Method for preparing indole naphthopyran

Abstract

Provided is a synthetic intermediate having a core skeleton structure of formula (I) for preparing a photochromic indole naphthopyran compound: wherein m is 0 to 4, n is 0 to 4, R 1 and R 2 R is independently hydroxy, cyano, (meth)acrylate, amino, halide, substituted or unsubstituted alkyl, borate, boric acid, polyether, polyester, polycarbonate, polyurethane, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, ketone, aldehyde, ester, carboxylic acid, carboxylate, amide, carbonate, carbamate, urea, siloxane, alkoxysilane, or polysiloxane; 3 is substituted or unsubstituted 2-pyridyl or substituted or unsubstituted 2-quinolyl; and R 4 is hydrogen, substituted or unsubstituted alkyl, alkoxymethyl, substituted or unsubstituted silyl, or acyl. Also provided is a method for producing an indole naphthol compound, the method comprising cyclizing a phenylnaphthol compound of formula (I) in the presence of a catalyst.

Description

Technical Field

[0001] The present invention relates to photochromic compounds, such as photochromic indole naphthopyran compounds, and to an efficient method for producing photochromic indole naphthopyran compounds from phenylnaphthol synthetic intermediates. Background Art

[0002] Photochromic compounds undergo a transition from one state (or form) to another state in response to certain wavelengths of electromagnetic radiation (e.g., "actinic radiation"). Each state has a characteristic absorption spectrum. For example, many photochromic compounds transition from an unactivated (e.g., whitish or substantially colorless) state to an activated (e.g., colored) state when exposed to actinic radiation. When the actinic radiation is removed, the photochromic compound reversibly transitions from the activated state back to the unactivated state.

[0003] The synthesis of photochromic indole naphthopyran compounds was previously described in WO 99 / 23071. The specific steps in the preparation use an azide synthetic intermediate shown in formula A below, which is photochemically decomposed to obtain the corresponding indole naphthol compound shown in formula B.

[0004] The indole naphthol compound is further reacted to form an indole naphthopyran compound.

[0005]

[0006] This synthetic route has several disadvantages. The UV light required for this photochemical reaction makes this step difficult to carry out on a large scale, because the reaction rate is subject to the limitation of the UV light exposure of the reactant. In addition, due to the potential release of hydrazoic acid (explosive liquid) from the hydrolysis of sodium azide at room temperature and pressure, the production of the azide intermediate shown in Formula A causes potential safety hazards. In addition, organic azide compounds must be handled with care, because they may be sensitive to heat and shock, and may decompose explosively. Therefore, it is desirable to provide a method for producing photochromic indole naphthopyran compounds, which can be scaled up and avoid the preparation of azide intermediates.

[0007] The phenylnaphthol compounds of the present invention provide useful synthetic intermediates for the preparation of photochromic indole naphthopyran compounds. The methods disclosed herein avoid the problems associated with prior art methods and provide a synthetic route for the preparation of photochromic compounds with a scalable reaction suitable for a variety of substituents with good yields. Summary of the invention

[0008] Provided is a phenylnaphthol compound comprising a core skeleton structure represented by the following formula (I):

[0009]

[0010] Where m is 0 to 4, n is 0 to 4, R 1 and R 2 R is independently a hydroxyl group, a cyano group, a (meth)acrylate group, an amino group, a halide group, a substituted or unsubstituted alkyl group, a borate group, a boric acid group, a polyether group, a polyester group, a polycarbonate group, a polyurethane group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a ketone group, an aldehyde group, an ester group, a carboxylic acid group, a carboxylate group, an amide group, a carbonate group, a carbamate group, a urea group, a siloxane group, an alkoxysilane group, or a polysiloxane group, and the two R on adjacent carbon atoms are 1 Group and / or two R 2 The groups can be linked to form a ring; R 3 is selected from substituted or unsubstituted 2-pyridyl or substituted or unsubstituted 2-quinolyl; and R 4 is selected from hydrogen, substituted or unsubstituted alkyl, alkoxymethyl, substituted or unsubstituted silyl, or acyl.

[0011] Also provided is a method for producing an indole naphthol compound comprising a core skeleton structure represented by the following formula (II):

[0012]

[0013] Where R 1 , R 2 and R 4 As described above, the method comprises cyclizing a phenylnaphthol compound shown in formula (I) in the presence of a catalyst.

[0014] The features that characterize the present invention are particularly pointed out in the claims, which are attached to and constitute a part of this disclosure. These and other features of the present invention, its operating advantages and specific objects obtained by its use will be more fully understood from the following detailed description, in which non-limiting embodiments of the present invention are shown and described. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 A general scheme of an exemplary method for preparing photochromic indole naphthopyran compounds of the present invention is shown, Scheme 1. DETAILED DESCRIPTION

[0016] As used herein, the articles "a," "an," and "the" include plural referents unless expressly and unequivocally limited to one referent.

[0017] As used herein, the term "includes" is synonymous with "comprises."

[0018] Unless otherwise indicated, all ranges or ratios disclosed herein should be understood to encompass any and all subranges or subratios contained therein. For example, a recited range or ratio of "1 to 10" should be considered to include any and all subranges between (and including) a minimum of 1 and a maximum of 10; that is, all subranges or subratios starting with a minimum of 1 or greater and ending with a maximum of 10 or less, such as, but not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.

[0019] As used herein, unless otherwise indicated, left-to-right representation of a linking group (such as a divalent linking group) includes other suitable orientations, such as but not limited to right-to-left orientation. For non-limiting illustration purposes, a divalent linking group or equivalently, the left-to-right representation of -C(O)O- includes its right-to-left representation or equivalently -O(O)C- or -OC(O)-.

[0020] Except in the operating examples, or where otherwise indicated, all numbers used in the specification and claims to indicate the amount of ingredients, reaction conditions, etc. should be understood to be modified in all cases by the term "about". "About" means plus or minus 25 percent of the value, such as plus or minus 10 percent of the value. However, it should not be regarded as a limitation on any analysis of values ​​under the principle of equivalents.

[0021] As used herein, molecular weight values, such as weight average molecular weight (Mw) and number average molecular weight (Mn) of polymers are determined by gel permeation chromatography using appropriate standards, such as polystyrene standards.

