Indenonaphthopyrane having a perfluoroalkyl-substituted aryl / heteroaryl sulfide at position 11

Abstract

The present invention relates to the following formula (I) This relates to the indenonaphthopyrane compound represented by JPEG2026517214000025.jpg60160. With respect to formula (I), m, n and R 4 ~R 7 This is as described herein. Furthermore, with respect to formula (I), R 1 is an aryl or heteroaryl substituted with at least one perfluoroalkyl group, and R 2 is an alkoxy, and R 3 R is an alkoxy, amino, or substituted or unsubstituted nitrogen-containing heterocycle, 3 If R is not an alkoxy, 3 This is conditional on the nitrogen atom being covalently bonded at position 7. The present invention also relates to photochromic compositions and photochromic articles comprising an indenonaphthopyrane compound represented by formula (I).

Description

[Technical Field]

[0001] The present invention relates to indenonaphthopyrane compounds having a perfluoroalkyl-substituted aryl group or a perfluoroalkyl-substituted heteroaryl group bonded at the 11th position by a sulfide bond, as well as photochromic compositions and photochromic articles containing such compounds. [Background technology]

[0002] In response to specific wavelengths of electromagnetic radiation (or "chemical rays"), photochromic compounds such as indenonaphthopyran (or indenocondensed naphthopyran) typically undergo transformation from one form or state to another, each form having its own characteristic or distinguishable absorption spectrum. Typically, when exposed to chemical rays, many photochromic compounds transform from a ring-closed form corresponding to the inactive (or decolorized, e.g., substantially colorless) state of the photochromic compound to an open-ring form corresponding to the activated (or colored) state of the photochromic compound. In the absence of exposure to chemical rays, such photochromic compounds reversibly transform back from the activated (or colored) state to the inactive (or decolorized) state. Compositions containing or coated with photochromic compounds (e.g., in the form of photochromic coating compositions) and articles such as eyeglass lenses typically exhibit colorless (e.g., transparent) and colored states corresponding to the colorless and colored states of the photochromic compound contained therein or coated thereon.

[0003] Photochromic indenonaphthopyrane compounds are generally desirable to provide a significant level of dark color when exposed to chemical radiation. It is also generally desirable that photochromic indenonaphthopyrane compounds rapidly decolorize to an inactive (or decolorized) state when not exposed to chemical radiation. Indenonaphthopyrane compounds that provide a combination of a significant or high level of dark color when exposed to chemical radiation and a rapid decolorization rate when not exposed typically and undesirably have an overly dark decolorized state (or color) and / or insufficient fatigue resistance. [Overview of the project] [Problems that the invention aims to solve]

[0004] It would be desirable to develop novel indenonaphthopyran compounds that provide a combination of a marked or high level of darkening upon exposure to chemical radiation and a rapid fading rate in the absence of chemical radiation exposure, without excessively dark decolorization (or bleaching) and / or poor fatigue resistance. [Means for solving the problem]

[0005] According to the present invention, the following formula (I) [ka] An indenonaphthopyran compound represented by is provided.

[0006] Regarding equation (I), m is between 0 and 3, n is between 0 and 3, and R 1 is an aryl or heteroaryl substituted with at least one perfluoroalkyl group, and R 2 is an alkoxy, and R 3 R is an alkoxy, amino, or substituted or unsubstituted nitrogen-containing heterocycle, 3 If R is not an alkoxy, 3 This is conditional on the nitrogen atom being covalently bonded at position 7. Furthermore, with respect to equation (I), R4 and R 5 is each independently selected from substituted or unsubstituted alkyl, or R 4 and R 5 together form a substituted or unsubstituted spiro ring. Further, with respect to formula (I), R 6 is independently for each n, and R 7 is independently for each m, and in each case independently, is selected from amino, a substituted or unsubstituted nitrogen-containing heterocyclic ring, a halo group, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkoxy, a perfluoroalkyl, or a substituted or unsubstituted alkylthio.

[0007] According to the present invention, a photochromic composition containing the indeno naphthopyran compound of the present invention is also provided.

[0008] Furthermore, according to the present invention, a photochromic article containing the indeno naphthopyran compound of the present invention is provided.

[0009] The features characterizing the present invention are pointed out in detail in the claims that are attached to and form a part of this disclosure. These and other features of the present invention, the advantages of its operation, and the specific objects obtained by its use will be more particularly understood from the following detailed description in which non-limiting embodiments of the present invention are illustrated and described.

Embodiments for Carrying Out the Invention

[0010] As used herein, the articles "a", "an", and "the" include plural referents unless expressly and specifically limited to one referent.

[0011] Unless otherwise indicated, all ranges or ratios disclosed herein should be understood to encompass all subranges or sub-ratios contained therein. For example, a specified range or ratio of "1 to 10" should be considered to include all subranges from a minimum value of 1 to a maximum value of 10 (including both endpoints), i.e., all subranges or sub-ratios that begin with a minimum value of 1 or greater and end with a maximum value of 10 or less, such as 1 to 6.1, 3.5 to 7.8, and 5.5 to 10, but are not limited to these.

[0012] In this specification, unless otherwise indicated, the left-to-right representation of bonding groups, such as divalent bonds, is not limited to but includes other appropriate directions, such as right-to-left. For non-limiting illustrative purposes, divalent bonds [ka] Or, the left-to-right representation of the equal -C(O)O- is the right-to-left representation [ka] Or it contains equal amounts of -O(O)C- or -OC(O)-.

[0013] Unless otherwise indicated in the operational examples or elsewhere, all figures used in this specification and in the claims, representing amounts of components, reaction conditions, etc., should be understood to be modified in all cases by the term "approximately".

[0014] 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.

[0015] As used herein, the terms “(meth)acrylate” and similar terms such as “(meth)acrylic acid ester” mean methacrylate and / or acrylate. As used herein, the term “(meth)acrylic acid” means methacrylic acid and / or acrylic acid.

[0016] The indenonaphthopyran compounds of the present invention are also referred to herein as photochromic indenonaphthopyran compounds and / or photochromic indenonaphthopyran.

[0017] The indenonaphthopyrane compounds of the present invention described herein, including but not limited to indenonaphthopyrane compounds represented by formula (I), may further optionally include one or more co-products obtained from the synthesis of such compounds.

[0018] As used herein, the terms “photochromic” and similar terms such as “photochromic compound” mean having at least a visible light absorption spectrum that changes in response to the absorption of chemical rays. Furthermore, as used herein, the term “photochromic material” means any substance that is adapted to exhibit photochromic properties (such as being adapted to have at least a visible light absorption spectrum that changes in response to the absorption of chemical rays) and contains at least one photochromic compound.

[0019] As used herein, the term “chemical radiation” means electromagnetic radiation capable of producing a response in a material, such as transforming a photochromic material from one form or state to another, as will be further described herein.

[0020] As used herein, the term “photochromic material” includes both thermoreversible and non-thermally reversible photochromic materials and compounds. As used herein, the term “thermally reversible photochromic compound / material” means a compound / material that can transform from a first state, e.g., “transparent state,” to a second state, e.g., “colored state,” in response to a chemical beam, and return to the first state in response to thermal energy. As used herein, the term “non-thermally reversible photochromic compound / material” means a compound / material that can transform from a first state, e.g., “transparent state,” to a second state, e.g., “colored state,” in response to a chemical beam, and return to the first state in response to a chemical beam of substantially the same wavelength as the absorption of the colored state (e.g., by ceasing exposure to such chemical beam).

[0021] Where used herein to modify the term “state,” the terms “first” and “second” are intended to refer to two distinct states or properties, and not to any particular order or time series. For non-limiting illustrative purposes, the first and second states of a photochromic compound may differ with respect to at least one optical property, such as absorption of visible light and / or UV irradiation, but not to limit. Accordingly, 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, a photochromic compound of the present invention may be colorless and transparent in the first state and colored in the second state, although this is not limited herein. Alternatively, a photochromic compound of the present invention may have a first color in the first state and a second color in the second state.

[0022] As used herein, the term “optical” means relating to or associated with light and / or vision. For example, according to various non-limiting embodiments disclosed herein, optical articles or elements or devices 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.

