Indenonaphthopyrans with perfluoroalkyl substituted aryl / heteroaryl sulfides at position-11

Abstract

The present invention relates to an indeno-naphthopyran compound represented by the following formula (I). In reference to formula (I), m, n, and R4-R7 are as described in the specification. Further referring to formula (I), R1 is an aryl group substituted by at least one perfluoroalkyl group, or a heteroaryl group substituted by at least one perfluoroalkyl group; r2 is an alkoxy group; and R3 is an alkoxy group, an amino group, or a substituted or unsubstituted nitrogen-containing heterocyclic ring, with the proviso that when R3 is not an alkoxy group, R3 is covalently bonded to position-7 via a nitrogen atom. The present invention also relates to a photochromic composition and a photochromic article comprising the indeno-naphthopyran compound represented by formula (I). (I)

Description

Technical Field

[0001] The present invention relates to indobenzopyran compounds having a perfluoroalkyl-substituted aryl or a perfluoroalkyl-substituted heteroaryl group bonded to position -11 by a sulfide bond, as well as photochromic compositions and photochromic articles comprising such compounds. Background Technology

[0002] In response to certain wavelengths of electromagnetic radiation (or “photochemical radiation”), photochromic compounds such as indo-naphthopyran (or indo-fused naphthopyran) typically undergo a transition from one form or state to another, each form having a characteristic or distinguishable absorption spectrum associated with it. Typically, upon exposure to photochemical radiation, many photochromic compounds transition from a closed form corresponding to the inactive (or bleached, e.g., substantially colorless) state of the photochromic compound to an open form corresponding to the activated (or colored) state of the photochromic compound. Without exposure to photochemical radiation, such photochromic compounds reversibly transition from the activated (or colored) state back to the inactive (or bleached) state. Compositions and articles containing or having a photochromic compound applied thereto (e.g., in the form of a photochromic coating composition) typically exhibit colorless (e.g., transparent) and colored states corresponding to the colorless and colored states of the photochromic compounds contained therein or applied thereto.

[0003] Photochromic indene-naphthopyran compounds are generally expected to provide a significant level of darkness upon exposure to photochemical radiation. They are also generally expected to rapidly fade to an inactive (or whitish) state even without exposure to photochemical radiation. Indene-naphthopyran compounds that provide this combination of significant or high levels of darkness upon exposure to photochemical radiation and a rapid fading rate in the absence of photochemical radiation typically and undesirably have an excessively dark whitish state (or color) and / or poor fatigue resistance.

[0004] The goal is to develop new indene-naphthopyran compounds that provide a combination of significant or high levels of darkness upon exposure to photochemical radiation and a rapid fading rate in the absence of photochemical radiation, without an excessively dark whitish state (or whitish color) and / or poor fatigue resistance. Summary of the Invention

[0005] According to the present invention, an indene-naphthopyran compound represented by the following formula (I) is provided.

[0006] (I)

[0007] Reference formula (I): m is 0 to 3; n is 0 to 3; R1 It is an aryl group substituted with at least one perfluoroalkyl group, or a heteroaryl group substituted with at least one perfluoroalkyl group; R 2 It is an alkoxy group; and R 3 It is an alkoxy, amino, or substituted or unsubstituted nitrogen-containing heterocycle, provided that R is... 3 When it is not alkoxy, R 3 The nitrogen atom is covalently bonded to position -7. Further referring to equation (I), R... 4 and R 5 Each is independently selected from: substituted or unsubstituted alkyl groups; or R 4 and R 5 Together they form substituted or unsubstituted spirorings. Also refer to formula (I), R 6 For each n independently, and R 7 For each m, independently, in each case, it is selected from: amino; substituted or unsubstituted nitrogen-containing heterocycle; halogen group; substituted or unsubstituted alkyl; substituted or unsubstituted alkoxy; perfluoroalkyl; or substituted or unsubstituted alkylthio.

[0008] According to the present invention, a photochromic composition comprising the indo-naphtho-pyran compound of the present invention is also provided.

[0009] According to the present invention, a photochromic article comprising the indo-naphtho-pyran compound of the present invention is further provided.

[0010] The features characterizing the invention are specifically set forth in the claims, which are appended to and form part of this disclosure. These and other features of the invention, its operational advantages, and the specific objectives obtained by using it will be more fully understood from the following detailed description, in which non-limiting embodiments of the invention are illustrated and described. Detailed Implementation

[0011] As used herein, the articles “a / an” and “the” include plural indicators unless otherwise clearly and explicitly limited to an indicator of a / an.

[0012] Unless otherwise specified, all ranges or ratios disclosed herein shall be construed as encompassing any and all subranges or subratios contained therein. For example, the stated range or ratio “1 to 10” shall be considered as including any and all subranges between (and including) the minimum value of 1 and the maximum value of 10; that is, all subranges or subratios that begin with a minimum value of 1 or greater and end with a maximum value of 10 or less, such as, but not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.

[0013] As used herein, unless otherwise specified, left-to-right orientation of linking groups, such as divalent linking groups, includes other suitable orientations, such as, but not limited to, right-to-left orientations. For purposes of non-limiting illustration, divalent linking groups... 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)-.

[0014] Except in operational examples, or where otherwise specified, all figures used in the specification and claims to indicate the amount of ingredients, reaction conditions, etc., shall be understood to be modified by the term “about” in all cases.

[0015] As used herein, the term “polymer” means homopolymer (e.g., prepared from a single monomer species), copolymer (e.g., prepared from at least two monomer species), and graft polymer.

[0016] As used herein, the term "(meth)acrylate" and similar terms (such as "(meth)acrylic acid ester") mean methacrylate and / or acrylate. As used herein, the term "(meth)acrylic" means methacrylic acid and / or acrylic acid.

[0017] The indo-naphthopyran compounds of the present invention are also referred to herein as photochromic indo-naphthopyran compounds and / or photochromic indo-naphthopyran.

[0018] As described herein, the indo-naphthopyran compounds of the present invention, including but not limited to indo-naphthopyran compounds represented by formula (I), may optionally further include one or more byproducts generated from the synthesis of such compounds.

[0019] As used herein, the term "photochromic" and similar terms (such as "photochromic compound") mean having an absorption spectrum for at least visible radiation that changes in response to absorption of at least photochemical radiation. Further, as used herein, the term "photochromic material" means any substance suitable for exhibiting photochromic properties (such as having an absorption spectrum for at least visible radiation that changes in response to absorption of at least photochemical radiation) and comprising at least one photochromic compound.

[0020] As used herein, the term “photochemical radiation” means electromagnetic radiation that can cause a material to react (e.g., but not limited to changing a photochromic material from one form or state to another, as will be discussed in further detail herein).

[0021] As used herein, the term "photochromic material" includes both thermally reversible photochromic materials and compounds and non-thermally reversible photochromic materials and compounds. As used herein, the term "thermally reversible photochromic compound / material" means a compound / material capable of transitioning from a first state (e.g., a "transparent state") to a second state (e.g., a "colored state") in response to photochemical radiation and capable of returning to the first state in response to thermal energy. As used herein, the term "non-thermally reversible photochromic compound / material" means a compound / material capable of transitioning from a first state (e.g., a "transparent state") to a second state (e.g., a "colored state") in response to photochemical radiation and returning to the first state in response to photochemical radiation of substantially the same wavelength absorbed by the colored state (e.g., cessation of exposure to such photochemical radiation).

[0022] As used herein, the terms "first" and "second" are not intended to refer to any particular order or sequence, but rather to two different conditions or characteristics, for the purpose of modifying the term "state". For non-limiting purposes, the first and second states of the photochromic compound may differ in at least one optical property, such as, but not limited to, absorption of visible and / or UV radiation. Thus, according to the various non-limiting embodiments disclosed herein, the photochromic compound 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 compound of the present invention may be transparent in the first state and colored in the second state. Alternatively, the photochromic compound of the present invention may have a first color in the first state and a second color in the second state.

[0023] As used herein, the term "optical" means relating to or related to light and / or vision. For example, according to the various non-limiting embodiments disclosed herein, optical articles, elements, or devices may be selected from ophthalmic articles, elements, and devices, display articles, elements, and devices, windows, mirrors, and active and passive liquid crystal cell articles, elements, and devices.

[0024] As used herein, the term “ophthalmology” means anything relating to or related to the eyes and vision. Non-limiting examples of ophthalmic articles or components include corrective and uncorrective lenses (including single or multiple vision lenses, which may be segmented or non-segmented multiple vision lenses (such as, but not limited to, bifocal, trifocal, and progressive lenses)) and other components used to correct, protect, or enhance (cosmetic or other) vision (including, but not limited to, contact lenses, intraocular lenses, magnifying lenses, and protective lenses or goggles).

