample at 390 nanometers is measured before measuring on the optical table.

[0207] The percent transmittance of Examples 1 to 11, 1A and 2A and each of Comparative Examples CE1 to CE4 was determined using CIE Y values ​​according to CIE 15:2004 colorimetry, using a D 65 illuminant and a 10° observer. The a* and b* values ​​as used herein in the specification and claims refer to the a* and b* values ​​measured using a Hunter UltraScan Pro device according to CIE 15:2004 spatial colorimetry, using a D 65 illuminant and a 10° observer. The percent spectral blue light transmittance (reported herein as τ) was determined according to ISO 12311:2013 (E), Section 7.4. SB ).

[0208] 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 2.1e) was used on the BMP to control timing, irradiance, gas 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 test samples for response and color measurements. 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 the 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.Use the same Zeiss (Zeiss) spectrophotometer, fiber optic cable for transmitting light from a tungsten halogen lamp and passing through the test sample to measure the dynamic photochromic response and color measurement of the test sample.Maintain the collimated monitoring beam from the fiber optic cable 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 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 from the vertical line at the sample placement point is =30 °.

[0209] The response measurement is determined by establishing an initial unactivated transmission, opening a shutter from one or more xenon lamps, and measuring the transmission through activation at selected time intervals, based on the change in optical density (ΔOD) from an unactivated or whitish state to an 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 transmission in the whitish state and % Ta is the percent transmission 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.

[0210] Fatigue testing:

[0211] Prior to initial performance testing, the procedures and results for fatigue testing were determined on an optical bench. To activate the photochromic molecules, the test samples were conditioned by exposing them to 365 nm ultraviolet light for 15 minutes at a distance of approximately 14 cm from the source. The UVA irradiance at the test piece was measured with a Licor model Li-1800 spectroradiometer and was found to be 22.2 watts per square meter. The test samples were then placed in an oven at 75°C for 1 hour. The test samples were then exposed to room lights for 3 hours. Finally, the test samples were then kept in a dark environment for at least 1 hour prior to testing to allow for continued fading back to the base state prior to testing.

[0212] An optical bench equipped with a Schott 3mm KG-2 bandpass filter, one or more neutral density filters, and a Newport Model #67005 300-watt xenon arc lamp (with a Model #69911 power supply and a Newport Model 689456 digital exposure / timer) was used to control the intensity of the irradiation beam used to activate each coated test sample. A Uniblitz model #CS25S3ZMO high-speed shutter with a model #VMM-D3 controller and a fused silica condenser lens for activating beam collimation and focusing were used to maintain sample temperature through a quartz water bag / sample holder into which each test sample to be tested was inserted. The temperature in the water pool was controlled with a pumped water circulation system, where the water passed through a copper coil placed in a reservoir of a refrigeration unit. The water bag used to hold the test sample contained fused silica plates on both the front and back sides to eliminate spectral variations of the activation or monitoring beam. Filtered water passing through the water tank was maintained at 100°F ± 2° for photochromic testing before and after exposure to the Atlas Weatherometer.

[0213] The customized broadband light source for monitoring response measurement is positioned in a manner perpendicular to the surface of the pool assembly. The wide beam light source is obtained by collecting and merging the light filtered individually from a 100-watt halogen tungsten lamp (controlled by a Lambda UP60-14 constant voltage power supply) and the split end, bifurcated fiber optic cable to enhance the short wavelength light intensity. After passing through the test sample, the monitoring light is refocused in a 2-inch integrating sphere and fed to an Ocean Optics S2000 spectrophotometer by a fiber optic cable. Ocean Optics SpectraSuite and proprietary software are used to measure the response and control the operation of the optical platform.

[0214] An International Light Research Radiometer, Model IL-1700, with a detector system consisting of a Model SED033 detector, B filter, and diffuser was used to verify irradiance prior to testing. 18.0 W / m 2 The adjusted value is used as the irradiance verification set point. The output display of the radiometer is calibrated relative to the Licor 1800-02 optical calibration calibrator (factor value setting) so that the display represents a value of watts per square meter of UVA. The xenon lamp output is adjusted by increasing or decreasing the current through the controller to the lamp and / or by adding or removing neutral density filters in the activating light path. The test sample is exposed to the activating light at 31° perpendicular to the test sample surface.

[0215] The change in optical density (ΔOD) from the bleached first state to the colored second state is determined by establishing an initial transmittance, opening the shutter of the xenon lamp to provide UV radiation, causing the test sample to change from the bleached first state to the activated second (i.e., colored) state, and measuring the transmittance in the activated state after typically 5 minutes of activation. The change in optical density is calculated using the following formula: ΔOD log (%Tb / %Ta), where %Tb is the percent transmittance in the whitish first state, %Ta is the percent transmittance in the activated state, and the logarithm is to base 10. This provides the OD 初始 .

[0216] Atlas Ci4000 weathering tester was used to simulate solar radiation accelerated aging. The test samples were exposed to a 1-hour dark cycle and then a 65-hour light cycle using a boron / borosilicate filtered xenon arc lamp (output 0.25 watts per square meter at 340nm). The temperature in the weathering tester was maintained at 45°C, and the relative humidity was controlled at 70% humidity. The temperature of the black plate was maintained at 55°C.

[0217] After the test samples were subjected to this UV exposure fatigue cycle, they were pre-conditioned as described above and measured on the optical bench to obtain a final ΔOD under the same conditions as described for the initial testing. 最终 .

[0218] The percent fatigue is determined by measuring the difference between the change in optical density (ΔOD) of the test sample before and after accelerated weathering according to the following formula: % fatigue = (ΔOD 初始 -ΔOD 最终 / ΔOD 初始 )×100.