[0022] As used herein, the term "polymer" means homopolymers (eg, prepared from a single monomer species), copolymers (eg, prepared from at least two monomer species), and grafted polymers.

[0023] As used herein, the term "(meth)acrylate" and similar terms, such as "(meth)acrylic acid ester", means derivatives of acrylic acid and methacrylic acid, including acrylates, methacrylates, acrylamides, methacrylamides, acrylic acid and methacrylic acid. As used herein, the term "(meth)acrylic acid" means methacrylic acid and / or acrylic acid.

[0024] For some embodiments, the photochromic compounds of the present invention are also referred to herein as photochromic-dichroic compounds (eg, when they include one or more mesogen-containing groups).

[0025] The compounds of the present invention, as described herein, include but are not limited to photochromic compounds represented by Formula (I), Formula (II), Formula (III) and Formula (IV), in each case optionally further comprising one or more by-products resulting from the synthesis of such compounds.

[0026] As used herein, the term "photochromic" and similar terms (such as "photochromic compound" means having an absorption spectrum of at least visible radiation that changes in response to absorption of at least actinic radiation. Further, as used herein, the term "photochromic material" means any substance suitable for displaying photochromic properties (such as suitable for having an absorption spectrum of at least visible radiation that changes in response to absorption of at least actinic radiation) and including at least one photochromic compound.

[0027] As used herein, the term "actinic radiation" means electromagnetic radiation capable of inducing a response in a material, such as, but not limited to, transforming a photochromic material from one form or state to another, as discussed in further detail herein.

[0028] As used herein, the term "dichroic" means the ability to absorb one of two orthogonal plane-polarized components of at least transmitted radiation more strongly than the other.

[0029] As used herein, the term "photochromic-dichroic" and similar terms (such as "photochromic-dichroic compound") mean a compound that possesses and / or provides both photochromic properties (i.e., having an absorption spectrum of at least visible radiation that varies in response to at least actinic radiation) and dichroic properties (i.e., being able to absorb one of two orthogonal plane-polarized components of at least transmitted radiation more strongly than the other).

[0030] As used herein, and unless otherwise specified or limited, the term "photochromic material" includes thermally reversible photochromic materials and compounds and non-thermally reversible photochromic materials and compounds. As used herein, the term "thermally reversible photochromic compound / material" means a compound / material that can be switched from a first state (e.g., a "transparent state") to a second state (e.g., a "colored state") in response to actinic radiation, and returned to the first state in response to thermal energy. As used herein, the term "non-thermally reversible photochromic compound / material" means a compound / material that can be switched from a first state (e.g., a "transparent state") to a second state (e.g., a "colored state") in response to actinic radiation, and returned to the first state in response to actinic radiation of substantially the same wavelength as the absorption of the colored state (e.g., cessation of exposure to such actinic radiation).

[0031] As used herein, the terms "first" and "second" are not intended to refer to any particular order or temporal sequence, but rather to two different conditions or properties, for purposes of non-limiting illustration. For purposes of non-limiting illustration, the first state and the second state of the photochromic compound may differ in at least one optical property, such as, but not limited to, the absorption of visible radiation and / or UV radiation. Thus, according to various non-limiting embodiments disclosed herein, the photochromic compounds of the present invention may have different absorption spectra in each of the first and second states. For example, although not limited herein, the photochromic compounds of the present invention may be transparent in the first state and colored in the second state. Alternatively, the photochromic compounds of the present invention may have a first color in the first state and a second color in the second state.

[0032] As used herein, the term "optical" means relating to or associated with light and / or vision. For example, according to various non-limiting embodiments disclosed herein, the optical article or element or device can be selected from ophthalmic articles, elements and devices; display articles, elements and devices; windows; mirrors; or active and passive liquid crystal cell articles, elements and devices.

[0033] As used herein, the term "ophthalmic" means pertaining to or relating to the eye and vision. Non-limiting examples of ophthalmic articles or elements include corrective and non-corrective lenses (which include single-vision or multi-vision lenses, which may be segmented or non-segmented multi-vision lenses (such as but not limited to bifocal lenses, trifocal lenses, and progressive lenses), and other elements for correcting, protecting, or enhancing (cosmetic or other) vision (which include but are not limited to contact lenses, intraocular lenses, magnifying lenses, and protective lenses or goggles).

[0034] As used herein, the term "display" means a visible or machine-readable representation of information in the form of words, numbers, symbols, designs, or diagrams. Non-limiting examples of display elements include screens, monitors, and security elements such as security markings.

[0035] As used herein, the term "window" means an aperture adapted to allow radiation to be transmitted therethrough. Non-limiting examples of windows include automotive and aircraft transparencies, windshields, filters, shutters, and optical switches.

[0036] As used herein, the term "mirror" means a surface that specularly reflects a significant portion of incident light.

[0037] As used herein, the term "liquid crystal cell" refers to a structure containing liquid crystal material that is capable of being ordered. A non-limiting example of a liquid crystal cell element is a liquid crystal display.

[0038] As used herein, the terms "formed over", "deposited over", "provided over", "applied over", "residing over", or "positioned over" mean formed, deposited, provided, applied, applied, residing, or positioned over, but not necessarily in direct (or adjacent) contact with an underlying element, or a surface of an underlying element. For example, a layer "positioned over" does not exclude the presence of one or more other layers, coatings, or films of the same or different composition between the positioned or formed layer and the substrate.

[0039] As used herein, statements concerning ring positions (such as, but not limited to, position-x (e.g., position-3 or position-13) refer to specific positions of chemical compounds (such as the indole naphthopyran photochromic compounds of the present invention) in a ring structure (such as a core skeleton structure), and are depicted herein according to some embodiments by numbers within the ring structure of representative chemical formulas (such as, but not limited to, formula (I) and / or (Ia)).

[0040] "Core skeleton structure" means a compound comprising at least the skeleton structure depicted in the relevant formula. The core skeleton structure is provided for the purpose of identifying the numbered ring positions. However, it should be understood that, unless explicitly shown to the contrary, one or more core skeleton structures may have one or more atoms or one or more groups (not specifically shown in the corresponding formula) bonded to one or more numbered ring positions on the core skeleton structure, which may be the same or different from each other.