[0025] As used herein, the term "display" means a visible or machine-readable representation of information that is text, numbers, symbols, designs, or graphics. Non-limiting examples of display elements include screens, monitors, and security elements such as security signs.

[0026] As used herein, the term "window" refers to an opening that allows radiation to be transmitted through it. Non-limiting examples of windows include transparent bodies in automobiles and aircraft, windshields, filters, shades, and optical switches.

[0027] As used in this article, the term "mirror" refers to a surface that reflects a large portion of incident light.

[0028] As used herein, the term "liquid crystal cell" refers to a structure containing liquid crystal material that can be ordered. A non-limiting example of a liquid crystal cell element is a liquid crystal display.

[0029] As used herein, the term “ring position” and similar terms (such as position-X or position-X) refer to a specific position in the ring structure (such as a fused ring structure) of a compound (such as the indo-naphtho-pyran compound of the present invention), and are described herein by numbers within the ring structure having a representative chemical formula (such as formula (I)) according to some embodiments.

[0030] All references to this document (such as, but not limited to, authorized patents and patent applications) are incorporated herein by reference in their entirety unless otherwise indicated.

[0031] As used herein, the description of “straight-chain or branched” groups (such as straight-chain or branched alkyl groups) should be understood to include: methylene or methyl groups; straight-chain groups, such as straight-chain C2-C... 20 Alkyl groups; and appropriately branched groups, such as branched C3-C groups. 20 alkyl.

[0032] As used herein, the term "alkyl" refers to a straight-chain or branched C1-C... 25 Alkyl groups. Straight-chain or branched alkyl groups may include C1-C12 groups. 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 various alkyl groups selected from the present invention include, but are not limited to, those further listed herein.

[0033] As used herein, the term "cycloalkyl" means a suitable cyclic group, such as, but not limited to, C3-C4. 12 cycloalkyl groups (including but not limited to cyclic C3-C) 10Alkyl, or cyclic C5-C7 alkyl). Examples of cycloalkyl include, but are not limited to, those further listed herein. As used herein, the term “cycloalkyl” also includes: bridged ring polycycloalkyl group (or bridged ring polycyclic alkyl group) such as, but not limited to, bicyclo[2.2.1]heptyl (or norbornyl) and bicyclo[2.2.2]octyl; and polycycloalkyl (or polycyclic alkyl) such as, but not limited to, octahydro-1H-indenyl and decahydronaphthyl.

[0034] As used herein, the term "heterocyclic alkyl" means a suitably cyclic group, such as, but not limited to, C2-C... 12 Heterocyclic alkyl groups, such as C2-C 10 Heterocyclic alkyl groups, such as C5-C7 heterocyclic alkyl groups, having at least one heteroatom in the cyclic ring, such as, but not limited to, O, S, N, P, and combinations thereof. Examples of heterocyclic alkyl groups include, but are not limited to, imidazolyl, tetrahydrofuranyl, tetrahydropyranyl, piperidinyl, morpholinyl, and piperazineyl. As used herein, the term "heterocyclic alkyl group" also includes: bridged polycyclic heterocyclic alkyl groups, such as, but not limited to, 7-oxabicyclo[2.2.1]heptyl; and fused polycyclic heterocyclic alkyl groups, such as, but not limited to, octahydrocyclopentano[b]pyranyl, and octahydro-1H-isocyanyl.

[0035] For example, regarding R 3 As used herein, the term "nitrogen-containing heterocycle" means a cyclic ring comprising at least one nitrogen atom (e.g., one or two nitrogen atoms) and optionally at least one other heteroatom besides nitrogen (e.g., oxygen), and in some embodiments, it is covalently bonded to another group via the nitrogen atom in the ring, such as the indo-naphtho-pyran compound according to the invention. Examples of nitrogen-containing heterocycles include, but are not limited to: cyclic amino groups, such as piperidinyl, pyrrolidinyl, piperazineyl, and morpholinyl; cyclic amides (or lactams), such as C3-C6 cyclic amides, such as β-propiolactam, γ-butyrolactam, δ-valerolactam, or ε-caprolactam; and heteroaromatic compounds, such as imidazole, pyrrole, indole, and carbazole.

[0036] The descriptions, types, and examples provided in this article regarding alkyl, cycloalkyl, heterocycloalkyl, and haloalkyl groups also apply to alkane groups, cycloalkane groups, heterocycloalkane groups, haloalkane groups, and such, but not limited to, polyvalent alkane groups, such as polyvalent alkane linking groups, such as divalent alkane linking groups.

[0037] As used herein, the term "aryl" and related terms such as "aryl group" refer to an aromatic cyclic monovalent hydrocarbon group. As used herein, the term "aromatic" and related terms such as "aromatic group" refer to a cyclic conjugated hydrocarbon exhibiting stability (due to the delocalization of π electrons) significantly greater than the stability assumed by a localized structure. Examples of aryl groups include C6-C... 14 Aryl groups, such as, but not limited to, phenyl, naphthyl, phenanthryl, and anthracene.

[0038] 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-ring polycyclic heteroaryl) and means an aryl group having at least one heteroatom in at least one aromatic ring, or in the case of fused-ring polycyclic heteroaryl. Examples of heteroaryl include, but are not limited to, furanyl, pyranyl, pyridyl, quinolinyl, isoquinolinyl, and pyrimidinyl.

[0039] Representative alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl. Representative alkenyl groups include, but are not limited to, vinyl, allyl, and propenyl. Representative alkynyl groups include, but are not limited to, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, and 2-butynyl. Representative cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

[0040] As used herein, the term "halogen" and related terms such as "halo group," "halo substituent," "halogen group," and "halogen substituent" refer to a single-bonded halogen group, such as -F, -Cl, -Br, and -I.

[0041] As used herein, the description of “halogen-substituted” and related terms (such as, but not limited to, halogenated alkyl, halogenated alkenyl, halogenated alkynyl, halogenated aryl, and halogenated heteroaryl) means at least one, and at most, all of them, groups in which a hydrogen group may be substituted by a halogen group (such as, but not limited to, F, Cl, or Br). The term “halogen-substituted” includes “fully halogen-substituted”.

[0042] As used herein, the term "perfluoroalkyl" means an alkyl group in which all of its available hydrogen groups are replaced (or substituted) by fluorine (F) groups in every case.

[0043] As used herein, “at least one of…” is synonymous with “one or more of…”, regardless of whether the elements are listed together 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.

[0044] As used herein, “selected from” and “chosen from” are synonymous, regardless of whether the elements are listed together or separately. Furthermore, the phrases “selected from A, B, and C” and “selected from A, B, or C” each refer to 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.

[0045] As used herein, and according to some embodiments, the term "ketone" (such as groups and substituents of various groups in relation to the photochromic compounds of the present invention) and related terms such as "ketone group" and "ketone substituent" include materials represented by -C(O)R, wherein R is selected from those groups described below.

[0046] As used herein, and according to some embodiments, the term "carboxylic acid" (such as groups and substituents of various groups in relation to the photochromic compounds of the present invention) and related terms (such as "carboxylic acid group" and "carboxylic acid substituent") include materials represented by -C(O)OH.

[0047] As used herein, and according to some embodiments, the term "ester" (such as groups and substituents of various groups in relation to the compounds and components of the present invention) and related terms (such as "ester group" and "ester substituent") mean a carboxylic acid ester group represented by -C(O)OR, wherein R is selected from those groups described below.

[0048] As used herein, and according to some embodiments, the term “carbonate” (such as groups and substituents of various groups in relation to the compounds and components of the present invention) and related terms (such as “carbonate group” and “carbonate substituent”) include materials represented by -OC(O)OR, wherein R is selected from those groups described below.

[0049] As used herein, and according to some embodiments, the term "carbamate" (such as groups and substituents of various groups in relation to the compounds and components of the present invention) and related terms (such as "carbamate group" and "carbamate substituent") include materials represented by -OC(O)N(R)(H) or -N(H)C(O)OR, wherein R in each case is independently selected from those groups described below.

[0050] Unless otherwise stated, each R group of each of the ketone, ester (carboxylic acid ester), carbonate and carbamate groups described above is independently selected in each case from alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof (including those types and examples of which have been previously listed herein).

[0051] The indo-naphtho-pyran compounds according to the present invention, such as, but not limited to, those represented by formula (I) and their various groups, are further described in detail herein.