[0219] The ΔOD at saturation is after 15 minutes of activation, and the fading half-life ("T1 / 2") value is the time interval, in seconds, for the ΔOD of the activated form of the photochromic-dichroic material in the coating to reach half of the ΔOD at fifteen minutes at 73.4°F (23°C) after the activating light source is removed.

[0220] Under full activation, two absorption maxima ΔOD are observed for the indole naphthopyran compounds of the present invention. Wavelength A ("λA") is the wavelength with the maximum ΔOD between 420nm-500nm, and wavelength B ("λB") is the wavelength with the maximum ΔOD between 500nm-650nm. The A-band to B-band absorption ratio ("AB ratio") is calculated by the following formula:

[0221] AB ratio = maximum ΔOD wavelength A / maximum ΔOD wavelength B

[0222] The test results are presented in Table 3 below.

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229] The data presented in Table 3 above illustrate that the photochromic indole naphthopyran compounds used to prepare the articles of the present invention provide excellent (low) blue light transmittance (reported as τ SB ) while maintaining very good kinetic and fatigue properties compared to the art-recognized photochromic compounds of comparative examples CE1 to CE4 which have a similar yellow color in the activated (second) state

[0230] The present invention may be further characterized by one or more of the following non-limiting clauses.

[0231] Item 1. An article that changes from a first state to a second state in response to electromagnetic radiation, the article comprising an indole naphthopyran, wherein:

[0232] In the first state, the article exhibits a percent transmittance greater than 80%, and a b* value of -5 to 15, such as -5 to 10, such as -5 to 5; and

[0233] In the second state, the article exhibits a percent transmittance between 35% and 75%, and a τ of less than 20%. SB value.

[0234] Clause 2. The article of clause 1, wherein in the first state, the article exhibits a percent transmittance greater than 80%, and a b* value of 0 to 15, such as 0 to 10, such as 0 to 5.

[0235] Clause 3. The article of clause 1 or 2, wherein in the second state, the article exhibits a transmittance percentage between 35% and 75%, and a τ of 3.0% to less than 20%, such as 4.0% to less than 20%, such as 5.0% to less than 20%. SB value.

[0236] Item 4. The article of Items 1 to 3, wherein the indole naphthopyran is a photochromic indole naphthopyran comprising a core skeleton structure represented by the following formula (I):

[0237]

[0238] in,

[0239] R 1 and R 2 are each independently hydrogen, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted ether, substituted or unsubstituted thioether, amino, nitrogen-containing heterocycle, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, -NHC(O)R a , or -OC(O)R a ,

[0240] Where R a is a substituted or unsubstituted alkyl 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, or a substituted or unsubstituted arylthio group;

[0241] R 4 is selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heterocycloalkyl, allyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; and

[0242] B and B' are each independently substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, wherein each substituted aryl or substituted heteroaryl is substituted with a Hammett's sigma greater than -0.50 p Value group substitution.

Claims

1. An article that changes from a first state to a second state in response to actinic radiation, the article comprising an indole naphthopyran, wherein: In the first state, the article exhibits a percent transmittance greater than 80%, and In the second state, the article exhibits a percent transmittance between 40% and 70%, and a τ of less than 20%. SB value, The indole naphthopyran is a photochromic indole naphthopyran comprising a core skeleton structure represented by the following formula (Ia): in, R 1 and R 2 are each independently an unsubstituted C1-C6 alkoxy group, an unsubstituted phenoxy group, an unsubstituted phenylthio group, a phenylthio group substituted with a C1-C6 alkyl group, or an unsubstituted C1-C6 alkyl group, R 4 is selected from hydrogen, unsubstituted C1-C6 alkyl, unsubstituted phenyl, C1-C6 alkyl substituted phenyl, or C1-C6 perfluoroalkyl substituted phenyl; and B and B' are each independently substituted or unsubstituted phenyl, wherein each substituted phenyl is replaced by a Hammett sigma greater than -0.50 p The group substitution values ​​are those with a Hammett σ greater than -0.50 p The group having the value is selected from fluoro, bromo, C1-C6 alkyl, C1-C6 perfluoroalkyl, phenyl, methyl, phenyl ether, ethoxy, or methoxy, m is 0 to 4; and For each m, R 3 are independently C1-C6 perfluoroalkyl.

2. The article of claim 1 having a b* value ranging from -5 to 15 in the first state.

3. The article of claim 1, wherein: R 1 is an unsubstituted C1-C6 alkoxy group, and R 2 It is an unsubstituted C1-C6 alkoxy group, an unsubstituted phenylthio group, or a phenylthio group substituted by a C1-C6 alkyl group.

4. The article according to any one of claims 1 to 3, wherein B and B' are each independently unsubstituted phenyl, or substituted with a Hammett's σ of -0.5 to 0.

8. p A phenyl group substituted with a Hammett σ of -0.5 to 0.8 p The value of the group is selected from fluoro and methoxy.

5. The article of claim 1, wherein: R 3 At 11-position.

6. The article according to any one of claims 1 to 3, wherein The indole naphthopyran has a bimodal absorption curve, wherein the absorption ratio of the A band to the B band ranges from 3.0 to 7.0:

1.

7. The article according to any one of claims 1 to 3, wherein The article is a photochromic article 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.

8. The product according to any one of claims 1 to 3, wherein The article is a photochromic ophthalmic article selected from the group consisting of corrective lenses, non-corrective lenses, contact lenses, intraocular lenses, magnifying lenses, protection lenses, and goggles.

9. The product according to any one of claims 1 to 3, wherein The article is a photochromic display article selected from the group consisting of a screen, a monitor, and a security element.

Images