[0041] With respect to the term "core skeleton structure" as used herein in relation to the photochromic compounds of the present invention, the term may be represented by one or more formulae, such as but not limited to formulae (I), (II), (III) and / or (IV).

[0042] All documents or portions of documents (such as but not limited to published patents and patent applications) referred to herein, and unless otherwise indicated, are deemed to be "incorporated by reference in their entirety."

[0043] "Aryl" refers to an aromatic cyclic monovalent hydrocarbon radical, and the term "aromatic" refers to a cyclic conjugated hydrocarbon having a stability (due to delocalization) significantly greater than the stability of a presumed localized structure. Examples of aryl groups include C6-C 14 Aryl groups such as, but not limited to, phenyl, naphthyl, phenanthrenyl, and anthracenyl.

[0044] As used herein, the description of "halo" and related terms (such as, but not limited to, haloalkyl, haloalkenyl, haloalkynyl, halogenated aryl and halogenated heteroaryl) means a group in which at least one, and at most, all available hydrogen groups are replaced by halogen groups. The term "halo" includes "perhalogenated". As used herein, the term perhalogenated group and related terms (such as, but not limited to, perhaloalkyl, perhaloalkenyl, perhaloalkynyl, perhalogenated aryl or perhalogenated heteroaryl) means a group in which all available hydrogen groups are replaced by halogen groups. For example, perhalomethyl is -CX3; perhalophenyl is -C6X5, wherein X represents one or more halo groups, such as, but not limited to, F, Cl or Br.

[0045] As used herein, descriptions of "straight or branched" groups (such as straight or branched alkyl groups) are understood herein to include: straight chain (or "straight chain") groups, such as straight chain C1-C 25 Alkyl; and appropriately branched groups, such as branched C3-C 25 alkyl.

[0046] The term "alkyl" as used herein refers to a linear or branched, cyclic or non-cyclic C1-C 25 Alkyl. A straight chain or branched chain alkyl may include C1-C25 Alkyl groups, such as C1-C 20 Alkyl groups, such as C2-C 10 Alkyl groups, such as C1-C 12 Alkyl groups such as C1-C6 alkyl groups. Examples of alkyl groups from which the various alkyl groups of the present invention may be selected include, but are not limited to, those further listed herein. Alkyl groups may include "cycloalkyl" groups. The term "cycloalkyl" as used herein means a suitable cyclic group such as, but not limited to, C3-C 12 Cycloalkyl (including but not limited to cyclic C5-C7 alkyl, or cyclic C3-C 10 Examples of cycloalkyl groups include, but are not limited to, those further listed herein. The term "cycloalkyl" as used herein also includes: bridged polycycloalkyl groups (or bridged polycyclic (polycyclic) alkyl), such as, but not limited to, bicyclo [2.2.1] heptyl (or norbornyl) and bicyclo [2.2.2] octyl; and condensed polycycloalkyl groups (or condensed polycyclic (polycyclic) alkyl), such as, but not limited to, octahydro-1H-indenyl, and decahydronaphthyl.

[0047] The term "heterocycloalkyl" as used herein refers to a suitable cyclic group such as but not limited to C2-C 12 Heterocycloalkyl, such as C5-C7 heterocycloalkyl, such as C2-C 10 Heterocycloalkyl, and it has at least one heteroatom in the cyclic ring, such as but not limited to O, S, N, P, and combinations thereof. Examples of heterocycloalkyl include, but are not limited to, imidazolyl, tetrahydrofuranyl, tetrahydropyranyl, and piperidinyl. The term "heterocycloalkyl" as used herein also includes: bridged polycyclic heterocycloalkyl, such as but not limited to 7-oxabicyclo[2.2.1]heptyl; and fused polycyclic heterocycloalkyl, such as but not limited to octahydrocyclopenta[b]pyranyl and octahydro-1H-isochromenyl.

[0048] As used herein, the term "heteroaryl" includes, but is not limited to, C3-C 18 Heteroaryl, such as but not limited to C3-C 10 Heteroaryl (including fused polycyclic heteroaryl) and means an aryl having at least one heteroatom in an aromatic ring or in at least one aromatic ring in the case of a fused polycyclic heteroaryl. Examples of heteroaryl include, but are not limited to, furanyl, pyranyl, pyridyl, isoquinoline, and pyrimidinyl.

[0049] As used herein, the term "fused polycyclic-aryl-alkyl" and similar terms (such as fused polycyclic-alkyl-aryl, fused polycyclic-aryl-alkyl, and fused polycyclic-alkyl-aryl) means a fused polycyclic group comprising at least one aryl ring and at least one cycloalkyl ring fused together to form a fused ring structure. For non-limiting purposes, examples of fused polycyclic-aryl-alkyl include, but are not limited to, indenyl, 9H-fluorenyl, cyclopentanaphthenyl, and indacenyl.

[0050] As used herein, the term "aralkyl" includes, but is not limited to, C6-C 24 Arylalkyl, such as but not limited to C6-C 10 Aralkyl refers to an alkyl group substituted by an aryl group. Examples of aralkyl groups include, but are not limited to, benzyl and phenethyl.

[0051] Representative alkyl includes but is not limited to methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl. Representative alkenyl includes but is not limited to vinyl, allyl and propenyl. Representative alkynyl includes but is not limited to ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, and 2-butynyl. Representative cycloalkyl includes but is not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl substituents. Representative heterocycloalkyl includes but is not limited to imidazolyl, tetrahydrofuranyl, tetrahydropyranyl and piperidinyl. Representative aryl includes but is not limited to phenyl, naphthyl, anthracenyl, phenanthrenyl and tetraphenyl (including their structural isomers). Representative heteroaryl includes but is not limited to furanyl, pyranyl, pyridyl, isoquinolinyl, and pyrimidinyl. Representative aralkyl includes but is not limited to benzyl and phenethyl.

[0052] As used herein, the term "nitrogen-containing heterocycle" includes, but is not limited to, a nitrogen-containing ring, wherein the nitrogen-containing ring is bonded via a ring nitrogen. Examples of nitrogen-containing heterocycles include, but are not limited to, cyclic amino groups such as morpholino, piperidino, and pyrrolidino; and heteroaromatic compounds such as imidazole, pyrrole, indole, and carbazole.