[0052] As used herein, the description of "substituted" groups in relation to the indo-naphthopyran compounds of the present invention means, but is not limited to, alkyl, heterocyclic alkyl, aryl, and / or heteroaryl groups, wherein at least one hydrogen atom has been replaced or substituted by a group other than hydrogen. For some embodiments, the substituents of the "substituted" groups in the indo-naphthopyran compounds according to the present invention are independently selected in each case from: alkoxy; halogen groups (e.g., F, Cl, I, and Br); hydroxyl; thiol groups; alkylthio; arylthio; ketone groups; aldehyde groups; ester groups; carboxylic acid groups; cyano; alkyl; alkenyl; alkynyl; haloalkyl; perhaloalkyl; cycloalkyl; heterocyclic alkyl; aryl (including alkylaryl, including hydroxyl-substituted aryl, such as phenol, and including polycyclic aryl); heteroaryl (including polycyclic heteroaryl); amino, such as -N(R 11’ (R) 12’ ), where R 11’ and R 12’The substituents are independently selected from, for example, hydrogen, alkyl, heterocyclic alkyl, aryl, or heteroaryl; carboxylate groups; amide groups; urethane groups; carbonate groups; urea groups; vinylphenyl; acrylate groups; methacrylate groups; acrylamide groups; methacrylamide groups; nitrogen-containing heterocyclic compounds; or combinations thereof, including those types and examples further described herein. For some additional embodiments, the substituents of the "substituted" groups of the indo-naphthopyran compounds according to the invention are independently selected in each case from: alkoxy; halogen groups (e.g., F, Cl, I, and Br); hydroxyl; thiol groups; ketone groups; aldehyde groups; ester groups; carboxylate groups; cyano; alkyl; haloalkyl; perhaloalkyl; cycloalkyl; heterocyclic alkyl; aryl; and heteroaryl. Substituents of the substituted groups are more particularly listed in some embodiments of the invention.

[0053] Referring to formula (I): m is 0 to 3 (e.g., 0, 1, 2, or 3); and n is 0 to 3 (e.g., 0, 1, 2, or 3). In some embodiments of the invention, at least one of m and n is at least 1. In some other embodiments of the invention, m is 1 and / or n is 1. In some other embodiments of the invention, m is 1, and n is 1.

[0054] Referring to equation (I), and for some embodiments, R 1 It is an aryl group substituted with at least one perfluoroalkyl group, or a heteroaryl group substituted with at least one perfluoroalkyl group. In some embodiments, R... 1 It is composed of at least one straight or branched C1-C 10 A perfluoroalkyl-substituted aryl group, or a C1-C group consisting of at least one straight or branched chain. 10 Perfluoroalkyl-substituted heteroaryl groups.

[0055] According to some embodiments of the present invention, and referring to formula (I), R 2 It is an alkoxy group. As used in this article, "R" 2 The description "is alkoxy" etc. means that the oxygen of the alkoxy group is bonded to position -6 of the indo-naphthopyran represented by formula (I). For some embodiments, R 2 Is it a straight or branched C1-C? 10 Alkyl group.

[0056] According to some embodiments of the present invention, and referring to formula (I), R 3 It is an alkoxy, amino, or substituted or unsubstituted nitrogen-containing heterocycle. When R 3 When R is not an alkoxy group (i.e., amino, or a substituted or unsubstituted nitrogen-containing heterocycle), 3 Through covalent bonding of the nitrogen atom to position -7. As used in this paper, "R" 3The description of "alkoxy group" etc. means that the oxygen of the alkoxy group is bonded to position -7 of the indenonaphthopyran represented by formula (I). For some embodiments, R 3 Selected from amino, or substituted or unsubstituted nitrogen-containing heterocycles (and not selected from alkoxy).

[0057] For some embodiments, R has formula (I) 3 C1-C selected from straight or branched chains 10 Alkyl group. Further referring to formula (I), for some embodiments, R... 3 Choose a secondary or tertiary amino group represented by formula (II).

[0058] (II)

[0059] Referring to equation (II), R 8 and R 9 Each is independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, or substituted or unsubstituted aryl, provided that R 8 and R 9 At least one of them is not hydrogen.

[0060] Additionally, referring to equation (I), for some embodiments, R 3 It is selected from the following nitrogen-containing heterocycles: substituted or unsubstituted piperidinyl (wherein its cyclic nitrogen is covalently bonded to position -7); substituted or unsubstituted morpholino (wherein its cyclic nitrogen is covalently bonded to position -7); and substituted or unsubstituted C3-C6 cyclic amide (wherein its cyclic / amide nitrogen is covalently bonded to position -7).

[0061] For some embodiments, R has formula (I) 3 The group is selected from the substituted or unsubstituted piperazine group represented by formula (III) below.

[0062] (III)

[0063] Referring to equation (III), R 10 It is selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, alkylsulfonyl, or perhaloalkylsulfonyl.

[0064] Referring to equation (I), R 4 and R 5 Each is independently selected from: substituted or unsubstituted alkyl groups; or R 4 and R 5 Together they form substituted or unsubstituted spiral rings. In some other embodiments, R 4 and R 5Together they form a spirocycle that is a complete carbon ring (containing only carbon atoms), such as C3-C. 10 Threaded rings or C5-C8 threaded rings. For some other embodiments, R... 4 and R 5 Together they form an unsubstituted helical ring. In some embodiments, R 4 and R 5 Each is independently selected from unsubstituted straight-chain or branched C1-C6 alkyl groups.

[0065] Referring to formula (I), and according to some embodiments, R 6 For each n independently, and R 7 For each m independently, and in each case independently selected from: amino; substituted or unsubstituted nitrogen-containing heterocycles; halogen groups; substituted or unsubstituted alkyl groups; substituted or unsubstituted alkoxy groups; perfluoroalkyl groups; or substituted or unsubstituted alkylthio groups. For some additional embodiments, R... 6 For each n independently, and R 7 For each m independently, in each case, it is selected from: substituted or unsubstituted piperidinyl; substituted or unsubstituted morpholinyl; substituted or unsubstituted piperazine, independently as described above and further referenced herein to formula (III); fluorine, chlorine, or bromine; substituted or unsubstituted straight-chain or branched C1-C 18 Alkyl; substituted or unsubstituted straight-chain or branched C1-C6 alkyl; substituted or unsubstituted straight-chain or branched C1-C6 alkyl 18 Alkoxy; or substituted or unsubstituted straight-chain or branched C1-C6 alkoxy.

[0066] According to some embodiments of the present invention and referring to formula (I), R 1 It is a phenyl group substituted with at least one straight-chain or branched C1-C4 perfluoroalkyl group, a pyridyl group substituted with at least one straight-chain or branched C1-C4 perfluoroalkyl group, or a pyrimidinyl group substituted with at least one straight-chain or branched C1-C4 perfluoroalkyl group. For some embodiments, R having formula (I) 2 It is a straight-chain or branched C1-C4 alkoxy group.

[0067] Referring to formula (I), and according to some embodiments, R 3 Selected from straight-chain or branched C1-C6 alkoxy groups. For some other embodiments, R... 3 Choose a secondary or tertiary amino group represented by formula (II), where for formula (II), R 8 and R 9 Each is independently selected from hydrogen, substituted or unsubstituted straight-chain or branched C1-C6 alkyl, substituted or unsubstituted C5-C7 cycloalkyl, or substituted or unsubstituted aryl, provided that R 8 and R9 At least one of them is not hydrogen. For some other embodiments, R 3 Selected from: unsubstituted piperidinyl; substituted or unsubstituted morpholino; or unsubstituted C3-C6 cyclic amides. Additionally, and according to some examples, R 3 Choose a substituted or unsubstituted piperazine group represented by formula (III), where for formula (III): R 10 It is selected from hydrogen; substituted or unsubstituted straight-chain or branched C1-C6 alkyl; substituted or unsubstituted phenyl; or straight-chain or branched C1-C6 perhaloalkylsulfonyl.

[0068] According to some embodiments, and referring to formula (I), R 3 Selected from: straight-chain or branched C1-C4 alkoxy groups; substituted or unsubstituted piperidinyl groups; substituted or unsubstituted morpholinyl groups; or unsubstituted C3-C6 cyclic amides. For some additional examples, R... 3 Choose a secondary or tertiary amino group represented by formula (II), where for formula (II), R 8 and R 9 Each is independently selected from unsubstituted straight-chain or branched C1-C4 alkyl groups, or straight-chain or branched C1-C4 fully haloalkyl groups, provided that R 8 and R 9 At least one of them is a straight-chain or branched C1-C4 fully haloalkyl group. For some other embodiments, R... 3 Choose the substituted piperazine group represented by formula (III), where for formula (III), R 10 Selected from substituted or unsubstituted straight-chain or branched C1-C4 alkyl groups, substituted or unsubstituted phenyl groups, or straight-chain or branched C1-C4 perhaloalkylsulfonyl groups.

[0069] Referring to equation (I), and for some embodiments, R 4 and R 5 Each is independently selected from unsubstituted straight-chain or branched C1-C4 alkyl groups.