[0023] As used herein, the term “ophthalmic” means relating to or associated with the eye and vision. Non-exclusive examples of ophthalmic articles or elements include corrective and non-corrective lenses, including multivision lenses (such as bifocal lenses, trifocal lenses and progressive lenses, but not limited to single-vision or segmented or non-segmented multivision lenses), and other elements used to correct, protect or enhance vision (cosmetic or otherwise), such as contact lenses, intraocular lenses, magnifying lenses and protective lenses or visors.

[0024] As used herein, the term “display” means a visible or machine-readable representation of information in words, numbers, symbols, designs, or diagrams. Non-exclusive examples of display elements include screens, monitors, and security elements such as security marks.

[0025] As used herein, the term “window” means an opening adapted to allow the transmission of radiation. Non-limiting examples of windows include automotive and aircraft transparency, windshields, filters, shutters, and optical switches.

[0026] As used herein, the term “mirror” means a surface that specularly reflects most of the incident light.

[0027] As used herein, the term “liquid crystal cell” refers to a structure comprising liquid crystal material that can be aligned. A non-limiting example of a liquid crystal cell element is a liquid crystal display.

[0028] As used herein, the terms “ring position” and similar terms such as “position X” or “position-X” refer to a specific position in the ring structure, for example, in a fused ring structure, of a compound such as the indenonaphthopyran compound of the present invention, and are indicated herein by a number within the ring structure of a representative chemical formula, such as formula (I), according to several embodiments.

[0029] Without limitation, all documents, including issued patents and patent applications, referred to herein should be considered "incorporated by reference" unless otherwise indicated.

[0030] When used herein, the description of a "linear or branched" group, such as a linear or branched alkyl group, means a methylene group or a methyl group, or a linear C2-C2 group. 20 Linear groups such as alkyl groups and branched C3-C 20 This is understood herein to include appropriately branched groups such as alkyl groups.

[0031] As used herein, the term "alkyl" refers to a linear or branched C1-C chain. 25 This refers to alkyl groups. Linear or branched alkyl groups include C1-C 25 Alkyl, for example, C1-C 20 Alkyl, for example, C2~C 10 Alkyl, for example, C1-C 12 Examples of alkyl groups include, for example, C1-C6 alkyl groups. Various alkyl groups of the present invention can be selected, but are not limited to, those listed further herein.

[0032] As used herein, the term "cycloalkyl" is not limited to C3-C3 12 Cycloalkyl (not limited to, but cyclic C3-C) 10This refers to appropriately cyclic groups such as alkyl or cyclic C5-C7 alkyl groups. Examples of cycloalkyl groups include, but are not limited to, those listed further herein. As used herein, the term "cycloalkyl" includes, but is not limited to, crosslinked ring polycycloalkyl groups (or crosslinked ring polycyclic alkyl groups) such as bicyclo[2.2.1]heptyl (or norbornyl) and bicyclo[2.2.2]octyl, as well as, but is not limited to, fused ring polycycloalkyl groups (or fused ring polycyclic alkyl groups) such as octahydro-1H-indenyl and decahydronaphthalenyl.

[0033] As used herein, the term "heterocycloalkyl" does not limit itself to C2-C5 heterocycloalkyl groups such as C5-C7 heterocycloalkyl groups. 10 C2-C such as heterocycloalkyl groups 12 The term "heterocycloalkyl" means a group that is appropriately cyclic and has at least one heteroatom in the cyclic ring, such as, but not limited to, O, S, N, P, or combinations thereof, including heterocycloalkyl groups. Examples of heterocycloalkyl groups include, but are not limited to, imidazolyl, tetrahydrofuranil, tetrahydropyranil, piperidinil, morpholinil, and piperazinil. As used herein, the term "heterocycloalkyl" also includes, but is not limited to, bridging ring polycyclic heterocycloalkyl groups such as 7-oxabicyclo[2.2.1]heptanil, and, but is not limited to, fused ring polycyclic heterocycloalkyl groups such as octahydrocyclopenta[b]pyranil and octahydro-1H-isoclomenil.

[0034] When used herein, for example, R 3The term "nitrogen-containing heterocycle" as used in relation to this refers to a ring containing at least one nitrogen atom, e.g., one or two nitrogen atoms, and optionally at least one additional heteroatom other than nitrogen, such as oxygen, which in some embodiments is covalently bonded to another group, such as an indenonaphthopyran compound according to the present invention, via the nitrogen atoms within the ring. Examples of nitrogen-containing heterocycles include, but are not limited to, cyclic aminos such as piperidino, pyrrolidino, piperazino, and morpholino; C3-C6 cyclic amides, cyclic amides (or lactams) such as β-propiolactam, γ-butyrolactam, δ-valerolactam, or ε-caprolactam; and heteroaromatic compounds such as imidazole, pyrrole, indole, and carbazole.

[0035] The descriptions, classes, and examples given herein with respect to alkyl groups, cycloalkyl groups, heterocycloalkyl groups, haloalkyl groups, etc., also apply to alkane groups, cycloalkane groups, heterocycloalkane groups, haloalkane groups, etc., and, for example, but not limited to, polyvalent alkane groups, such as polyvalent alkane bond groups, such as divalent alkane bond groups.

[0036] As used herein, the terms "aryl" and related terms such as "aryl group" mean aromatic cyclic monovalent hydrocarbon groups. As used herein, the terms "aromatic" and related terms such as "aromatic group" mean cyclic conjugated hydrocarbons that have significantly higher stability than the hypothetical localized structure (due to delocalization of π electrons). Examples of aryl groups include, but are not limited to, C6-C6 groups such as phenyl, naphthyl, phenanthryl, and anthracenyl. 14 An example is the aryl group.

[0037] As used herein, the term "heteroaryl" includes, but is not limited to, C3-C 10 Heteroaryl groups (such as fused polycyclic heteroaryl groups) and other C3-C groups 18This term includes, but is not limited to, heteroaryl groups, and in the case of heteroaryl groups in aromatic rings or polycyclic fused rings, it means aryl groups having at least one heteroatom in at least one aromatic ring. Examples of heteroaryl groups include, but are not limited to, furanyl, pyranyl, pyridinyl, quinolinyl, isoquinolinyl, and pyrimidinyl.

[0038] Typical 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. Typical alkenyl groups include, but are not limited to, vinyl, allyl, and propenyl. Typical alkynyl groups include, but are not limited to, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, and 2-butynyl. Typical cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

[0039] As used herein, the term "halo" 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.

[0040] As used herein, the terms “halo-substituted” and related terms (including, but not limited to, haloalkyl groups, haloalkenyl groups, haloalkynyl groups, haloaryl groups, and halo-heteroaryl groups) mean a group in which at least one and all of its available hydrogen groups are substituted with a halo group such as F, Cl, or Br, but not limited to. The term “halo-substituted” includes “perhalo-substituted.”

[0041] As used herein, the term "perfluoroalkyl group" means an alkyl group in which all of its available hydrogen groups are substituted (or replaced) with fluoro(F) groups, in each case.

[0042] As used herein, "at least one of ~" is synonymous with "one or more of ~," regardless of whether the elements are listed associatively or disassociatively. For example, the phrases "at least one of A, B, and C" and "at least one of A, B, or C" mean one of A, B, or C, or any combination of any two or more of A, B, or C, respectively. For example, A only, or B only, or C only, or A and B, or A and C, or B and C, or all of A, B, and C.

[0043] As used herein, “selected from” is synonymous with “chosen from,” whether the elements are listed associatively or disassociatively. Furthermore, the phrases “selected from A, B, and C” and “selected from A, B, or C” mean one of A, B, or C, or any combination of any two or more of A, B, or C, respectively. For example, A only, or B only, or C only, or A and B, or A and C, or B and C, or all of A, B, and C.

[0044] As used herein, according to some embodiments, the terms “ketone” and related terms such as “ketone group” and “ketone substituent” relating to the groups and substituents of various groups of the photochromic compounds of the present invention include substances represented by the formula -C(O)R, where R is selected from the groups listed below.

[0045] As used herein, according to some embodiments, the terms "carboxylic acid" and related terms such as "carboxylic acid group" and "carboxylic acid substituent," which relate to the groups and substituents of various groups of the photochromic compounds of the present invention, include substances represented by -C(O)OH.

[0046] As used herein, according to some embodiments, the terms “ester” and related terms such as “ester group” and “ester substituent” relating to the groups and substituents of various groups of the compounds and components of the present invention mean a carboxylic acid ester group represented by -C(O)OR, where R is selected from the groups listed below.