[0053] As used herein, the term "acyl" includes, but is not limited to, a CO-alkanoyl or aroyl, where R a represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

[0054] As used herein, the term "polysiloxane" (such as a substituent for various groups of the photochromic compound of the present invention) includes materials represented by the following formula (G):

[0055]

[0056] With respect to formula (G), in each case, the subscript t' is from 2 to 200, such as from 2 to 100, or 2 to 50, or from 2 to 25, or from 2 to 15, or from 2 to 10, or from 2 to 5, inclusive. Further with respect to the following formula (G): for each t', R 32 and R 33 are each independently selected from alkyl or aryl; and R 34 is selected from hydrogen, alkyl, or aryl. In some embodiments: for each t', R 32 and R 33 are each independently selected from methyl, ethyl, or phenyl; and R 34 is selected from hydrogen, methyl, ethyl, or phenyl.

[0057] As used herein, the term "polysiloxane", as a substituent with respect to various groups of the photochromic compound of the present invention, instead of or in addition to the substance represented by formula (G), includes a material represented by the following formula (H):

[0058]

[0059] With respect to formula (H), subscript u' is 0-2 and subscript x' is 1-3, provided that u'+x' is 3; and subscript v' is 0-2 and subscript w' is 1-3, provided that v'+w' is 3. Further with respect to formula (H), in each case, for each u', R 35 Independently, for each v' and each x', R 36 Independently, and for each w' and each x', each R 37 Independently selected from alkyl (such as but not limited to methyl or ethyl) or aryl (such as but not limited to phenyl).

[0060] As used herein, the recitation of a "substituted" group is intended to include, but is not limited to, groups including: alkyl, heterocycloalkyl, aryl and / or heteroaryl groups in which at least one hydrogen has been replaced or substituted by a group other than hydrogen (such as, but not limited to, alkoxy); halogen groups (e.g., F, Cl, I, and Br); hydroxyl groups; thiol groups; alkylthio groups; arylthio groups; ketone groups; aldehyde groups; ester groups; carboxylic acid groups; phosphoric acid groups; phosphate ester groups; sulfonic acid groups; sulfonate ester groups; nitro groups; cyano groups; alkyl (including aralkyl); alkenyl groups; alkynyl groups; haloalkyl groups; perhaloalkyl groups; heterocycloalkyl groups; aryl groups (including alkaryl groups, including hydroxy-substituted aryl groups such as phenol, and including polycondensed ring aryl groups); heteroaryl groups (including polycondensed ring heteroaryl groups); amino groups such as -N(R 11’ )(R 12’ ), where R 11’ and R 12’Each is independently selected from, for example, hydrogen, alkyl, heterocycloalkyl, aryl, or heteroaryl; a carboxylate group; a siloxane group; an alkoxysilane group; a polysiloxane group; an amide group; a urethane group; a carbonate group; a urea group; a polyester group; a polyether group; a polycarbonate group; a polyurethane group; an acrylate group; a methacrylate group; a nitrogen-containing heterocyclic compound; or a combination thereof, including those classes and examples as further described herein.

[0061] As used herein, the terms "phenylnaphthol" and "indolenaphthol" include protected phenylnaphthol and indolenaphthol compounds, and phenylnaphthol and indolenaphthol derivatives.

[0062] As used herein, "at least one of" is synonymous with "one or more of," whether the elements are listed in conjunction or separately. For example, the phrases "at least one of A, B, and C" and "at least one of A, B, or C" each mean any one of A, B, or C, or any combination of any two or more of A, B, or C. For example, A alone; or B alone; or C alone; or A and B; or A and C; or B and C; or all of A, B, and C.

[0063] As used herein, "selected from" is synonymous with "chosen from", regardless of whether the elements are listed in conjunction or separately. For example, the phrases "selected from A, B, and C" and "selected from A, B, or C" each mean any one of A, B, or C, or any combination of any two or more of A, B, or C. For example, A alone; or B alone; or C alone; or A and B; or A and C; or B and C; or all of A, B, and C.

[0064] The discussion of the present invention may describe certain features as "particularly" or "preferably" within certain limitations (e.g., "preferably", "more preferably", or "even more preferably" within certain limitations). It should be understood that the present invention is not limited to these specific or preferred limitations, but encompasses the entire scope of the disclosure.

[0065] The present invention comprises, or consists essentially of, the following aspects of the invention in any combination.

[0066] The compounds according to the present invention may be represented by one or more of the core skeleton structures described below.

[0067]

[0068] Regarding formula (I), R 1 and R 2Each of the R groups is independently a hydroxyl group, a cyano group, a (meth)acrylate group, an amino group, a halogen group (such as fluorine, chlorine, bromine or iodine), a substituted or unsubstituted alkyl group, a borate or boric acid group, a polyether, a polyester, a polycarbonate, a polyurethane, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocycloalkyl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a ketone, an aldehyde, an ester, a carboxylic acid, a carboxylate, an amide, a carbonate, a carbamate, a urea, a siloxane, an alkoxysilane, or a polysiloxane. The two R groups on adjacent carbon atoms are 1 Group or two R 2 The groups may be linked to form a ring. 3 R is selected from substituted or unsubstituted 2-pyridyl or substituted or unsubstituted 2-quinolyl. The substituents of the substituted 2-pyridyl and substituted 2-quinolyl are each independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, halogen, amino, ester, carboxylate, or hydroxyl. 4 is selected from hydrogen, substituted or unsubstituted alkyl, alkoxymethyl, substituted or unsubstituted silyl, or acyl.

[0069] From which you can choose R 1 Examples of the group include, but are not limited to, halogen (such as fluorine), substituted or unsubstituted alkyl (such as methyl), substituted or unsubstituted heteroaryl, substituted or unsubstituted alkoxy (such as methoxy), substituted or unsubstituted alkylthio, or substituted or unsubstituted arylthio. 2 Examples of groups include, but are not limited to, halogen (such as fluorine), substituted or unsubstituted alkyl (such as methyl or trifluoromethyl), substituted or unsubstituted heteroaryl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, or substituted or unsubstituted arylthio. 3 Examples of groups including, but not limited to, 2-pyridyl. 4 Examples of the group include, but are not limited to, substituted or unsubstituted alkyl, substituted silyl (eg, trialkylsilyl, such as trimethylsilyl), alkoxymethyl (eg, methoxymethyl), or acyl (eg, acetyl or benzoyl).