[0070] According to some embodiments, and referring to formula (I), R 6 For each n independently, and R 7 For each m, independently, in each case, it is selected from: unsubstituted piperidinyl; unsubstituted morpholinyl; fluorine, chlorine, or bromine; unsubstituted straight-chain or branched C1-C4 alkyl; or unsubstituted straight-chain or branched C1-C4 alkoxy.

[0071] Referring to formula (I), and according to some embodiments, R 6 and R 7 At least one of them is an unsubstituted straight or branched C1-C18 Alkoxy, or unsubstituted straight-chain or branched C1-C6 alkoxy, or unsubstituted straight-chain or branched C1-C4 alkoxy.

[0072] Some embodiments of the indo-naphtho-pyran compounds according to the present invention, and referring to formula (I), R 1 Selected from: 4-(trifluoromethyl)phenyl; 2-(trifluoromethyl)phenyl; 2,4-bis(trifluoromethyl)phenyl; 3,5-bis(trifluoromethyl)phenyl; 3,4-bis(trifluoromethyl)phenyl; or 5-(trifluoromethyl)pyridin-2-yl. Some further embodiments of the indo-naphthopyran compounds according to the present invention, and referring to formula (I), R 2 Selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, or branched butoxy, such as tert-butoxy; and R 3 Selected from morpholino, 2,6-dimethylmorpholino, 4-phenylpiperazinyl, 4-(trifluoromethyl)sulfonylpiperazinyl, γ-butyrolactam, δ-valerolactam, or ε-caprolactam. Some further examples of indene-naphthopyran compounds according to the present invention, and referring to formula (I): R 4 and R 5 Each is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, or branched butyl, such as tert-butyl; and R 6 and R 7 Each is independently selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, or branched butoxy, such as tert-butoxy.

[0073] Some embodiments of the indo-naphtho-pyran compounds according to the present invention, and referring to formula (I), R 1 Selected from: 4-(trifluoromethyl)phenyl; 2-(trifluoromethyl)phenyl; 2,4-bis(trifluoromethyl)phenyl; 3,5-bis(trifluoromethyl)phenyl; 3,4-bis(trifluoromethyl)phenyl; or 5-(trifluoromethyl)pyridin-2-yl. Some further embodiments of the indo-naphthopyran compounds according to the present invention, and referring to formula (I): R 2 It is a methoxy group; and R 3 Selected from morpholino, 2,6-dimethylmorpholino, 4-phenylpiperazinyl, 4-(trifluoromethyl)sulfonylpiperazinyl, γ-butyrolactam, δ-valerolactam, or ε-caprolactam. Some further examples of indene-naphthopyran compounds according to the present invention, and referring to formula (I): R 4 and R 5 Each is n-propyl; and R 6 and R 7 Each is independently selected from methoxy or n-butoxy.

[0074] The indo-naphtho-pyran compounds according to the present invention can be prepared according to methods recognized in the art.

[0075] In some embodiments, the indo-naphtho-pyran compound of the present invention is a photochromic indo-naphtho-pyran compound. According to the present invention, a photochromic composition comprising at least one indo-naphtho-pyran compound according to the present invention, which is a photochromic indo-naphtho-pyran compound, as represented by formula (I).

[0076] The photochromic indo-naphtho-pyran compounds of the present invention can be used in combination with mixtures of other photochromic compounds. For example, while 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, lines 66 through 13, lines 19, which describes the parameters defining neutral gray and brown.

[0077] Examples of other photochromic compounds that can be used in combination with the photochromic indo-naphthopyran compounds of the present invention include, but are not limited to, indo-fused naphthopyran, naphtho[1,2-b]pyran, naphtho[2,1-b]pyran, spirofluoren[1,2-b]pyran, phenanthropyran, quinoline pyran, fluoranthropyran, spiropyran, benzoxazine, naphthopyran, spiro(dihydroindole)naphthopyran, spiro(dihydroindole)pyridinobenzoxazine, spiro(dihydroindole)fluoranthropyran, spiro(dihydroindole)quinoline pyran, succinic anhydride, succinic imide, diarylethene, diarylealkylethylene, diaryleleneethylene, thermally reversible photochromic compounds, non-thermally reversible photochromic compounds, and mixtures thereof.

[0078] In some embodiments, the photochromic compositions of the present invention may further comprise one or more fixed-tint dyes. As used herein, the term "fixed-tint dye" and related terms (such as "fixed colorant," "static colorant," "fixed dye," and "static dye") refer to a dye that is a non-photosensitive material that, in terms of its visually observed color, has no physical or chemical response to electromagnetic radiation. As used herein, the term "fixed-tint dye" and related terms do not include photochromic compounds and are distinguishable from them. As used herein, the term "non-photosensitive material" refers to a material that, in terms of its visually observed color, has no physical or chemical response to electromagnetic radiation, including but not limited to fixed-tint dyes.

[0079] One or more fixed-hue dyes may be present in the photochromic composition of the present invention, the purpose of which includes, but is not limited to, providing for articles prepared from the photochromic composition: at least one basic (or first) color feature of the fixed-hue dye when the photochromic compound is not activated; and optionally, a second color feature of the combination of the fixed-hue dye and the photochromic compound when activated (e.g., by exposure to photochemical radiation).

[0080] In some embodiments, the optional fixed-hue dyes of the photochromic composition include at least one of the following: azo dyes, anthraquinone dyes, xanthene dyes, azime dyes, iodine, iodide salts, polyazo dyes, stilbene dyes, pyrazolone dyes, triphenylmethane dyes, quinoline dyes, oxazine dyes, thiazine dyes, and polyene dyes.

[0081] Fixed-hue dyes can be present in different amounts in the photochromic composition to provide the desired effect in the cured articles prepared therefrom. In some embodiments, the fixed-hue dye is present in the photochromic composition in amounts of 0.001 to 15 weight percent, or 0.01 to 10 weight percent, or 0.1 to 2.5 weight percent, these weight percentages being based on the total resin solids weight of the photochromic composition in each case.

[0082] According to some embodiments of the present invention, the photochromic composition comprises: (i) a matrix-forming material, wherein the matrix-forming material is at least one of a polymeric material, an oligomeric material, and / or a monomeric material; and (ii) an indene-naphthopyran compound according to the present invention, which is a photochromic indene-naphthopyran compound, as represented by formula (I). The photochromic indene-naphthopyran compound may be incorporated into a portion of the organic material by methods including, but not limited to, blending or combining the photochromic compound with at least one of the organic material or a precursor of the organic material. As used herein with reference to incorporating a photochromic compound into an organic material, the terms “blending” and “blending” mean mixing or blending the photochromic compound / material with at least a portion of the organic material, but not combining it with the organic material. Further, as used herein with reference to incorporating a photochromic compound into an organic material, the terms “combining” or “combining” mean that the photochromic compound / material is, for example, linked to a portion of the organic material or a precursor by one or more covalent bonds. For example, although not limited herein, photochromic materials can be attached to organic materials by reactive substituents such as, but not limited to, hydroxyl, primary amine and / or secondary amine groups.

[0083] When the organic material is a polymer, the photochromic compound can be incorporated into at least a portion of the polymer or into at least a portion of the monomer or oligomer material forming the polymer. For example, one or more photochromic compounds having reactive substituents according to the present invention can be combined with organic materials such as monomers, oligomers, or polymers, the organic material having groups to which the reactive portion can react, or the reactive portion can be reacted as a comonomer in a polymerization reaction forming the organic material, such as in a copolymerization process.

[0084] As discussed above, in some embodiments, the photochromic compositions according to the present invention may comprise organic materials selected from polymeric materials, oligomeric materials, and / or monomeric materials. Examples of polymeric materials that can be used with the photochromic compositions of the present invention include, but are not limited to: poly(carbonate); copolymers of ethylene and vinyl acetate; copolymers of ethylene and vinyl alcohol; copolymers of ethylene, vinyl acetate, and vinyl alcohol (such as those produced by partial saponification of copolymers of ethylene and vinyl acetate); cellulose acetate butyrate; poly(urethane); poly(acrylate); poly(methacrylate); epoxy resins; amino-functionalized polymers; poly(anhydride); poly(urea-urethane); N-alkoxymethyl(meth)acrylamide functional polymers; poly(siloxane); poly(silane); and combinations and mixtures thereof. Other types and examples of polymeric materials that can be used with the photochromic compositions of the present invention include, but are not limited to, those disclosed in column 39, line 45 to column 40, line 67 of US 9,028,728 B2.