[0047] As used herein, according to some embodiments, the terms “carbonate” and related terms such as “carbonate group” and “carbonate substituent” relating to the groups and substituents of various groups of the compounds and components of the present invention include substances represented by -OC(O)OR, where R is selected from the groups listed below.

[0048] As used herein, according to some embodiments, the terms “urethane” and related terms such as “urethane group” and “urethane substituent” relating to the groups and substituents of various groups of the compounds and components of the present invention include substances represented by -OC(O)N(R)(H) or -N(H)C(O)OR, where R is independently selected from the groups described below in each case.

[0049] Unless otherwise stated, each R group of the ketones, esters (carboxylic acid esters), carbonates, and urethane groups described above is independently selected from alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof (including those listed earlier in this specification).

[0050] The indenonaphthopyrane compounds and various groups thereof according to the present invention, including but not limited to those represented by formula (I), will be described in further detail below.

[0051] As used herein, the term “substituted” group in relation to the indenonaphthopyran compounds of the present invention means a group such as an alkyl group, heterocycloalkyl group, aryl group and / or heteroaryl group (but not limited to these) in which at least one hydrogen is substituted or replaced by a group other than hydrogen. In some embodiments, the substituents of the “substituted” group in the indenonaphthopyran compounds of the present invention are, in each case, alkoxy groups, halo groups (e.g., F, Cl, I and Br), hydroxyl groups, thiol groups, alkylthio groups, arylthio groups, ketone groups, aldehyde groups, ester groups, carboxylic acid groups, cyano groups, alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, perhaloalkyl groups, cycloalkyl groups, heteroalkyl groups, aryl groups (including alkaryl groups, hydroxyl-substituted aryl groups, e.g., phenol and condensed polycyclic aryl groups), heteroaryl groups (including condensed polycyclic aryl groups), amino groups, e.g., -N(R) 11’ )(R 12’ )(R 11’ and R 12’ Each of these groups is independently selected from, for example, hydrogen, alkyl, heterocycloalkyl, aryl, or heteroaryl groups, carboxylate groups, amide groups, urethane groups, carbonate groups, urea groups, vinylphenyl groups, acrylate groups, methacrylate groups, acrylamide groups, methacrylamide groups, nitrogen-containing heterocyclic groups, or combinations thereof, including classifications and examples further described herein. In some further embodiments, the substituents of the "substituted" groups of the indenonaphthopyran compounds according to the present invention are independently selected in each case from alkoxy groups, halo groups (e.g., F, Cl, I, and Br), hydroxyl groups, thiol groups, ketone groups, aldehyde groups, ester groups, carboxylic acid groups, cyano groups, alkyl groups, haloalkyl groups, perhaloalkyl groups, cycloalkyl groups, heterocycloalkyl groups, aryl groups, and heteroaryl groups. According to some embodiments of the present invention, the substituents of the substituted groups are more specifically listed.

[0052] With respect 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 present invention, at least one of m and n is at least 1. In some further embodiments of the present invention, m is 1 and / or n is 1. In some further embodiments of the present invention, m is 1 and n is 1.

[0053] With respect to formula (I) and in some embodiments, R 1 is an aryl or heteroaryl substituted with at least one perfluoroalkyl group. In some embodiments, R 1 This is at least one linear or branched C1-C 10 A perfluoroalkyl group substituted with an aryl group or at least one linear or branched C1-C group. 10 It is a heteroaryl compound substituted with a perfluoroalkyl group.

[0054] According to some embodiments of the present invention, with respect to formula (I), R 2 It is an alkoxy. When used herein, "R 2 The statement "is an alkoxy" means that the oxygen of the alkoxy group is bonded to the 6-position of the indenonaphthopyrane represented by formula (I). In some embodiments, R 2 C1~C is either linear or branched. 10 It is an alkoxy.

[0055] According to some embodiments of the present invention, with respect to formula (I), R 3 R is an alkoxy, amino, or substituted or unsubstituted nitrogen-containing heterocycle. 3 If R is not an alkoxy (i.e., an amino or a substituted or unsubstituted nitrogen-containing heterocycle), 3 It is covalently bonded at position 7 by a nitrogen atom. When used herein, "R 3The statement "is an alkoxy" means that the oxygen of the alkoxy group is bonded to the 7-position of the indenonaphthopyrane represented by formula (I). In some embodiments, R 3 This is selected from amino or substituted or unsubstituted nitrogen-containing heterocycles (not selected from alkoxys).

[0056] In some embodiments, R of formula (I) 3 C1~C is either linear or branched. 10 Selected from alkoxy. Furthermore, with respect to formula (I), R 3 In some embodiments, this is selected from secondary or tertiary amino acids represented by the following formula (II). [ka]

[0057] Regarding 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, but R 8 and R 9 The condition is that at least one of them is not hydrogen.

[0058] Furthermore, regarding equation (I), R 3 In some embodiments, this is a nitrogen-containing heterocycle selected from substituted or unsubstituted piperidinos (whose ring nitrogen is covalently bonded at position 7), substituted or unsubstituted morpholinos (whose ring nitrogen is covalently bonded at position 7), and C3-C6 cyclic amides (whose ring / amide nitrogen is covalently bonded at position 7).

[0059] R in equation (I) 3 In some embodiments, the base is selected from substituted or unsubstituted piperazinos represented by the following formula (III). [ka]

[0060] Regarding equation (III), R 10 This is selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, alkylsulfonyl, or perhaloalkylsulfonyl.

[0061] Regarding equation (I), R 4 and R 5 Each of these is independently selected from substituted or unsubstituted alkyl groups, or R 4 and R 5 These together form a substituted or unsubstituted spiro ring. In some further embodiments, R 4 and R 5 Together, C3~C 10 It forms a spiro ring, which is a complete carbon ring (containing only carbon atoms in the spiro ring), such as a spiro ring or a C5-C8 spiro ring. In some further embodiments, R 4 and R 5 These combine to form an unsubstituted spiro ring. In some embodiments, R 4 and R 5 Each of these is independently selected from unsubstituted linear or branched C1-C6 alkyl groups.

[0062] With respect to formula (I), according to some embodiments, R 6 This is independent for each n, and R 7 For each m, independently and in each case, is selected from amino, substituted or unsubstituted nitrogen-containing heterocycle, halo group, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, perfluoroalkyl, or substituted or unsubstituted alkylthio. In some further embodiments, R 6 This is independent for each n, and R 7For each m independently, and in each case independently, substituted or unsubstituted piperidino, substituted or unsubstituted morpholino, independently with respect to formula (III) above and as further described herein, substituted or unsubstituted piperidino, fluoro, chloro or bromo, substituted or unsubstituted linear or branched C1-C6 alkyl, substituted or unsubstituted linear or branched C1-C6 alkyl, substituted or unsubstituted linear or branched C1-C 18 Alkyl or substituted or unsubstituted linear or branched C1-C chains 18 Selected from alkoxy.

[0063] According to some embodiments of the present invention, with respect to formula (I), R 1 R is a phenyl molecule substituted with at least one linear or branched C1-C4 perfluoroalkyl group, a pyridinyl molecule substituted with at least one linear or branched C1-C4 perfluoroalkyl group, or a pyrimidinyl molecule substituted with at least one linear or branched C1-C4 perfluoroalkyl group. In some embodiments, R of formula (I) 2 These are linear or branched C1-C4 alkoxy compounds.

[0064] With respect to formula (I) and according to some embodiments, R 3 R is selected from linear or branched C1-C6 alkoxys. In some further embodiments, R 3 R is selected from a secondary or tertiary amino represented by formula (II), and for formula (II), 8 and R 9 Each is independently selected from hydrogen, substituted or unsubstituted linear or branched C1-C6 alkyl groups, substituted or unsubstituted C5-C7 cycloalkyl groups, or substituted or unsubstituted aryl groups, but R 8 and R 9 The condition is that at least one of them is not hydrogen. In some further embodiments, R 3 R is selected from unsubstituted piperidino, substituted or unsubstituted morpholino, or unsubstituted C3-C6 cyclic amide. In addition, according to some embodiments, 3is selected from substituted or unsubstituted piperazino represented by formula (III), and for formula (III), R 10 is selected from hydrogen, substituted or unsubstituted linear or branched C1-C6 alkyl, substituted or unsubstituted phenyl or linear or branched C1-C6 perhaloalkylsulfonyl.