[0070] The compounds of the present invention can be prepared as follows according to art-recognized methods. For non-limiting illustrative purposes and with reference to Figure 1 , General Synthesis Scheme 1, the preparation of compounds according to the present invention is described below. Further detailed descriptions of the preparation of compounds of the present invention are further provided in the Examples herein. Figure 1 In the various intermediates, reactants, and / or compounds depicted, various groups such as R 1 , R2 , R 3 , R 4 , B, B', R 芳基 , and R 烷基 Each is as described herein, and / or represents a precursor of such a group.

[0071] The synthesis of the compound represented by the following formula (Ia) has been described in many documents, such as US Pat. No. 6,296,785 or US Pat. No. 7,262,295, which has various substituents.

[0072]

[0073] Hydroxyl groups and carboxylic acids may be protected. For example, a hydroxyl group may be benzylated by reaction with benzyl chloride and a base such as sodium carbonate or potassium carbonate to form a group in which R 4 The resulting carboxylic acid ester can then be converted to a carboxylic acid by an acid or base method for ester hydrolysis. The resulting product is shown in the following formula (Ib).

[0074]

[0075] The carboxylic acid group can then be converted to an NH2 group via Curtius rearrangement conditions using diphenylphosphoryl azide (which generates an isocyanate group which then hydrolyzes to produce an amine group), as shown below in formula (Ic).

[0076]

[0077] The amine group is converted to an amide group by conventional amide forming reactions, such as reacting the amine with an acyl chloride, ester or carboxylic acid group, as shown in formula (I). For example, the amine reacts with picolinoyl chloride and a base such as triethylamine to give picolinamide in high yield, wherein R3 is 2-pyridyl.

[0078] The method according to the present invention involves the production of an indole naphthol compound including a core skeleton structure represented by the following formula (II).

[0079]

[0080] Regarding formula (II), m, n, R 1 , R 2 and R 4 As described above in formula (I).

[0081] The method for producing an indole naphthol compound comprises cyclizing the phenyl naphthol compound shown in formula (I) in the presence of a catalyst. See the reaction depicted below. The catalyst can be a transition metal catalyst. Suitable transition metal catalysts can include copper, zinc, palladium, platinum, rhodium or iridium. The cyclization can be carried out under a copper catalyst, as described in Takumatso, K. et al. Org. Lett. [Organic Express] 2014, 16, 2892.

[0082]

[0083] The method of the present invention may further include alkylating or arylating the indolenaphthol compound of formula (II) to produce an indolenaphthol compound including a core skeleton structure represented by the following formula (III).

[0084]

[0085] Regarding formula (III), m, n, R 1 , R 2 and R 4 As described above in formula (I). 5 R can be selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or acyl. 5 Examples of the group include, but are not limited to, alkyl, phenyl or substituted phenyl. Non-limiting suitable alkylation and arylation reactions for this method are described below.

[0086] Alkylation of the indole group as shown in formula (IIIa) can be accomplished by reacting with an alkyl halide, triflate or tosylate in the presence of a base. Suitable bases include sodium tert-butoxide or potassium tert-butoxide. The indole can be deprotonated by a strong base such as sodium hydride or n-butyllithium, and then the anion is reacted with an alkyl halide, triflate or tosylate. See the reaction depicted below.

[0087]

[0088] The indole group can be arylated by a cross-coupling reaction with a transition metal catalyst and an aryl halide, as shown in formula (IIIb). The cross-coupling reaction can be an Ullmann coupling reaction with a copper catalyst and an aryl halide such as a phenyl halide. See the reaction depicted below.

[0089]

[0090] Indoles can also be arylated by nucleophilic aromatic substitution, such as by reaction with an aryl fluoride in a suitable solvent such as tetrahydrofuran or dimethylformamide, as shown in formula (IIIb).

[0091] The method of the present invention may further include: 4 When R is a substituted or unsubstituted alkyl group, an alkoxymethyl group, a substituted or unsubstituted silyl group, or an acyl group, 4 Deprotection to generate a hydroxyl group. The protecting group can be removed by palladium hydrogenation conditions or with a strong acid. See the reaction shown below, where R of formula (III) 4 is a substituted or unsubstituted alkyl group, an alkoxymethyl group, a substituted or unsubstituted silyl group, or an acyl group, and the deprotected product is shown in formula (IIId).

[0092]

[0093] The method may further include reacting with a diaryl propargyl alcohol to form an indole naphthopyran compound including a core skeleton structure shown in the following formula (IV).

[0094]

[0095] Regarding formula (IV), m, n, R 1 , R 2 and R 4 As described above in formula (I), and R 5 As described in formula (III) above. B and B' are each independently selected from substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. B and B' may each independently be substituted or unsubstituted phenyl. Each phenyl substituent may be selected from alkoxy, halogen, alkyl, or aryloxy.

[0096] The indole naphthol compound shown in formula (III) can be reacted with an aryl propargyl alcohol under acidic conditions to produce an indole naphthopyran compound, as shown in formula (IV).

[0097] See the reaction depicted below.

[0098]

[0099] The photochromic indole naphthopyran compounds prepared according to the method of the present invention, such as those described above with respect to formula (IV), can be used individually or in combination with one or more other photochromic compounds. For example, the photochromic compounds of the present invention can be used in combination with one or more other photochromic compounds having an activation absorption maximum in the range of 300 nanometers to 1,000 nanometers. In addition, the indole naphthopyran compounds prepared according to the present invention can be used in combination with one or more complementary conventional polymerizable or compatible photochromic compounds, such as those described in U.S. Pat. Nos. 6,113,814 (column 2, lines 39 to 8, line 41) and 6,555,028 (column 2, lines 65 to 12, line 56); or in combination with a mixture of other photochromic compounds to obtain certain activated colors, such as near-neutral gray or near-neutral brown. See, for example, US Patent No. 5,645,767 at column 12, line 66 to column 13, line 19, which describes parameters defining neutral grays and browns.