[0085] The photochromic composition of the present invention may include at least one of the following: complementary photochromic materials (including one or more of the other photochromic materials and compounds previously described herein), photoinitiators, thermal initiators, polymerization initiators, solvents, light stabilizers, heat stabilizers, release agents, rheology modifiers, leveling agents, free radical scavengers, and / or adhesion promoters.

[0086] The photochromic composition according to the present invention can be a photochromic coating composition. The photochromic coating composition of the present invention may comprise: a photochromic compound according to the present invention, as previously described herein with respect to formula (I); optionally a curable resin composition; and optionally a solvent. The photochromic coating composition may be in the form of liquid coatings and powder coatings recognized in the art. The photochromic coating composition of the present invention may be a thermoplastic or curable (e.g., thermosetting and / or photocurable) coating composition.

[0087] The curable resin composition of the curable photochromic coating composition according to the present invention may comprise: a first reactant (or component) having functional groups, such as an epoxide-functionalized polymer reactant; and a second reactant (or component) having functional groups as a crosslinking agent, wherein these functional groups are reactive to the functional groups of the first reactant and can form covalent bonds with them. The first and second reactants of the curable resin composition of the curable photochromic coating composition may each independently comprise one or more functional substances, and each is present in an amount sufficient to provide a cured photochromic coating having desired physical properties, such as a combination of smoothness, optical clarity, solvent resistance, and hardness.

[0088] Examples of curable resin compositions that can be used with the curable photochromic coating compositions according to the present invention include, but are not limited to: curable resin compositions comprising an epoxide-functionalized polymer (e.g., a (meth)acrylic acid polymer containing glycidyl methacrylate residues) and an epoxide reactive crosslinking agent (e.g., containing active hydrogen, such as hydroxyl, thiol, and amine); and curable resin compositions comprising an active hydrogen-functionalized polymer (e.g., a hydroxyl, thiol, and / or amine-functionalized polymer) and a terminated (or blocked) isocyanate-functionalized crosslinking agent. “Terminated (or blocked) isocyanate-functionalized crosslinking agent” means a crosslinking agent having two or more terminated isocyanate groups that can be determinated (deblocked) under curing conditions (e.g., at elevated temperatures) to form free isocyanate groups and free terminated groups. The free isocyanate groups formed by determining the crosslinking agent are preferably capable of reacting with the active hydrogen groups of the active hydrogen-functionalized polymer (e.g., with the hydroxyl groups of the hydroxyl-functionalized polymer) and forming substantially permanent covalent bonds therewith. Further examples of curable resin compositions that can be used with curable photochromic coating compositions according to the present invention include, but are not limited to, those disclosed below: 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.

[0089] The curable photochromic coating compositions according to the invention may optionally contain additives such as waxes for flow and wetting, flow modifiers (e.g., poly(2-ethylhexyl) acrylate), auxiliary resins for modifying and optimizing coating properties, antioxidants, and ultraviolet (UV) light absorbers. Examples of useful antioxidants and UV light absorbers include those commercially available from BASF under the trademarks IRGANOX and TINUVIN. These optional additives are typically present in an amount of up to 20% by weight (e.g., 0.5 to 10% by weight) based on the total weight of the resin solids in the curable resin composition when used.

[0090] The photochromic compositions, photochromic articles, and photochromic coating compositions according to the present invention may further comprise additives recognized in the art that contribute to or assist in the processing and / or performance of the compositions or articles. Non-limiting examples of such additives include photoinitiators, thermal initiators, polymerization initiators, solvents, light stabilizers (such as, but not limited to, ultraviolet light absorbers and light stabilizers, such as hindered amine light stabilizers (HALS)), heat stabilizers, release agents, rheology modifiers, leveling agents (such as, but not limited to, surfactants), free radical scavengers, adhesion promoters (such as hexanediol diacrylate and coupling agents), and combinations and mixtures thereof.

[0091] In some embodiments, the photochromic composition of the present invention may contain one or more solvents, such as one or more organic solvents.

[0092] The types of organic solvents that may be present in the photochromic compositions of the present invention include, but are not limited to: ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers, such as dimethyl ether and methyl ethyl ether; cyclic ethers, such as tetrahydrofuran and dioxane; esters, such as ethyl acetate, ethyl lactate, ethylene carbonate, and propylene carbonate; nitrogen-containing cyclic compounds, such as pyrrolidone, N-methyl-2-pyrrolidone, 1-butyl-pyrrolidone, and 1,3-dimethyl-2-imidazolium ketone; sulfur-containing compounds, such as dimethyl sulfoxide and tetramethyl sulfone; aromatic compounds, such as toluene, xylene, anisole, and butyl benzoate; and mixtures of aromatic compounds, such as, but not limited to, Aromatic 100 Fluid (which is a commercially available C9-C...). 10 A mixture of dialkylbenzene and trialkylbenzene), and Aromatic 150 Fluid (which is a commercially available C 10 -C 12 A mixture of alkylbenzene and alkylnaphthalene.

[0093] The solvent may be present in the photochromic composition of the present invention in an amount of 5 to 95% by weight, or 15 to 80% by weight, 30 to 70% by weight, or 30 to 60% by weight, in each case based on the total weight of the photochromic composition (including the weight of the solvent).

[0094] The photochromic compounds of the present invention can be used in amounts (or ratios) such that compositions, organic materials, or substrates (e.g., photochromic articles and photochromic coatings) incorporating or additionally bonded with the photochromic compound exhibit desired optical properties. The amount and type of photochromic material can be selected such that the composition, organic material, or substrate is transparent or colorless when the photochromic compound is in a closed form (e.g., in a whitish or unactivated state) and exhibits the desired color when the photochromic compound (such as the photochromic indo-fused naphthopyran of the present invention) is in an open form (e.g., when activated by photochemical radiation). The precise amount of photochromic material used in the various photochromic compositions and articles described herein is not critical, provided that a sufficient amount is used to produce the desired effect. The specific amount of photochromic material used can depend on various factors, such as, but not limited to, the absorption characteristics of the photochromic compound, the desired color and color intensity upon activation, and the method used to incorporate or bond the photochromic material to the substrate. The photochromic composition according to the invention may comprise a photochromic compound according to the invention, including a compound represented by formula (I), in an amount of 0.01 to 40 weight percent, such as 0.05 to 15 weight percent, or 0.1 to 5 weight percent based on the weight of the photochromic composition. For further non-limiting purposes, the amount of photochromic compound / material incorporating an organic material, comprising one or more compounds represented by formula (I), may be in the range of 0.01 to 40 weight percent, such as 0.05 to 15 weight percent, or 0.1 to 5 weight percent based on the weight of the organic material.

[0095] The present invention also relates to photochromic articles comprising one or more photochromic compounds according to the invention, such as those represented by formula (I). These photochromic articles can be prepared by methods recognized in the art, such as, but not limited to, inhalation, in-situ casting, coating, in-mold coating, overmolding, and lamination.

[0096] For example, these photochromic products can be selected from ophthalmic products, display products, windows, mirrors, active liquid crystal cell products, and passive liquid crystal cell products.

[0097] In some embodiments, the photochromic articles of the present invention may be ophthalmic articles, and these ophthalmic articles may be selected from corrective lenses, uncorrective lenses, contact lenses, intraocular lenses, magnifying lenses, protective lenses, and goggles.

[0098] In some other embodiments, the photochromic articles of the present invention may be display articles, and these display articles may be selected from screens, monitors, and security elements.

[0099] The present invention may be further characterized by one or more of the following non-limiting aspects.

[0100] Aspect 1: An indo-naphtho-pyran compound represented by formula (I),

[0101] (I)

[0102] in,

[0103] m is between 0 and 3;

[0104] n is between 0 and 3;

[0105] R 1 It is an aryl group substituted with at least one perfluoroalkyl group, or a heteroaryl group substituted with at least one perfluoroalkyl group;

[0106] R 2 It is an alkoxy group;

[0107] R 3 It is an alkoxy, amino, or substituted or unsubstituted nitrogen-containing heterocycle, wherein when R 3 When it is not alkoxy, R 3 Through covalent bonding of nitrogen atoms to position -7;

[0108] R 4 and R 5 Each was selected independently.

[0109] Substituted or unsubstituted alkyl groups; or

[0110] R 4 and R 5 Together they form substituted or unsubstituted spiral rings; and

[0111] R 6 For each n independently, and R 7 For each m, independently selected, in each case independently,

[0112] amino;

[0113] Substituted or unsubstituted nitrogen-containing heterocycles;

[0114] Halogen groups;

[0115] Substituted or unsubstituted alkyl groups;

[0116] Substituted or unsubstituted alkoxy groups;

[0117] Perfluoroalkyl; or

[0118] Substituted or unsubstituted alkylthio groups.