[0065] According to some embodiments, for formula (I), R 3 is independently selected from linear or branched C1-C4 alkoxy, substituted or unsubstituted piperidino, substituted or unsubstituted morpholino or unsubstituted C3-C6 cyclic amide. In some further embodiments, R 3 is selected from secondary or tertiary amino represented by formula (II), and 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 perhaloalkyl, provided that at least one of R 8 and R 9 is linear or branched C1-C4 perhaloalkyl. In some further embodiments, R 3 is selected from substituted piperazino represented by formula (III), and for formula (III), R 10 is selected from substituted or unsubstituted linear or branched C1-C4 alkyl, substituted or unsubstituted phenyl or linear or branched C1-C4 perhaloalkylsulfonyl.

[0066] Regarding formula (I) and in some embodiments, R 4 and R 5 are each independently selected from unsubstituted linear or branched C1-C4 alkyl.

[0067] According to some embodiments, for formula (I), R 6 is independently for each n, and R 7For each m, independently in each case, it is selected from unsubstituted piperidino, unsubstituted morpholino, fluoro, chloro or bromo, unsubstituted straight-chain or branched C1-C4 alkyl or unsubstituted straight-chain or branched C1-C4 alkoxy.

[0068] Regarding formula (I) and according to some embodiments, R 6 and R 7 at least one of which is unsubstituted straight-chain or branched C1-C 18 alkoxy, or unsubstituted straight-chain or branched C1-C6 alkoxy, or unsubstituted straight-chain or branched C1-C4 alkoxy.

[0069] According to some embodiments of the indenonaphthopyran compound of the present invention, regarding formula (I), R 1 is 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. According to some further embodiments of the indenonaphthopyran compound of the present invention, regarding formula (I), R 2 is selected from methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy or branched butoxy, such as t-butoxy, and R 3 is selected from morpholino, 2,6-dimethylmorpholino, 4-phenylpiperazino, 4-(trifluoromethyl)sulfonylpiperazino, γ-butyrolactam, δ-valerolactam or ε-caprolactam. According to some additional embodiments of the indenonaphthopyran compound of the present invention, regarding formula (I), R 4 and R 5 are each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl or branched butyl, such as t-butyl, and R 6 and R 7 are each independently selected from methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy or branched butoxy, such as t-butoxy.

[0070] According to some embodiments of the indenonaphthopyrane compound of the present invention, with respect to formula (I), R 1 R is 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)pyridine-2-yl. According to some further embodiments of the indenonaphthopyrane compounds of the present invention, with respect to formula (I), R 2 It is methoxy, and R 3 R is selected from morpholino, 2,6-dimethylmorpholino, 4-phenylpiperazino, 4-(trifluoromethyl)sulfonylpiperazino, γ-butyrolactam, δ-valerolactam, or ε-caprolactam. According to some additional embodiments of the indenonaphthopyran compounds of the present invention, with respect to formula (I), 4 and R 5 These are n-propyl, and R 6 and R 7 Each is independently selected from methoxy or n-butoxy.

[0071] The indenonaphthopyrane compounds according to the present invention can be prepared according to methods recognized in the art.

[0072] In some embodiments, the indenonaphthopyran compounds of the present invention are photochromic indenonaphthopyran compounds. According to the present invention, a photochromic composition is also provided which comprises at least one indenonaphthopyran compound according to the present invention, which is a photochromic indenonaphthopyran compound such as that represented by formula (I).

[0073] The photochromic indenonaphthopyrane compounds of the present invention may be used in combination with mixtures of other photochromic compounds. For example, mixtures of photochromic compounds may be used to achieve certain activated colors, such as nearly neutral gray or nearly neutral brown, although this is not limited herein. See, for example, U.S. Patent No. 5,645,767, column 12, line 66 to column 13, line 19, which describes the parameters that define neutral gray and brown colors.

[0074] Examples of other photochromic compounds that can be used in combination with the photochromic indenonaphthopyran compounds of the present invention include, but are not limited to, indenocondensed naphthopyran, naphtho[1,2-b]pyran, naphtho[2,1-b]pyran, spirofluoroeno[1,2-b]pyran, phenantrenopyran, quinolinopyran, fluoroantenopyran, spiropyran, benzoxazine, naphthoxazine, spiro(indoline)naphthoxazine, spiro(indoline)pyridobenzoxazine, spiro(indoline)fluorantenoxazine, spiro(indoline)quinoxazine, flugido, flugimid, diarylethene, diarylalkylethene, diarylalkenylethene, thermoreversible photochromic compounds and non-thermoreversible photochromic compounds, and mixtures thereof.

[0075] In some embodiments, the photochromic composition of the present invention may further comprise one or more fixed-color dyes. As used herein, the term “fixed-color dye” and related terms such as “fixed colorant,” “static colorant,” “fixed pigment,” and “static pigment” mean dyes that are non-photosensitive materials that do not react physically or chemically to electromagnetic radiation with respect to their visible color. As used herein, the term “fixed-color dye” and related terms do not include photochromic compounds and are distinguished from them. As used herein, the term “non-photosensitive material” means materials that do not react physically or chemically to electromagnetic radiation with respect to their visible color, including, but not limited to, fixed-color dyes.

[0076] One or more fixed coloring dyes may be present in the photochromic composition of the present invention, not limited to articles prepared from the photochromic composition, for the purpose of imparting at least a basic (or first) color characteristic of the fixed coloring dye when the photochromic compound is not activated, and optionally a second color characteristic of the combination of the fixed coloring dye and the photochromic compound when activated, for example, by exposure to chemical rays.

[0077] In some embodiments, the optional fixed coloring dyes of the photochromic composition include at least one of azo dyes, anthraquinone dyes, xanthene dyes, azim dyes, iodine, iodide salts, polyazo dyes, stilbene dyes, pyrazolone dyes, triphenylmethane dyes, quinoline dyes, oxazine dyes, thiadin dyes, and polyene dyes.

[0078] Fixed coloring dyes are present in varying amounts in the photochromic composition and can provide the intended effect in the cured articles produced thereby. In some embodiments, the fixed coloring dyes are present in the photochromic composition in amounts of 0.001 to 15 weight percent, 0.01 to 10 weight percent, or 0.1 to 2.5 weight percent based on the total resin solids weight of the photochromic composition.

[0079] According to some embodiments of the present invention, a photochromic composition comprises (i) a matrix-forming material which is at least one polymer-based material, an oligomeric material, and / or a monomer-based material, and (ii) an indenonaphthopyran compound according to the present invention which is a photochromic indenonaphthopyran compound such as that represented by formula (I). The photochromic indenonaphthopyran compound can be incorporated into a portion of an organic material by at least one (but not limited to) method of blending or bonding the photochromic compound with an organic material or a precursor of an organic material. In this specification, the terms “blended” and “blended” as used in relation to incorporating a photochromic compound into an organic material mean that the photochromic compound / material is mixed or combined with at least a portion of the organic material but is not bonded to the organic material. Furthermore, the terms “bonded” or “bonded” as used in this specification in relation to incorporating a photochromic compound into an organic material mean that the photochromic compound / material is bonded to a portion of the organic material or a precursor thereof by one or more covalent bonds, etc. For example, in this specification, though not limited thereto, photochromic materials may be linked to organic materials via reactive substituents such as hydroxyl groups, primary amine groups, and / or secondary amine groups.

[0080] When the organic material is a polymer-based material, the photochromic compound can be incorporated into at least a portion of the polymer-based material or at least a portion of the monomer-based or oligomer-based material for forming the polymer-based material. For example, the photochromic compound according to the present invention having a reactive substituent can be bonded to an organic material such as a monomer, oligomer, or polymer having a reactive group, or the reactive site can react as a comonomer in a polymerization reaction for forming the organic material, such as a copolymerization process.

[0081] As described above, the photochromic compositions according to the present invention may, in some embodiments, include organic materials selected from polymer materials, oligomeric materials and / or monomer materials. Examples of polymer materials that may be used in 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 obtained by partial saponification of copolymers of ethylene and vinyl acetate), cellulose acetate butyrate, poly(urethane), poly(acrylate), poly(methacrylate), epoxy, aminoplast functional polymers, poly(anhydrous), poly(urea urethane), N-alkoxymethyl (meth)acrylamide functional polymers, poly(siloxane), poly(silane), and combinations and mixtures thereof. Additional classifications and examples of polymer-based materials that can be used with the photochromic composition of the present invention include, but are not limited to, those disclosed in column 39, line 45 to column 40, line 67 of U.S. Patent No. 9,028,728B2.