[0100] Indole naphthopyran compounds prepared according to the present invention can be used alone or in combination with other photochromic compounds as just discussed above to prepare photochromic compositions. For example, such photochromic compositions may include: (i) an organic material, wherein the organic material is at least one of a polymeric material, an oligomeric material, or a monomeric material; and (ii) an indole naphthopyran photochromic compound (alone or in combination with other photochromic compounds) as prepared according to the present invention, which is incorporated into at least a portion of the organic material. For some embodiments, examples of suitable organic materials may include, but are not limited to, any one of those 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(carbonates), copolymers of ethylene and vinyl acetate; copolymers of ethylene and vinyl alcohol; copolymers of ethylene, vinyl acetate, and vinyl alcohol (such as those obtained by partial saponification of copolymers of ethylene and vinyl acetate); cellulose acetate butyrate; polyurethanes; poly(acrylates); poly(methacrylates); epoxy compounds; aminoplast functional polymers; poly(anhydrides); poly(urea urethanes); N-alkoxymethyl(meth)acrylamide functional polymers; poly(siloxanes); poly(silanes); and combinations and mixtures thereof. Further classes 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 at column 39, line 45 through column 40, line 67 of US 9,028,728 B2. Such photochromic compositions may include additive materials such as photoinitiators, thermal initiators, inhibitors, solvents, light stabilizers, thermal stabilizers, release agents, rheology control agents, leveling agents, free radical scavengers, and / or adhesion promoters. The photochromic composition according to the present invention may be a photochromic coating composition, which 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 or curable coating composition. Such compositions may be used to prepare photochromic articles, such as ophthalmic articles, display articles, windows, mirrors, active liquid crystal cell articles, and passive liquid crystal cell articles. Such photochromic articles (e.g., photochromic lenses) may be transformed from a first unactivated state (e.g., transparent and non-blue light blocking state) to a second activated state (e.g., tinted and blue light blocking state) when exposed to actinic radiation. After removing the actinic radiation source, the article may be restored to a first unactivated (and transparent) state. Thus, photochromic articles according to the present invention provide enhanced protection against health risks associated with blue light exposure during outdoor activities while maintaining acceptable aesthetics indoors.

[0101] The present invention is more particularly described in the following examples, which are intended to be illustrative only, since numerous modifications and variations therein will be apparent to those skilled in the art.

[0102] Examples

[0103] The following examples are provided to illustrate the compounds of the present invention, methods for producing the compounds of the present invention, and methods for using such compounds to prepare photochromic compounds. These examples provide a description of the synthesis of the phenylnaphthol compounds of the present invention and a description of the methods of the present invention for producing indolenaphthol and indolenaphthopyran compounds.

[0104] Preparation of Examples 1-10

[0105] In the following examples, representative synthetic procedures for the preparation of benzyl-protected phenylnaphthol and indolenaphthol compounds are detailed.

[0106] Example 1

[0107] The scheme for synthesizing Example 1 is shown below. "Ac" refers to acetyl, "Bn" refers to benzyl, "DPPA" refers to diphenylphosphoryl azide, "EtOH" refers to ethanol, "DCC" refers to N,N'-dicyclohexylcarbodiimide, "DMF" refers to dimethylformamide, "iPrOH" refers to isopropanol, "DMAP" refers to 4-(dimethylamino)pyridine, and "DCM" refers to dichloromethane. Each step of the synthesis is further described below.

[0108]

[0109] Step 1

[0110] While stirring under nitrogen, benzophenone (84.0g, 461mmol) and dimethyl succinate (80.84g, 553mmol) were dissolved in toluene (1.0L). Tert-potassium pentoxide (1.7M in toluene, 352.5mL, 599mmol) was added dropwise at room temperature within 2 hours. After 20 hours, water (1.5L) was added to the reaction mixture and the layers were separated. The organic phase was discarded. The aqueous phase was extracted with toluene (1×200ml) and the organic phase was discarded. The aqueous phase was acidified to pH 4 with 2N hydrochloric acid solution, and then the solution became turbid. The product was separated by extracting the mixture with ethyl acetate (3×300ml). The organic layers were combined, dried with sodium sulfate and concentrated under reduced pressure. The resulting solid was washed with hexane, collected and dried under vacuum to give 132.8g (97% yield) of colorless powder.

[0111] Step 2

[0112] The product from step 1 (132.8 g, 448.2 mmol) was combined with acetic anhydride (254.2 mL, 2.69 mol) and toluene (250 ml) and heated to reflux while stirring under nitrogen. After 16 hours, the reaction mixture was concentrated under reduced pressure and the resulting oil was precipitated in hexanes to give an off-white solid. The solid was collected and dried to give 125.5 g (88% yield).

[0113] Step 3

[0114] Under stirring, the product (150g, 468mmol) from step 2 is suspended in methanol (400ml). In the suspension, concentrated hydrochloric acid (10ml) is added and the reaction mixture is heated to reflux for 2 hours. Once completed, the reaction mixture is cooled to room temperature and left to stand for 50 hours without stirring, while the product is recrystallized. Crystals are collected and dried to give complete conversion (130g).

[0115] Step 4

[0116] While stirring under nitrogen, the product from step 3 (130 g, 467 mmol) was dissolved in anhydrous dimethylformamide (400 ml). Potassium carbonate (130 g, 934 mmol) was suspended in the mixture, followed by the slow addition of benzyl chloride (71.0 g, 560 mmol). The reaction mixture was heated at 75 ° C for 16 hours. Once cooled, the reaction mixture was slowly poured into ice water and extracted into ethyl acetate (3 × 500 ml). The organic layers were combined, washed with brine (2 × 300 ml), dried over sodium sulfate and concentrated under reduced pressure. The resulting solid was washed with methanol, collected and dried under vacuum to give a colorless solid (155.4 g, 90% yield).

[0117] Step 5

[0118] The product from step 4 (155.4 g, 422 mmol) was suspended in 2-propanol (300 ml) under stirring. Sodium hydroxide solution (10% w / w in water, 300 ml) was added and the reaction mixture was heated to reflux for 18 hours. Once cooled, the reaction mixture was poured into an acidic ice-water bath (pH 3-4) to form a colorless precipitate. The powder was collected and dried to give 148.9 g (99% yield).