[0119] Aspect 2: The indo-naphtho-pyran compound as described in aspect 1, wherein,

[0120] R 1 It is composed of at least one straight or branched C1-C 10 A perfluoroalkyl-substituted aryl group, or a C1-C group consisting of at least one straight or branched chain. 10 Perfluoroalkyl-substituted heteroaryl groups;

[0121] R 2 Is it a straight or branched C1-C? 10 Alkoxy;

[0122] R 3 Selected from,

[0123] C1-C of straight or branched chains 10 Alkoxy

[0124] The secondary or tertiary amino group represented by formula (II) below,

[0125] (II)

[0126] For equation (II), R 8 and R 9 Each is independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, or substituted or unsubstituted aryl, provided that R 8 and R 9 At least one of them is not hydrogen.

[0127] Substituted or unsubstituted piperidinyl group,

[0128] Substituted or unsubstituted morpholino group,

[0129] Substituted or unsubstituted C3-C6 cyclic amides, or

[0130] Substituted or unsubstituted piperazine group represented by formula (III),

[0131] (III)

[0132] For equation (III),

[0133] R 10 It is selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, alkylsulfonyl, or perhaloalkylsulfonyl.

[0134] Aspect 3: Indo-naphtho-pyran compounds as described in aspect 2, wherein,

[0135] R 1 It is an aryl group substituted with at least one straight-chain or branched C1-C6 perfluoroalkyl group, or a heteroaryl group substituted with at least one straight-chain or branched C1-C6 perfluoroalkyl group.

[0136] R 2 It is a straight-chain or branched C1-C6 alkoxy group;

[0137] R 3 Selected from,

[0138] Straight-chain or branched C1-C6 alkoxy groups

[0139] The secondary or tertiary amino group represented by formula (II),

[0140] For equation (II), R 8 and R 9 Each of the following is independently selected from hydrogen, substituted or unsubstituted straight-chain or branched C1-C6 alkyl, substituted or unsubstituted C5-C7 cycloalkyl, or substituted or unsubstituted aryl, provided that at least one of R8 and R9 is not hydrogen.

[0141] Unsubstituted piperidinyl group,

[0142] Substituted or unsubstituted morpholino group,

[0143] Unsubstituted C3-C6 cyclic amides, or

[0144] The substituted or unsubstituted piperazine group represented by formula (III),

[0145] For equation (III),

[0146] R 10 Selected from hydrogen, substituted or unsubstituted straight-chain or branched C1-C6 alkyl, substituted or unsubstituted phenyl, or straight-chain or branched C1-C6 perhaloalkylsulfonyl.

[0147] R 4 and R 5 Each was selected independently.

[0148] Unsubstituted straight-chain or branched C1-C6 alkyl groups; and

[0149] R 6 For each n independently, and R 7 For each m, independently selected, in each case independently,

[0150] Substituted or unsubstituted piperidinyl group,

[0151] Substituted or unsubstituted morpholino group,

[0152] Substituted or unsubstituted piperazine group, independently as described in reference formula (III),

[0153] Fluorine, chlorine, or bromine

[0154] Substituted or unsubstituted straight-chain or branched C1-C6 alkyl groups, or

[0155] Substituted or unsubstituted straight-chain or branched C1-C6 alkoxy groups.

[0156] Aspect 4: Indo-naphtho-pyran compounds as described in aspect 2 or aspect 3, wherein,

[0157] R 1 It is a phenyl group substituted with at least one straight-chain or branched C1-C4 perfluoroalkyl group, or a pyridyl group substituted with at least one straight-chain or branched C1-C4 perfluoroalkyl group.

[0158] R 2 It is a straight-chain or branched C1-C4 alkoxy group;

[0159] R 3 Selected from,

[0160] Straight-chain or branched C1-C4 alkoxy groups

[0161] The secondary or tertiary amino group represented by formula (II),

[0162] For equation (II), R 8 and R 9 Each is independently selected from unsubstituted straight-chain or branched C1-C4 alkyl groups, or straight-chain or branched C1-C4 fully haloalkyl groups, provided that R 8 and R 9 At least one of them is a straight-chain or branched C1-C4 fully haloalkyl group.

[0163] Substituted or unsubstituted piperidinyl group,

[0164] Substituted or unsubstituted morpholino group,

[0165] The substituted piperazine group represented by formula (III),

[0166] For equation (III),

[0167] R 10 Selected from substituted or unsubstituted straight-chain or branched C1-C4 alkyl groups, substituted or unsubstituted phenyl groups, or straight-chain or branched C1-C4 perhaloalkylsulfonyl groups, or

[0168] Unsubstituted C3-C6 cyclic amides;

[0169] R 4 and R5 Each was selected independently.

[0170] Unsubstituted straight-chain or branched C1-C4 alkyl groups; and

[0171] R 6 For each n independently, and R 7 For each m, independently selected, in each case independently,

[0172] Unsubstituted piperidinyl group,

[0173] Unsubstituted morpholino group,

[0174] Fluorine, chlorine, or bromine

[0175] Unsubstituted straight-chain or branched C1-C4 alkyl groups, or

[0176] Unsubstituted straight-chain or branched C1-C4 alkoxy groups.

[0177] Aspect 5: Indo-naphtho-pyran compounds as described in any one of Aspects 1 to 4, provided that R 6 and R 7 At least one of them is an unsubstituted straight-chain or branched C1-C4 alkoxy group.

[0178] Aspect 6: The indo-naphtho-pyran compound as described in any one of aspects 1 to 5, wherein,

[0179] R 1 Selected from,

[0180] 4-(trifluoromethyl)phenyl,

[0181] 2-(trifluoromethyl)phenyl,

[0182] 2,4-Bis(trifluoromethyl)phenyl,

[0183] 3,5-Bis(trifluoromethyl)phenyl,

[0184] 3,4-Bis(trifluoromethyl)phenyl, or

[0185] 5-(trifluoromethyl)pyridin-2-yl;

[0186] R 2 Selected from,

[0187] methoxy, or

[0188] ethoxy,

[0189] R 3 Selected from,

[0190] Morpholinyl,

[0191] 2,6-Dimethylmorpholino,

[0192] 4-Phenylopiratinyl,

[0193] 4-(trifluoromethyl)sulfonylpiperazinyl,

[0194] γ-Butyrolactam,

[0195] δ-valerol, or

[0196] ε-caprolactam;

[0197] R 4 and R 5 Each was selected independently.

[0198] methyl,

[0199] Ethyl,

[0200] n-propyl,

[0201] Isopropyl,

[0202] n-Butyl, or

[0203] Branched butyl groups, such as tert-butyl; and

[0204] R 6 and R 7 Each was selected independently.

[0205] methoxy

[0206] ethoxy,

[0207] n-Propoxy

[0208] Isopropoxy,

[0209] n-Butoxy, or

[0210] Branched butoxy groups, such as tert-butoxy groups.

[0211] Aspect 7: The indo-naphtho-pyran compound as described in any one of aspects 1 to 6, wherein,

[0212] R 1 Selected from,

[0213] 4-(trifluoromethyl)phenyl,

[0214] 2-(trifluoromethyl)phenyl,

[0215] 2,4-Bis(trifluoromethyl)phenyl,

[0216] 3,5-Bis(trifluoromethyl)phenyl,

[0217] 3,4-Bis(trifluoromethyl)phenyl, or

[0218] 5-(trifluoromethyl)pyridin-2-yl;

[0219] R 2 It is a methoxy group;

[0220] R 3 Selected from,

[0221] Morpholinyl,

[0222] 2,6-Dimethylmorpholino,

[0223] 4-Phenylopiratinyl,

[0224] 4-(trifluoromethyl)sulfonylpiperazinyl,

[0225] γ-Butyrolactam,

[0226] δ-valerol, or

[0227] ε-caprolactam;

[0228] R 4 and R 5 Each is n-propyl; and

[0229] R 6 and R 7 Each is independently selected from methoxy or n-butoxy.

[0230] Aspect 8: A photochromic composition comprising an indo-naphtho-pyran compound as described in any one of Aspects 1 to 7.

[0231] Aspect 9: A photochromic article comprising an indene-naphthopyran compound as described in any one of Aspects 1 to 7, wherein the photochromic article is selected from the group consisting of: ophthalmic articles, display articles, windows, mirrors, active liquid crystal cell articles, and passive liquid crystal cell articles.

[0232] Aspect 10: The photochromic article according to aspect 9, wherein the photochromic article is selected from ophthalmic articles, and the ophthalmic articles are selected from corrective lenses, uncorrective lenses, contact lenses, intraocular lenses, magnifying lenses, protective lenses, and goggles.