[0082] The photochromic composition of the present invention may comprise at least one of the following: a complementary photochromic material (including one or more of the other photochromic materials and compounds described herein), a photoinitiator, a thermal initiator, a polymerization inhibitor, a solvent, a light stabilizer, a thermal stabilizer, a mold release agent, a rheology control agent, a leveling agent, a free radical scavenger, and / or an adhesion promoter.

[0083] The photochromic composition according to the present invention may be a photochromic coating composition. The photochromic coating composition of the present invention may comprise a photochromic compound according to the present invention as 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 thermosetting (e.g., thermosetting and / or photocurable) coating composition.

[0084] The curable resin composition of the curable photochromic coating composition according to the present invention may comprise a first reactant (or component) having a functional group, for example, an epoxide functional polymer reactant, and a second reactant (or component) which is a crosslinking agent having a functional group that is reactive to the functional group of the first reactant and can form a covalent bond with the functional group of the first reactant. The first and second reactants of the curable resin composition of the curable photochromic coating composition may each independently comprise one or more functional species, and each is present in an amount sufficient to obtain a cured photochromic coating having a desirable combination of physical properties such as smoothness, optical transparency, solvent resistance, and hardness.

[0085] Examples of curable resin compositions that can be used with the curable photochromic coating composition according to the present invention include, but are not limited to, curable resin compositions comprising an epoxide-functional polymer (e.g., a (meth)acrylic polymer containing a glycidyl (meth)acrylate residue) and an epoxide-reactive crosslinking agent (e.g., one containing active hydrogen such as hydroxyl, thiol, and amine), and curable resin compositions comprising an active hydrogen-functional polymer (e.g., a hydroxy, thiol, and / or amine-functional polymer) and a capped (or blocked) isocyanate-functional crosslinking agent. "Capped (or blocked) isocyanate-functional crosslinking agent" means a crosslinking agent having two or more capped isocyanate groups that can be decapped (or deblocked) under curing conditions (e.g., high temperature) to form free isocyanate groups and free capping groups. The free isocyanate groups formed by decapping the crosslinking agent can preferably react with the active hydrogen groups of the active hydrogen-functional polymer (e.g., the hydroxyl groups of the hydroxyl-functional polymer) to form substantially permanent covalent bonds. Further examples of curable resin compositions that may be used in conjunction with the curable photochromic coating composition according to the present invention include, but are not limited to, those disclosed in paragraphs

[0176] to

[0190] of International Publication No. 2016 / 142496A1 and in paragraphs

[0005] ,

[0037] to

[0051] ,

[0056] to

[0059] and

[0063] to

[0065] of International Publication No. 2017 / 030545A1.

[0086] The curable photochromic coating compositions according to the present invention may optionally include additives such as waxes for flow and wetting, flow control agents, such as poly(2-ethylhexyl)acrylate, auxiliary resins for modifying and optimizing coating properties, antioxidants, and ultraviolet (UV) light absorbers. Examples of useful antioxidants and UV absorbers include those commercially available from BASF under the trademarks IRGANOX and TINUVIN. When used, these optional additives are typically present in an amount of up to 20 weight percent (e.g., 0.5 to 10 weight percent) based on the total weight of resin solids in the curable resin composition.

[0087] The photochromic compositions, photochromic articles, and photochromic coating compositions according to the present invention may further include additives recognized in the art that assist or support the processing and / or performance of the composition or article. Non-limiting examples of such additives include photoinitiators, thermal initiators, polymerization inhibitors, solvents, light stabilizers (but not limited to ultraviolet absorbers and light stabilizers, such as hindered amine light stabilizers (HALS)), thermal stabilizers, mold release agents, rheology control agents, leveling agents (but not limited to surfactants), free radical scavengers, adhesion promoters (such as hexanediol diacrylate and coupling agents), and combinations and mixtures thereof.

[0088] In some embodiments, the curable photochromic composition of the present invention may contain one or more solvents, such as one or more organic solvents.

[0089] The organic solvents that may be present in the photochromic composition of the present invention include, but are not limited to, ketones, e.g., acetone, methyl ethyl ketone and methyl isobutyl ketone; ethers, e.g., dimethyl ether and methyl ethyl ether; cyclic ethers, e.g., tetrahydrofuran and dioxane; esters, e.g., ethyl acetate, ethyl lactate, ethylene carbonate and propylene carbonate; nitrogen-containing cyclic compounds, e.g., pyrrolidone, N-methyl-2-pyrrolidone, 1-butyl-pyrrolidinone and 1,3-dimethyl-2-imidazolidinone; sulfur-containing compounds, e.g., dimethyl sulfoxide and tetramethylene sulfone; aromatic compounds, e.g., toluene, xylene, anisole and butyl benzoate; and mixtures of aromatic compounds, e.g., C9-C9 10 Aromatic 100 Fluid and C are commercially available mixtures of dialkylbenzene and trialkylbenzene. 10 ~C 12 One example is Aromatic 150 Fluid, a commercially available mixture of alkylbenzene and alkylnaphthalene.

[0090] The solvent may be present in the curable photochromic composition of the present invention in any case in an amount of 5 to 95 percent by weight, 15 to 80 percent by weight, 30 to 70 percent by weight, or 30 to 60 percent by weight, based on the total weight of the photochromic composition (including the weight of the solvent).

[0091] The photochromic compounds of the present invention may be used in amounts (or ratios) such that a composition, organic material, or substrate (e.g., a photochromic article and a photochromic coating) into which the photochromic compound is incorporated or otherwise bonded exhibits the desired optical properties. The amount and type of photochromic material may be selected so that when the photochromic compound is in a closed-ring form (e.g., a decolorized or inactivated state), the composition, organic material, or substrate is transparent or colorless, and when the photochromic compound (such as the photochromic indenocondensed naphthopyran of the present invention) is in an open-ring form (e.g., when activated by chemical radiation), it can exhibit the desired resulting color. The exact amount of photochromic material used in the various photochromic compositions and articles described herein is not important, as long as a sufficient amount is used to obtain the desired effect. The specific amount of photochromic material used may depend on various factors, but are not limited, such as 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 present invention may contain a photochromic compound according to the present invention, such as the compound represented by formula (I), in an amount of 0.01 to 40 weight percent, for example, 0.05 to 15 weight percent, or for example, 0.1 to 5 weight percent, based on the weight of the photochromic composition. For further non-limiting examples, the amount of photochromic compound / material containing the compound represented by formula (I) incorporated into an organic material may be in the range of 0.01 to 40 weight percent, for example, 0.05 to 15 weight percent, or for example, 0.1 to 5 weight percent, based on the weight of the organic material.

[0092] The present invention also relates to photochromic articles comprising one or more photochromic compounds according to the present invention, such as those represented by formula (I). Photochromic articles can be manufactured by methods accepted in the art, including, but not limited to, the induction method, the cast-in-place method, the coating method, the in-mold coating method, the overmolding method, and the lamination method.

[0093] For example, optical articles may be selected from ophthalmic articles, display articles, windows, mirrors, active liquid crystal cell articles, and passive liquid crystal cell articles.

[0094] According to some embodiments, the optical articles of the present invention may be ophthalmic articles, and the ophthalmic articles may be selected from corrective lenses, non-corrective lenses, contact lenses, intraocular lenses, magnifying lenses, protective lenses, and visors.

[0095] According to some further embodiments, the photochromic article of the present invention may be a display article, and the display article may be selected from screens, monitors, and security elements.

[0096] The present invention may be further characterized by one or more of the following non-limiting embodiments.

[0097] Appearance 1: The following formula (I) [ka] (In the formula, m is between 0 and 3. n is between 0 and 3. R 1 is an aryl or heteroaryl substituted with at least one perfluoroalkyl group. R 2 It is an alkoxy, R 3 R is an alkoxy, amino, or substituted or unsubstituted nitrogen-containing heterocycle, 3 If R is not an alkoxy, 3 It is covalently bonded at position 7 by a nitrogen atom, R 4 and R 5 Each of these is independently selected from substituted or unsubstituted alkyl groups, or R 4 and R 5 Together, they form a substituted or unsubstituted spiro ring, and R 6 This is independent for each n, and R 7 This is independent for each m, and independent for each case, amino, Substituted or unsubstituted nitrogen-containing heterocycles, Halo group, Substituted or unsubstituted alkyl groups Substituted or unsubstituted alkoxides, Perfluoroalkyl, or Substituted or unsubstituted alkylthio (Selected from) An indenonaphthopyran compound represented by [the specified symbol].