[0119] Step 6

[0120] While stirring under nitrogen, the product (149.1g, 421mmol) from step 5 is suspended in anhydrous toluene (800ml). Triethylamine (111g, 1.1mol) and anhydrous ethanol (100ml) are added to dissolve the suspension. Diphenylphosphoryl azide (174g, 632mmol) is added to the reaction mixture in batches, and the reaction mixture is exothermic to reflux by itself, and heat is added to reflux for a total of 2 hours. Once cooled, the reaction mixture is added to water (1.5L) and ethyl acetate (500ml) and each layer is separated. The organic layer is washed with water (3×1L), dried over sodium sulfate and concentrated under reduced pressure to give a reddish oil, which is used without further purification.

[0121] Step 7

[0122] The resulting oil from step 6 was dispersed in tetrahydrofuran (600 ml), ethanol (400 ml) and water (1.1 L) with sodium hydroxide (86 g, 2.2 mol). The reaction mixture was heated to reflux for 5 days. Once cooled, brine (200 ml) was added to the reaction mixture, the layers were separated, and the aqueous layer was washed with ethyl acetate (3×300 ml). The organic layers were combined, dried over sodium sulfate and concentrated under reduced pressure to give a reddish semi-solid, which was used without further purification.

[0123] Step 8, Example 1

[0124] While stirring under nitrogen, the product from step 7 is absorbed in dichloromethane (1.2 L). Picolinic acid (78 g, 632 mmol) and 4-(dimethylamino)pyridine (5.2 g, 42 mmol) are added, followed by N, N'-dicyclohexylcarbodiimide (130.4 g, 632 mmol). The reaction mixture is allowed to stir at room temperature for 16 hours. The reaction mixture is filtered and concentrated under reduced pressure to obtain a black solid, which is washed with methanol to obtain a protected phenylnaphthol compound (Example 1) (160.85 g, 89% yield in 3 steps) as an off-white powder.

[0125] Step 9, Example 1a

[0126] The product from step 8 (76.5 g, 178 mmol) was dissolved in anhydrous dimethylformamide (500 ml) and copper (II) acetate (65.0 g, 356 mmol) and glacial acetic acid (10.7 g, 178 mmol) were added thereto while stirring under nitrogen. The reaction mixture was heated to 150 ° C for 20 hours to give a 70% conversion of the starting material. The reaction mixture was filtered through a diatomaceous earth pad and the pad was washed with 500 ml of ethyl acetate. The filtrate was added to a separatory funnel along with water (1.0 L) containing ethylenediamine (10 ml) and the layers were separated. The organic layer was washed with water (3×300 ml), dried over sodium sulfate and concentrated under reduced pressure to give an off-white solid. The material was subjected to a second repetition of the reaction conditions and the same separation procedure. The resulting solid was washed twice with methanol (300 ml) to give an off-white powder (Example 1a, 49.5 g, 86% yield). The product was obtained by 1 H NMR and mass spectrometry confirmed.

[0127] Examples 2-9 and Examples 2a-9a were prepared in a similar manner and are summarized in Table 1. All compounds were prepared by 1 H NMR and mass spectrometry characterization.

[0128] Table 1

[0129]

[0130]

[0131]

[0132] 1 The yield corresponds to the isolated phenylnaphthol intermediate accumulated from steps 6-8;

[0133] 2 The yield corresponds to the isolated indole naphthol intermediate from step 9.

[0134] Preparation of Examples 11 and 12

[0135] In the following examples, representative synthetic procedures for preparing indole naphthopyran photochromic compounds are detailed. The schemes for synthesizing Examples 11 and 12 are shown below. "nBuI" refers to iodobutylene, "DMF" refers to dimethylformamide, "pTSA" refers to p-toluenesulfonic acid, and "Ph" refers to phenyl. Each step of the synthesis is further described below.

[0136]

[0137] Example 11

[0138] Step 1a

[0139] While stirring under nitrogen, Example 1a (4.0 g, 12.4 mmol) was dissolved in anhydrous dimethylformamide (30 ml) and sodium hydride (0.9 g, 37.1 mmol) was slowly added. After 15 minutes, iodobutane (2.50 g, 13.6 mmol) was added and the reaction mixture was stirred at room temperature for 45 minutes. The reaction mixture was absorbed in ethyl acetate (200 ml) and washed with water (3 × 200 ml). The organic layer was dried over sodium sulfate and concentrated under reduced pressure to give a brown solid. The solid was washed with methanol to produce an off-white powder (4.20 g, 89% yield).

[0140] Step 2a

[0141] The product from step 1 (4.0 g, 10.5 mmol) was combined with ammonium formate (2.75 g, 43.6 mmol) and palladium on carbon (Degussa model E1003 U / W, 0.37 g, 3.2 mmol) in dimethylformamide (100 ml) while stirring under nitrogen. The reaction mixture was heated to 85° C. for 2 hours. Once cooled, the reaction mixture was filtered through a pad of celite and the pad was washed with ethyl acetate (250 ml). The filtrate was washed with water (3×300 ml), dried over sodium sulfate and concentrated under reduced pressure to give a brown solid. The solid was precipitated from dichloromethane into hexanes to give an off-white powder (2.76 g, 91% yield).

[0142]

[0143] Step 3a

[0144] While stirring under nitrogen, the product from step 2 (0.85g, 2.90mmol) is combined with 1,1-diphenylpropane-2-yn-1-ol (0.73g, 3.5mmol) in toluene (25ml) and heated to reflux. Add p-toluenesulfonic acid (5-10mg) and heat the reaction mixture to reflux for 1 hour. Once cooled, the reaction mixture is absorbed in ethyl acetate (25ml), washed with saturated sodium bicarbonate solution (25ml) and water (2×50ml). The organic layer is dried over sodium sulfate and concentrated onto silica gel under reduced pressure. Chromatography (silica gel, 0-25% dichloromethane in hexane) produces a dark oil. The product is recrystallized twice from methyl tert-butyl ether, tetrahydrofuran and methanol to obtain Example 11 (0.73g, 53% yield) as an off-white powder, and confirmed by mass spectrometry.