[0233] The invention is described in more detail in the following examples, which are intended to be illustrative only, as many modifications and variations therein will be apparent to those skilled in the art. Example

[0234] In Part-1 of the following examples, a description is provided of the synthesis of comparative indo-naphtho-pyran compounds (comparative examples / compounds CE1, CE2, CE12, and CE13) and indo-naphtho-pyran compounds according to the present invention (examples / compounds 3-11, 14, and 15). In Part-2, a summary of the comparison of Part-1 and the evaluation of the indo-naphtho-pyran compounds of the present invention is provided.

[0235] Part-1

[0236] Synthesis Description

[0237] Scheme-1 below specifically provides a summary of the synthesis of the indo-naphtho-pyran compound of Comparative Example 1 (CE1). Scheme-1 also includes starting materials, and / or intermediates, and / or alternatives thereof for the synthesis of other comparative compounds and compounds of the present invention in the examples below.

[0238] Option-1

[0239] Comparative Example 1 (CE1)

[0240]

[0241] Comparison example CE1:

[0242] The comparative compound CE1 was prepared according to the following steps.

[0243] Step 1:

[0244] In a round-bottom flask, 9-bromo-2,3-dimethoxy-7,7-dipropyl-7H-benzo[c]fluorene-5-ol (20 g) (100), imidazole (4.48 g), 4-(dimethylamino)pyridine (0.54 g), and anhydrous N,N-dimethylformamide (60 mL) were combined and stirred. The mixture was cooled to between -5°C and 0°C by immersing the flask in a brine and ice bath. Tert-butyldimethylsilyl chloride (7.94 g) (TBDMSCl) was then added to the reaction mixture in four equal portions at 5-minute intervals. The reaction mixture was allowed to warm to room temperature and then stirred for 16 hours. It was then poured into ice water and extracted twice with ethyl acetate. The combined organic layers were washed twice with brine, dried over sodium sulfate, and concentrated to dryness. The resulting residue was filtered through a short silica gel stopper, and the filter was washed with a mixture of 25% ethyl acetate and 75% hexane. The mother liquor was concentrated to dryness to obtain an amber-colored oily substance consistent with the intermediate (103') described below and the intermediate (103) (25.02 g) in Scheme-1.

[0245] (103')

[0246] Step 2:

[0247] Hexane (55 mL) and morpholine (3.87 g) (106) were combined in a two-necked round-bottom flask. The flask was immersed in an ice bath, and then a solution of 2.5 M n-butyllithium (n-BuLi) in hexane (15.4 mL) was added dropwise via syringe over 5 minutes. The intermediate from step 1 (103) (11.00 g) was then added to the mixture, followed by anhydrous tetrahydrofuran (70 mL). The reaction mixture was heated to room temperature for 1 hour and then poured into ice water. It was extracted twice with ethyl acetate, and the combined organic layers were washed with brine, dried over sodium sulfate, and concentrated to dryness. The resulting residue was filtered through a short silica stopper, and the filter was washed with a mixture of 25% ethyl acetate and 75% hexane. The mother liquor was concentrated to dryness to give an amber oil consistent with the intermediate (9.23 g) (109') and the intermediate (109) of scheme-1.

[0248] (109')

[0249] Step 3:

[0250] The intermediate from step 2 (4.62 g) (109'), isooctyl 3-mercaptopropionate (1.78 g), N,N-diisopropylethylamine (1.91 g), and toluene (28 mL) were combined and stirred in a round-bottom flask. The mixture was purged with nitrogen for 20 minutes. Tris(dibenzylacetone)dipalladium(O) (0.20 g) and 4,5-bis(diphenylphosphino)-9,9-dimethyloxanthracene (0.26 g) were added to the mixture. It was heated to 110°C for 90 minutes and then cooled to room temperature. Anhydrous N,N-dimethylformamide (26 mL), followed by a 40% solution of sodium tert-pentoxide in toluene (8.13 g), was added to the reaction mixture and stirred for 10 minutes. Next, 1-bromo-4-fluorobenzene (5.17 g) was added, and the mixture was then heated to 120°C for 1 hour. After cooling to room temperature, the reaction mixture was poured into ice water, and then a dilute aqueous solution of hydrochloric acid was added until a pH of 5 was obtained. It was then extracted twice with ethyl acetate. The combined organic layers were washed twice with brine, dried over sodium sulfate, and then concentrated to dryness. The resulting residue was purified by rapid chromatography on silica gel, eluting with a mixture of 25% ethyl acetate and 75% hexane. Fractions containing the desired intermediate were combined and concentrated to dryness. The resulting solid was slurried in a mixture of 10% ethyl acetate and 90% hexane, and then collected by vacuum filtration to give the intermediate (1.50 g) represented by the following structure (112).

[0251] (112)

[0252] Step 4:

[0253] The intermediate from step 3 (112) (1.00 g), 1,1-bis(4-methoxyphenyl)prop-2-yn-1-ol (0.63 g) (115), 4-pyridinium p-toluenesulfonate (0.06 g) (PTSA), and 1,2-dichloroethane (20 mL) were combined in a round-bottom flask and heated to 83°C for two hours. After cooling to room temperature, the reaction mixture was filtered through a short silica gel stopper, and the filter was washed with a mixture of 25% ethyl acetate and 75% hexane. The mother liquor was concentrated to dryness. The resulting residue was purified by rapid chromatography on silica gel, eluting with a mixture of 25% ethyl acetate and 75% hexane. Fractions containing the desired product were combined and concentrated to dryness. Methanol was added to the resulting residue to precipitate a solid, which was then collected by vacuum filtration. NMR analysis of the solid was consistent with the following representative structure (0.97 g) (118).

[0254] (118)

[0255] Compare the compounds in Examples 2, 12, and 13 (CE2, CE12, and CE13) with those in Examples 3-11, 14, and 15:

[0256] The compounds depicted in Table A below are typically prepared according to the synthetic procedure described with respect to CE1, which uses: the corresponding amine precursor in step 2; the appropriately substituted bromobenzene compound in step 3; and the appropriately substituted propargyl alcohol in step 4. The compounds in Comparative Examples CE13 and CE14, and Examples 15 and 16, are typically prepared according to the synthetic procedure described with respect to CE1, but without amination in step 2 to obtain 6,7-dimethoxy-substituted compounds (instead of 6-methoxy,7-morpholino-substituted compounds).

[0257] Table 1

[0258]

[0259] Table 1

[0260] (Continued)

[0261]

[0262] Table 1

[0263] (Continued)

[0264]

[0265] Table 1

[0266] (Continued)

[0267]

[0268] Table 1

[0269] (Continued)

[0270]

[0271] Part 2

[0272] Evaluation of indene-naphthopyran compounds in part-1

[0273] Each of the indo-naphthopyran compounds in fraction-1 was incorporated into a polyurethane coating system (as described in U.S. Patent No. 8,608,988 B2, Examples 1-3) at the same molar percentage and applied with the same coating thickness as a 2” × 2” (5.1 cm × 5.1 cm) test chip made from CR-39® monomer (PPG Industrials, Inc.). All coated test chips were cured at 125°C for 1 hour.

[0274] Each of the coated test chips was conditioned by first exposing it to 365 nm UV light at a distance of approximately 14 cm for 10 minutes to activate the photochromic material within the coating. The UVA (315 to 380 nm) irradiance at the chip was measured using a LICOR® Li-1800 spectroradiometer and found to be 22.2 W / m². Each test chip was then placed under a 500 W high-intensity halogen lamp at a distance of approximately 36 cm for 10 minutes to cause the photochromic material to whiten (deactivate). The illuminance at the chip was measured using a LICOR® spectroradiometer and found to be 21.9 Klux. The coated test chips were then kept in darkness at room temperature (i.e., 70°F to 75°F, or 21°C to 24°C) for at least 1 hour before testing / measuring on the optical platform. The UV absorbance of the coated test chip at 390 nm was measured before measurement on the optical platform.

[0275] According to CIE 15:2004 colorimetric method, using a D 65 light source and a 10° observer, the CIE Y value is used to determine the percentage of transmittance (%T) of each coated test chip. As used herein, a and b The value refers to the a value measured using UltraScan Pro (HunterLabs) according to CIE 15:2004 spatial colorimetry, with a D 65 light source and a 10° observer. and b value.