[0098] Appearance 2: R 1 This is at least one linear or branched C1-C 10 A perfluoroalkyl group substituted with an aryl group or at least one linear or branched C1-C group. 10 It is a heteroaryl substituted with a perfluoroalkyl group, R 2 C1~C is either linear or branched. 10 It is an alkoxy, R 3 teeth, Linear or branched C1~C 10 Alkoxy, The following equation (II) [ka] (Regarding 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, but R 8 and R 9 (At least one of them must be something other than hydrogen.) Secondary or tertiary amino acids represented by Substituted or unsubstituted piperidino, Substituted or unsubstituted morpholino, Substituted or unsubstituted C3-C6 cyclic amides, or The following equation (III) [ka] (Regarding equation (III), R 10 (Selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, alkylsulfonyl, or perhaloalkylsulfonyl) Substituted or unsubstituted piperazino represented by An indenonaphthopyran compound according to embodiment 1, selected from the above.

[0099] Appearance 3: R 1 This is an aryl or heteroaryl substituted with at least one linear or branched C1-C6 perfluoroalkyl group. R 2 These are linear or branched C1-C6 alkoxy compounds. R 3 teeth, Linear or branched C1-C6 alkoxy, Formula (II) (Regarding equation (II), R 8 and R 9 Each is independently selected from hydrogen, substituted or unsubstituted linear or branched C1-C6 alkyl groups, substituted or unsubstituted C5-C7 cycloalkyl groups, or substituted or unsubstituted aryl groups, but R 8 and R 9 (At least one of them must be something other than hydrogen.) Secondary or tertiary amino acids represented by Unsubstituted piperidino, Substituted or unsubstituted morpholino, Unsubstituted C3-C6 cyclic amides, or Formula (III) (Regarding equation (III), R 10(Selected from hydrogen, substituted or unsubstituted linear or branched C1-C6 alkyl groups, substituted or unsubstituted phenyl groups, or linear or branched C1-C6 perhaloalkylsulfonyl groups) Substituted or unsubstituted piperazino represented by Selected from, R 4 and R 5 Each is independently selected from unsubstituted linear or branched C1-C6 alkyl groups, and R 6 This is independent for each n, and R 7 This is independent for each m, and independent for each case, Substituted or unsubstituted piperidino, Substituted or unsubstituted morpholino, Substituted or unsubstituted piperazinos described independently with respect to formula (III), Fluoro, chloro, or bromo Substituted or unsubstituted linear or branched C1-C6 alkyl groups, Substituted or unsubstituted linear or branched C1-C6 alkoxy chains An indenonaphthopyran compound according to embodiment 2, selected from the above.

[0100] Appearance 4: R 1 This is a phenyl compound substituted with at least one linear or branched C1-C4 perfluoroalkyl group, or a pyridinyl compound substituted with at least one linear or branched C1-C4 perfluoroalkyl group. R 2 These are linear or branched C1-C4 alkoxy compounds. R 3 teeth, Linear or branched C1-C4 alkoxy, Formula (II) (Regarding equation (II), R 8 and R 9 Each is independently selected from unsubstituted linear or branched C1-C4 alkyl groups or linear or branched C1-C4 perhaloalkyl groups, but R 8 and R 9(At least one of them is a linear or branched C1-C4 perhaloalkyl group.) Secondary or tertiary amino acids represented by Substituted or unsubstituted piperidino, Substituted or unsubstituted morpholino, Formula (III) (Regarding equation (III), R 10 (Selected from substituted or unsubstituted linear or branched C1-C4 alkyl groups, substituted or unsubstituted phenyl groups, or linear or branched C1-C4 perhaloalkylsulfonyl groups) Substitutive piperazino represented by, Unsubstituted C3-C6 cyclic amides Selected from, R 4 and R 5 Each is independently selected from unsubstituted linear or branched C1-C4 alkyl groups, and R 6 This is independent for each n, and R 7 This is independent for each m, and independent for each case, Unsubstituted piperidino, Unsubstituted morpholino, Fluoro, chloro, or bromo Unsubstituted linear or branched C1-C4 alkyl groups, Unsubstituted linear or branched C1-C4 alkoxys An indenonaphthopyran compound according to embodiment 2 or embodiment 3, selected from the above.

[0101] Appearance 5: R 6 and R 7 An indenonaphthopyrane compound according to any one of embodiments 1 to 4, provided that at least one of the components is an unsubstituted linear or branched C1-C4 alkoxy.

[0102] Appearance 6: R 1 teeth, 4-(trifluoromethyl)phenyl, 2-(trifluoromethyl)phenyl, 2,4-Bis(trifluoromethyl)phenyl, 3,5-Bis(trifluoromethyl)phenyl, 3,4-Bis(trifluoromethyl)phenyl, or 5-(trifluoromethyl)pyridine-2-yl Selected from, R 2 teeth, Methoxy, or Ethoxy Selected from, R 3 teeth, Morpholino, 2,6-dimethylmorpholino, 4-phenylpiperazino, 4-(trifluoromethyl)sulfonylpiperazino, γ-Butyrolactam, δ-valerolactam, or ε-caprolactam Selected from, R 4 and R 5 Each of them operates independently. Methyl, ethyl, n-propyl, Isopropyl, n-butyl, or Branched butyl, e.g., t-butyl Selected from, R 6 and R 7 Each of them operates independently. Methoxy, Ethoxy, n-propoxy, Isopropoxy, n-butoxy, or Branched butoxy, for example, t-butoxy An indenonaphthopyrane compound according to any one of embodiments 1 to 5, selected from the above.

[0103] Appearance 7: R 1 teeth, 4-(trifluoromethyl)phenyl, 2-(trifluoromethyl)phenyl, 2,4-Bis(trifluoromethyl)phenyl, 3,5-Bis(trifluoromethyl)phenyl, 3,4-Bis(trifluoromethyl)phenyl, or 5-(trifluoromethyl)pyridine-2-yl Selected from, R 2 It is methoxy, R 3 teeth, Morpholino, 2,6-dimethylmorpholino, 4-phenylpiperazino, 4-(trifluoromethyl)sulfonylpiperazino, γ-Butyrolactam, δ-valerolactam, or ε-caprolactam Selected from, R 4 and R 5 These are each n-propyl, R 6 and R 7 Each is independently selected from methoxy or n-butoxy, and is an indenonaphthopyrane compound according to any one of embodiments 1 to 6.

[0104] Embodiment 8: A photochromic composition comprising the indenonaphthopyran compound described in any one of Embodiments 1 to 7.

[0105] Embodiment 9: A photochromic article comprising an indenonaphthopyran compound according to any one of Embodiments 1 to 7, the photochromic article selected from the group consisting of ophthalmic articles, display articles, windows, mirrors, active liquid crystal cell articles and passive liquid crystal cell articles.

[0106] Embodiment 10: A photochromic article according to Embodiment 9, wherein the ophthalmic article is selected from ophthalmic articles, and the ophthalmic article is selected from corrective lenses, non-corrective lenses, contact lenses, intraocular lenses, magnifying lenses, protective lenses and visors.

[0107] The present invention will be described more specifically by the following embodiments, which are intended to be illustrative only, as many of its modifications and variations will be apparent to those skilled in the art. [Examples]

[0108] Part 1 of the following examples describes the synthetic preparation of comparative indenonaphthopyran compounds (Comparative Examples / Compounds CE1, CE2, CE12, and CE13) and indenonaphthopyran compounds according to the present invention (Examples / Compounds 3-11, 14, and 15). Part 2 provides an overview of the comparison in Part 1 and the evaluation of the indenonaphthopyran compounds of the present invention.

[0109] Part 1 Explanation of synthesis The following Scheme-1 outlines the synthesis of the indenonaphthopyran compound, particularly Comparative Example 1 (CE1). Scheme-1 also includes other comparative compounds in the following examples, as well as the starting materials and / or intermediates and / or alternative species used to synthesize the compounds of the present invention.