[0276] The BMP optical platform is equipped with two 150-watt ORIEL® Model #66057 xenon arc lamps positioned perpendicular to each other. The light path from lamp 1 is guided through a 3 mm SCFIOTT® KG-2 bandpass filter and an appropriate neutral density filter, contributing to the desired UV and partial visible irradiance levels. The light path from lamp 2 is guided through a 3 mm SCFIOTT® KG-2 bandpass filter, a SCFIOTT® short-band 400 nm cutoff filter, and an appropriate neutral density filter to provide supplemental visible irradiance. A 2-inch × 2-inch (5.1 cm × 5.1 cm) 50% Polka dot beam splitter at 45° to each lamp is used to mix the two beams. The irradiance intensity is adjusted using a combination of neutral density filters and xenon arc lamp voltage control. Proprietary software (i.e., BMPSoft version 2.1e) is used on the BMP to control timing, irradiance, chamber and sample temperatures, shielding, filter selection, and response measurements. Response and color measurements were performed using a ZEISS® spectrophotometer (model MCS 501) with an optical fiber cable for transmitting light through the coated test chips. Photopic response measurements were collected on each coated test chip. The power output of the optical platform (i.e., the dose of light exposed to the coated test chips) was adjusted to 6.7 watts per square meter (W / m²). 2 The power setpoint measurements were performed using an irradiance probe and a calibrated Zeiss spectrophotometer. The coated test chip sample cell was equipped with a quartz window and an automatically centering sample holder. The temperature in the sample cell was controlled at 23°C using a modified Facis FX-10 environmental simulator via software. Measurements of the dynamic photochromic response and color of the coated test chip were performed using the same Zeiss spectrophotometer with an optical fiber cable for transmitting light from the halogen tungsten lamp and through the sample. The collimated monitoring beam from the optical fiber cable was kept perpendicular to the test sample, passing through the coated test chip sample and being guided to the receiving optical fiber cable assembly attached to the spectrophotometer. The precise placement of the coated test chip sample in the sample cell was where the activated xenon arc beam and the monitoring beam intersected to form two concentric circles of light. The incident angle of the xenon arc beam at the sample placement point is 30° relative to the vertical.

[0277] The response measurement, expressed as the change in optical density (ΔOD) from an unactivated or whitish state to an activated or colored state, is determined by establishing an initial unactivated transmittance, opening the xenon lamp's shackle, and measuring the transmittance through activation at selected time intervals. The optical density change is determined according to the following formula:

[0278] ΔOD = Log (10) (% Tb / % Ta)

[0279] Referring to the above ΔOD formula: %Tb is the percentage of transmission in the whitened state; and %Ta is the percentage of transmission in the activated state. The ΔOD at saturation was measured 15 minutes after activation, and the fading half-life (T1 / 2) value is the time interval (in seconds) at which the ΔOD of the activated form of the photochromic material in the coating reaches half of the 15-minute ΔOD at 73.4°F (23°C) after the activation light source is removed.

[0280] The results of the above tests and evaluations are summarized in Tables 2 and 3 below.

[0281] Table 2

[0282]

[0283] Table 3

[0284]

[0285] The data summarized in Table 2 show that, compared with the comparative indonopyran compound (having a (fluoroaryl)thiosubstituent at position -11), the indonopyran compound according to the invention (having a (perfluoroalkyl)aryl)thiosubstituent at position -11) provides an improved fading rate without significant loss in the dark in the activated state. The data summarized in Table 3 further demonstrate the rapid fading rate provided by the indonopyran compounds according to the invention having various groups at positions -7 and -11.

[0286] The invention has been described in detail with reference to specific embodiments thereof. This is not intended to be construed as limiting the scope of the invention, except where such details are included in the appended claims.

Claims

1. An indenonaphthopyran compound represented by the following formula (I), (I) wherein, m is 0 to 3; n is 0 to 3; R 1 is aryl substituted by at least one perfluoroalkyl group, or heteroaryl substituted by at least one perfluoroalkyl group; R 2 is alkoxy; R 3 is alkoxy, amino, or a substituted or unsubstituted nitrogen-containing heterocycle, wherein when R 3 is not alkoxy, R 3 is covalently bonded to position -7 through a nitrogen atom; R 4 and R 5 are each independently selected from the group consisting of substituted or unsubstituted alkyl; or R 4 and R 5 together form a substituted or unsubstituted spiro ring; and R 6 for each n independently, and R 7 for each m independently, in each case independently selected from the group consisting of amino; substituted or unsubstituted nitrogen-containing heterocycle; halogen group; substituted or unsubstituted alkyl; substituted or unsubstituted alkoxy; perfluoroalkyl; or substituted or unsubstituted alkylthio.

2. The indenonaphthopyran compound according to claim 1, wherein, R 1 is aryl substituted by at least one straight-chained or branched C1-C 10 aryl substituted by at least one straight-chained or branched C1-C 10 heteroaryl substituted by at least one straight-chained or branched C1-C R 2 is linear or branched CrC 10 alkoxy; R 3 selected from, linear or branched C1-C 10 alkoxy, secondary or tertiary amino group represented by the following formula (II), (I) wherein for Formula (II), R 8 and R 9 are each independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, or substituted or unsubstituted aryl, provided that at least one of R 8 and R 9 is not hydrogen, substituted or unsubstituted piperidyl, substituted or unsubstituted morpholyl, substituted or unsubstituted C3-C6 cyclic amide, or substituted or unsubstituted piperazyl represented by the following formula (III), (III) wherein for formula (III), R 10 is selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, alkylsulfonyl, or perhaloalkylsulfonyl.

3. The indenonaphthopyran compound according to claim 2, wherein, R 1 is aryl substituted by at least one straight-chained or branched C1-C6perfluoroalkyl group, or heteroaryl substituted by at least one straight-chained or branched C1-C6perfluoroalkyl group; R 2 is linear or branched C1-C6alkoxy; R 3 selected from, straight chain or branched C1-C6 alkoxy, secondary or tertiary amino group represented by formula (II), wherein for Formula (II), R 8 and R 9 are each independently selected from hydrogen, substituted or unsubstituted linear or branched C1-C6alkyl, substituted or unsubstituted C5-C7cycloalkyl, or substituted or unsubstituted aryl, provided that at least one of R8and R9is not hydrogen, unsubstituted piperidyl, substituted or unsubstituted morpholyl, unsubstituted C3-C6 cyclic amide, or substituted or unsubstituted piperazyl represented by formula (III), wherein for formula (III), R 10 selected from hydrogen, substituted or unsubstituted linear or branched C1-C6alkyl, substituted or unsubstituted phenyl, or linear or branched C1-C6perhaloalkylsulfonyl, R 4 and R 5 are each independently selected from the group consisting of unsubstituted straight chain or branched C1-C6 alkyl; and R 6 for each n independently, and R 7 for each m independently, in each case independently selected from the group consisting of substituted or unsubstituted piperidyl, substituted or unsubstituted morpholyl, substituted or unsubstituted piperazyl independently as described with reference to formula (III), fluorine, chlorine, or bromine, substituted or unsubstituted straight chain or branched C1-C6 alkyl, or substituted or unsubstituted straight chain or branched C1-C6 alkoxy.

4. The indenonaphthopyran compound according to claim 3, wherein, R 1 is phenyl substituted by at least one straight-chained or branched C1-C4 perfluoroalkyl group, or pyridyl substituted by at least one straight-chained or branched C1-C4 perfluoroalkyl group; R 2 is linear or branched C1-C4alkoxy; R 3 selected from, straight chain or branched C1-C4 alkoxy, secondary or tertiary amino group represented by formula (II), wherein for formula (II), R 8 and R 9 are each independently selected from unsubstituted linear or branched C1-C4 alkyl, or linear or branched C1-C4 perhalogenated alkyl, with the proviso that at least one of R 8 and R 9 is linear or branched C1-C4 perhalogenated alkyl, substituted or unsubstituted piperidyl, substituted or unsubstituted morpholyl, substituted piperazyl represented by formula (III), wherein for formula (III), R 10 selected from substituted or unsubstituted linear or branched C1-C4alkyl, substituted or unsubstituted phenyl, or linear or branched C1-C4perhaloalkylsulfonyl, or unsubstituted C3-C6 cyclic amide; R 4 and R 5 are each independently selected from the group consisting of unsubstituted straight chain or branched C1-C4 alkyl; and R 6 for each n independently, and R 7 for each m independently, in each case independently selected from the group consisting of unsubstituted piperidyl, unsubstituted morpholyl, fluorine, chlorine, or bromine, unsubstituted straight chain or branched C1-C4 alkyl, or unsubstituted straight chain or branched C1-C4 alkoxy.

5. The indenonaphthopyran compound of claim 4, with the proviso that R 6 and at least one of R 7 is unsubstituted straight or branched C1-C4 alkoxy.

6. A photochromic composition comprising the indenonaphthopyran compound according to claim 1.

7. A photochromic article comprising the indenonaphthopyran compound of claim 1, 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.

8. The photochromic article of claim 7 wherein, The photochromic article is selected from an ophthalmic article, and the ophthalmic article is selected from a corrective lens, a non-corrective lens, a contact lens, an intraocular lens, a magnification lens, a protective lens, and eyewear.

Images