[0110] Scheme-1 Compound (CE1) of Comparative Example 1 [ka] Comparison compound CE1: Comparative compound CE1 was prepared according to the following procedure.

[0111] Step 1: 9-Bromo-2,3-dimethoxy-7,7-dipropyl-7H-benzo[c]fluoren-5-ol (20 g) (100), imidazole (4.48 g), 4-(dimethylamino)pyridine (0.54 g), and anhydrous N,N-dimethylformamide (60 mL) were placed together in a round-bottom flask and stirred. The mixture was cooled to -5 to 0°C by immersing the flask in saturated saline solution and an ice bath. Then, tert-butyldimethylsilyl chloride (7.94 g) (TBDMSCl) was added to the reaction mixture in four equal parts at 5-minute intervals. The reaction mixture was allowed to return to room temperature naturally, and then stirred for 16 hours. After that, it was poured into ice water and extracted twice with ethyl acetate. The combined organic layer was washed twice with saturated saline solution, dried over sodium sulfate, and concentrated to dryness. The resulting residue was filtered through a silica gel short plug, and the filter was washed with a mixture of 25% ethyl acetate and 75% hexane. By concentrating the mother liquor to dryness, an intermediate product (103') and an amber-colored oil (25.02 g) corresponding to (103) in Scheme-1 were obtained. [ka]

[0112] Step 2: In a two-necked round-bottom flask, hexane (55 mL) and morpholine (3.87 g) (106) were mixed. The flask was immersed in an ice bath, and then 15.4 mL of a 2.5 M n-butyllithium (n-BuLi) solution in hexane was added dropwise from a syringe over 5 minutes. Next, the intermediate product (103) (11.00 g) from step 1 was added to the mixture, followed by the addition of anhydrous tetrahydrofuran (70 mL). The reaction mixture was warmed to room temperature over 1 hour, and then poured into ice water. This was washed twice with ethyl acetate, and then the combined organic layers were washed with saturated brine, dried over sodium sulfate, and concentrated to dryness. The resulting residue was filtered through a silica gel short plug, and the filter was washed with a mixture of 25% ethyl acetate and 75% hexane. The mother liquor was concentrated to dryness to obtain the following intermediate products (9.23 g), (109'), and an amber-colored oil corresponding to (109) in Scheme-1. [ka]

[0113] Step 3: The intermediate product from Step 2 (4.62 g) (10⁹'), isooctyl 3-mercaptopropionate (1.78 g), N,N-diisopropylethylamine (1.91 g), and toluene (28 mL) were placed together in a round-bottom flask and stirred. The mixture was purged with nitrogen gas for 20 minutes. Tris(dibenzylideneacetone)dipalladium (0) (0.20 g) and 4,5-bis(diphenylphosphin)-9,9-dimethylxanthene (0.26 g) were added to the mixture. This was heated at 110°C for 90 minutes, and then cooled to room temperature. Anhydrous N,N-dimethylformamide (26 mL), followed by a 40% sodium tert-pentoxide solution 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 at 120°C for 1 hour. After cooling to room temperature, the reaction mixture was poured into ice water, and then dilute hydrochloric acid solution was added until the pH reached 5. This was then extracted twice with ethyl acetate. The combined organic layers were washed twice with saturated brine, dried over sodium sulfate, and then concentrated to dryness. The resulting residue was purified using silica gel flash chromatography and eluted with a mixture of 25% ethyl acetate and 75% hexane. The fractions containing the desired intermediate product were combined and concentrated to dryness. The resulting solid was slurryed in a mixture of 10% ethyl acetate and 90% hexane, and then recovered by vacuum filtration to obtain the intermediate product (1.50 g) (112) represented by the following structural formula. [ka]

[0114] Step 4: The intermediate product (112) (1.00 g) from Step 3, 1,1-bis(4-methoxyphenyl)prop-2-in-1-ol (0.63 g) (115), 4-pyridinium p-toluenesulfonate (0.06 g) (PTSA), and 1,2-dichloroethane (20 mL) were placed together in a round-bottom flask and heated at 83°C for 2 hours. After cooling to room temperature, the reaction mixture was filtered through a silica gel short plug, 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 using silica gel flash chromatography and eluted with a mixture of 25% ethyl acetate and 75% hexane. The fractions containing the target product were combined and concentrated to dryness. Methanol was added to the resulting residue to precipitate the solid, which was then recovered by vacuum filtration. NMR analysis of the solid was consistent with the following representative structure (0.97 g) (118). [ka]

[0115] Compounds of Comparative Examples 2, 12, and 13 (CE2, CE12, and CE13) and Examples 3-11, 14, and 15: The compounds shown in Table A below were prepared in general accordance with the synthesis procedure described for CE1, using 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 of Comparative Examples CE13 and CE14 and Examples 15 and 16 were prepared in general accordance with the synthesis procedure described for CE1, except that amination was not performed in step 2, resulting in the acquisition of 6,7-dimethoxy-substituted compounds (instead of 6-methoxy,7-morpholino-substituted compounds).

[0116] [Table 1]

[0117] [Table 2]

[0118] [Table 3]

[0119] [Table 4]

[0120] [Table 5]

[0121] Part 2 Evaluation of indenonaphthopyrane compounds in Part 1 Each indenonaphthopyran compound from Part-1 was incorporated into a polyurethane coating system in the same molar percentage as described in Examples 1-3 of U.S. Specification 8,608,988B2, and applied to 2-inch x 2-inch (5.1cm x 5.1cm) test chips made of CR-39® monomer (PPG Industries, Inc.) with the same coating thickness. All coated test chips were cured at 125°C for 1 hour.

[0122] Each coated test chip was first conditioned by irradiating it with 365 nanometer ultraviolet light at a distance of approximately 14 centimeters for 10 minutes to activate the photochromic material in the coating. The UVA (315-380 nm) irradiance at the chip was measured using a LICOR® Model Li-1800 spectroradiometer and found to be 22.2 watts per square meter. Subsequently, each test chip was placed under a 500 watt high-intensity halogen lamp at a distance of approximately 36 centimeters for approximately 10 minutes to decolorize (inactivate) the photochromic material. The irradiance at the chip was measured using a LICOR® spectroradiometer and found to be 21.9 Klux. After that, the coated test chips were placed in a dark environment at room temperature (i.e., 70-75°F, i.e., 21-24°C) for at least 1 hour before being tested / measured on an optical bench. Prior to optical bench measurement, the coated test chips were measured for ultraviolet absorbance at 390 nanometers.

[0123] The percentage transmittance (%T) of each coated test chip was determined using CIE Y values ​​according to the CIE 15:2004 colorimetric method using a D65 light source and a 10° observer. The a* and b* values ​​used herein refer to a* and b* values ​​measured using UltraScan Pro (Hunter Labs) according to the CIE 15:2004 spatial colorimetric method using a D65 light source and a 10° observer.

[0124] The BMP optical bench was fitted with two 150-watt ORIEL® Model #66057 xenon arc lamps positioned perpendicular to each other. The optical path from lamp 1 was directed to pass through a 3mm SCHOTT® KG-2 bandpass filter and appropriate ND filters to contribute to the required UV and partially visible irradiance levels. The optical path from lamp 2 was directed to pass through a 3mm SCHOTT® KG-2 bandpass filter, a SCHOTT® shortwave 400nm cutoff filter, and appropriate ND filters to provide supplemental visible irradiance. A 2-inch x 2-inch (5.1cm x 5.1cm) 50% polka dot beam splitter set at 45° to each lamp was used to mix the two beams. Irradiance intensity was adjusted using a combination of ND filters and voltage control of the xenon arc lamps. Dedicated software (i.e., BMPSoft version 2.1e) was used with the BMP to control timing, irradiance, air cell and sample temperatures, shutter, filter selection, and response measurements. A ZEISS® spectrophotometer, model MCS501, with a fiber optic cable for transmitting light through the coated test chips, was used for response and color measurements. Photopic response measurements were collected for each coated test chip. The output of the optical bench, i.e., the amount of light to which the coated test chips were exposed, was 6.7 watts / m² (W / m²) integrated at 315–380 nm. 2The irradiance was adjusted to 50 Klux, integrated over UVA and 380–780 nm. The setpoint measurement of this output was performed using an irradiance probe and a calibrated Zeiss spectrophotometer. A quartz window and a self-centering sample holder were mounted on the sample cell of the coated test chip. The temperature inside the sample cell was controlled to 23°C by software with a modified Facis model FX-10 environment simulator. Measurements of the dynamic photochromic response and color of the coated test chip were performed using the same Zeiss spectrophotometer with a fiber optic cable for transmitting light from a tungsten halogen lamp through the sample. A parallel monitoring light beam from the fiber optic cable was maintained perpendicular to the test sample as it passed through the coated test chip sample and directed towards a receiving fiber optic cable assembly mounted on 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 light beam intersected, forming concentric circles of light. The angle of incidence of the xenon arc beam at the sample placement point was approximately 30° to perpendicular.

[0125] The response measurement of the change in optical density (ΔOD) from the inactive or decolorized state to the activated or colored state was determined by confirming the initial inactive transmittance, opening the shutter from the xenon lamp, and measuring the transmittance due to activation at selected time intervals. The change in optical density was determined according to the following formula. ΔOD = Log (10) (%Tb / %Ta) In the above ΔOD formula, %Tb is the transmittance percentage in the decolorized state, and %Ta is the transmittance percentage in the activated state. The ΔOD at saturation is 15 minutes after activation, and the fading half-life ("T1 / 2") value is the time in seconds until the ΔOD of the activated state of the photochromic material in the coating reaches half of the ΔOD at 73.4°F (23°C) at 15 minutes, after the activation light source has been removed.

[0126] The results of the tests and evaluations described above are summarized in Tables 2 and 3 below.

[0127] [Table 6]

[0128] [Table 7]

[0129] The data summarized in Table 2 shows that the indenonaphthopyrane compound according to the present invention (having a (perfluoroalkyl)arylthio substituent at the 11th position) provides an improved fading rate compared to the comparative indenonaphthopyrane compound (having a (fluoroaryl)thio substituent at the 11th position) without significantly sacrificing the darkness of the activated state. The data summarized in Table 3 shows that the indenonenaphthopyrane compound according to the present invention, having various groups at the 11th and 7th positions, provides a faster fading rate.

[0130] The present invention has been described with reference to specific details of its concrete embodiments. Such details are not intended to be considered limitations on the scope of the invention unless they are included in the appended claims.

Claims

1. The following equation (I) 【Chemistry 1】 (In the formula, m is between 0 and 3. n is between 0 and 3. R １ is an aryl or heteroaryl substituted with at least one perfluoroalkyl group, R ２ It is an alkoxy, R ３ R is an alkoxy, amino, or substituted or unsubstituted nitrogen-containing heterocycle, ３ If R is not an alkoxy, ３ It is covalently bonded at position 7 by a nitrogen atom. R ４ and R ５ Each of these is independently selected from substituted or unsubstituted alkyl groups, or R ４ and R ５ together form a substituted or unsubstituted spiro ring, and R ６ This is independent for each n, and R ７ This is independent for each m, and independent for each case, amino, Substituted or unsubstituted nitrogen-containing heterocycles, Halo group, Substituted or unsubstituted alkyl groups Substituted or unsubstituted alkoxides, Perfluoroalkyl, or Substituted or unsubstituted alkylthio (Selected from) An indenonaphthopyran compound represented by [the specified symbol].

2. R １ is at least one linear or branched C １ ~C １０ A perfluoroalkyl group substituted with an aryl group or at least one linear or branched C group. １ ~C １０ It is a heteroaryl substituted with a perfluoroalkyl group, R ２ C is either linear or branched. １ ~C １０ It is an alkoxy, R ３ teeth, Linear or branched C １ ~C １０ Alkoxy, The following equation (II) 【Chemistry 2】 (Regarding 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, but R ８ and R ９ (At least one of them must be something other than hydrogen.) Secondary or tertiary amino acids represented by Substituted or unsubstituted piperidino, Substituted or unsubstituted morpholino, Substituted or unsubstituted C ３ ~C ６ Cyclic amide, or The following equation (III) 【Transformation 3】 (Regarding equation (III), R １０ (Selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, alkylsulfonyl, or perhaloalkylsulfonyl) Substituted or unsubstituted piperazino represented by An indenonaphthopyran compound according to claim 1, selected from the following.

3. R １ is at least one linear or branched C １ ~C ６ A perfluoroalkyl group substituted with an aryl group or at least one linear or branched C group. １ ~C ６ It is a heteroaryl substituted with a perfluoroalkyl group, R ２ C is either linear or branched. １ ~C ６ It is an alkoxy, R ３ teeth, Linear or branched C １ ~C ６ Alkoxy, Formula (II) (Regarding equation (II), R ８ and R ９ Each of these is independently a hydrogen atom, a substituted or unsubstituted linear or branched carbon atom. １ ~C ６ Alkyl, substituted, or unsubstituted C ５ ~C ７ Selected from cycloalkyl or substituted or unsubstituted aryl, R ８ and R ９ (At least one of them must be something other than hydrogen.) Secondary or tertiary amino acids represented by Unsubstituted piperidino, Substituted or unsubstituted morpholino, Unsubstituted C ３ ~C ６ Cyclic amide, or Formula (III) (Regarding equation (III), R １０ C is a hydrogen, substituted or unsubstituted linear or branched C １ ~C ６ Alkyl, substituted or unsubstituted phenyl, or linear or branched C １ ~C ６ (Selected from perhaloalkylsulfonyls) Substituted or unsubstituted piperazino represented by Selected from, R ４ and R ５ Each of these is independently an unsubstituted linear or branched C １ ~C ６ Selected from alkyl, and R ６ This is independent for each n, and R ７ This is independent for each m, and independent for each case, Substituted or unsubstituted piperidino, Substituted or unsubstituted morpholino, Substituted or unsubstituted piperazinos described independently with respect to formula (III), Fluoro, chloro, or bromo Substitutive or unsubstituted linear or branched C １ ~C ６ Alkyl, or Substitutive or unsubstituted linear or branched C １ ~C ６ Alkoxy An indenonaphthopyran compound according to claim 2, selected from the above.

4. R １ is at least one linear or branched C １ ~C ４ Phenyl substituted with a perfluoroalkyl group or at least one linear or branched C2 group. １ ~C ４ It is a pyridinyl substituted with a perfluoroalkyl group, R ２ C is either linear or branched. １ ~C ４ It is an alkoxy, R ３ teeth, Linear or branched C １ ~C ４ Alkoxy, Formula (II) (Regarding equation (II), R ８ and R ９ Each of these is independently a non-substituted linear or branched C １ ~C ４ Alkyl, linear, or branched C １ ~C ４ Selected from perhaloalkyl groups, R ８ and R ９ At least one of them is a linear or branched C １ ~C ４ (Required to be perhaloalkyl) Secondary or tertiary amino acids represented by Substituted or unsubstituted piperidino, Substituted or unsubstituted morpholino, Formula (III) (For formula (III), R １０ is selected from substituted or unsubstituted linear or branched C １ to C ４ alkyl, substituted or unsubstituted phenyl, or linear or branched C １ to C ４ perhaloalkylsulfonyl). Substitutive piperazino represented by, Unsubstituted C ３ ~C ６ Cyclic amide Selected from, R ４ and R ５ are each independently selected from unsubstituted linear or branched C １ -C ４ alkyl, and R ６ This is independent for each n, and R ７ This is independent for each m, and independent for each case, Unsubstituted piperidino, Unsubstituted morpholino, Fluoro, chloro, or bromo Unsubstituted linear or branched C １ ~C ４ Alkyl, or Unsubstituted linear or branched C １ ~C ４ Alkoxy An indenonaphthopyran compound according to claim 3, selected from the above.

5. R ６ and R ７ At least one of them is an unsubstituted linear or branched C １ ~C ４ The indenonaphthopyrane compound according to claim 4, provided that it is an alkoxy compound.

6. A photochromic composition comprising the indenonaphthopyran compound described in claim 1.

7. A photochromic article comprising the indenonaphthopyran compound described in claim 1, the photochromic article selected from the group consisting of ophthalmic articles, display articles, windows, mirrors, active liquid crystal cell articles and passive liquid crystal cell articles.

8. The photochromic article according to claim 7, wherein the ophthalmic article is selected from ophthalmic articles, and the ophthalmic article is selected from corrective lenses, non-corrective lenses, contact lenses, intraocular lenses, magnifying lenses, protective lenses and visors.

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