[0145] Example 12

[0146] Step 1b

[0147] Example 1a (7.0 g, 21.6 mmol) was combined with bromobenzene (13.6 g, 86.4 mmol), copper iodide (2.06 g, 10.8 mmol), potassium carbonate (6.0 g, 43.2 mmol), 1,10-phenanthroline (0.78 g, 4.30 mmol) and dibenzo-18-crown-6-ether (0.80 g, 2.20 mmol) in anhydrous dimethylformamide (50 ml) while stirring under nitrogen. The reaction mixture was heated to 150° C. for 4 hours. Once cooled, the reaction mixture was taken up in ethyl acetate (250 ml) and washed initially with water (200 ml), with ethylenediamine (10 ml), and subsequently with water (2×250 ml). The organic layer was dried over sodium sulfate and concentrated onto silica gel under reduced pressure. Chromatography (silica gel, 0-25% dichloromethane in hexanes) gave a colorless powder which was washed with hexanes and dried in vacuo (7.82 g, 90% yield).

[0148] Step 2b

[0149] The product from step 1 (2.5 g, 6.26 mmol) was combined with ammonium formate (1.60 g, 25.0 mmol) and palladium on carbon (Degussa model E1003 U / W, 0.22 g, 1.9 mmol) in dimethylformamide (30 ml) while stirring under nitrogen. The reaction mixture was heated to 80° C. for 2 hours. Once cooled, the reaction mixture was filtered through a pad of celite and the pad was washed with ethyl acetate (250 ml). The filtrate was washed with water (3×300 ml), dried over sodium sulfate and concentrated under reduced pressure to give a brown oil which was used without further purification.

[0150]

[0151] Step 3b

[0152] While stirring under nitrogen, the product from step 2 (0.50g, 1.60mmol) is combined with 1,1-diphenylpropane-2-yn-1-ol (0.40g, 2.0mmol) in toluene (30ml) and heated to reflux. Add p-toluenesulfonic acid (5-10mg) and heat the reaction mixture to reflux for 1 hour. Once cooled, the reaction mixture is concentrated onto silica gel under reduced pressure. Chromatography (silica gel, 0-5% dichloromethane in hexane) produces a yellow solid. The product is recrystallized twice from dichloromethane and hexane to obtain Example 12 (0.22g, 27% yield) in light yellow crystals and confirmed by mass spectrometry.

[0153] The present invention may be further characterized by one or more of the following non-limiting clauses.

[0154] Item 1. A phenylnaphthol compound having a core skeleton structure represented by formula (I):

[0155]

[0156] in,

[0157] m is 0 to 4;

[0158] n is 0 to 4;

[0159] R 1 and R 2 each independently represents a hydroxyl group, a cyano group, a (meth)acrylate group, an amino group, a halide group, a substituted or unsubstituted alkyl group, a borate group, a boric acid group, a polyether group, a polyester group, a polycarbonate group, a polyurethane group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocycloalkyl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a ketone group, an aldehyde group, an ester group, a carboxylic acid group, a carboxylate group, an amide group, a carbonate group, a carbamate group, a urea group, a siloxane group, an alkoxysilane group, or a polysiloxane group;

[0160] The two R 1 Group or two R 2 The groups can be linked to form rings;

[0161] R 3 is selected from substituted or unsubstituted 2-pyridyl or substituted or unsubstituted 2-quinolyl;

[0162] wherein the pyridyl and quinolyl substituents are selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, halogen, amino, ester, carboxylate, or hydroxyl; and

[0163] R 4 is selected from hydrogen, substituted or unsubstituted alkyl, alkoxymethyl, substituted or unsubstituted silyl, or acyl.

[0164] Item 2. A phenylnaphthol compound as described in Item 1, wherein each alkyl substituent, each aryl substituent, each heterocycloalkyl substituent, each heteroaryl substituent, each alkoxy substituent, each aryloxy substituent, each alkylthio substituent, each arylthio substituent and each silyl substituent is independently selected from halogen, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, perhaloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, hydroxyl, alkylthio, arylthio, ketone, aldehyde, ester, carboxylic acid, carboxylate, siloxane, alkoxysilane, polysiloxane, amide, amine, carbamate, carbonate, urea, polyester group, polyether group, polycarbonate group, polyurethane group, acrylate group, (meth)acrylate group, arylamine, alkylamine, cyclic amino group, heteroaromatic compound, or a combination thereof.

[0165] Item 3. The phenylnaphthol compound according to Item 1 or 2, wherein R 1 and R 2 are independently selected from halo, substituted or unsubstituted alkyl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkylthio, or substituted or unsubstituted arylthio.

[0166] Item 4. The phenylnaphthol compound as described in Item 3, wherein R 1 or R 2 It is an alkoxy group, an alkyl group, a halo group, a trihaloalkyl group, or an arylthio group.

[0167] Item 5. The phenylnaphthol compound according to Item 4, wherein R 1 or R 2 It is methoxy, methyl, fluoro, trifluoromethyl, or arylthio.

[0168] Item 6. The phenylnaphthol compound according to Item 4, wherein R 1 or R 2 It is an alkoxy group.

[0169] Item 7. The phenylnaphthol compound according to any one of Items 4 to 6, wherein R 1 or R 2 It's a methoxy group.

[0170] Item 8. The phenylnaphthol compound according to any one of Items 1 to 4, wherein R 1 or R 2 Each halo of is selected from fluorine, chlorine, bromine or iodine.

[0171] Item 9. The phenylnaphthol compound according to any one of Items 1 to 8, wherein R 3 It is 2-pyridyl.

[0172] Item 10. The phenylnaphthol compound according to any one of Items 1 to 9, wherein R 4 It's benzyl.

[0173] Item 11. The phenylnaphthol compound according to any one of Items 1 to 10, wherein R 1 At the positions shown in the core skeleton structure of the following formula (I'):

[0174]

[0175] wherein each z is independently 0 or 1.

[0176] Item 12. The phenylnaphthol compound according to any one of Items 1 to 11, wherein R 2 At the positions shown in the core skeleton structure of the following formula (I"):

[0177]

[0178] where each y is independently 0 or 1.

[0179] Item 13. A method for producing an indole naphthol compound comprising a core skeleton structure represented by formula (II):

[0180]

[0181] in,

[0182] m is 0 to 4;

[0183] n is 0 to 4;

[0184] R 1 and R 2 each independently represents a hydroxyl group, a cyano group, a (meth)acrylate group, an amino group, a halide group, a substituted or unsubstituted alkyl group, a borate group, a boric acid group, a polyether group, a polyester group, a polycarbonate group, a polyurethane group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocycloalkyl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a ketone group, an aldehyde group, an ester group, a carboxylic acid group, a carboxylate group, an amide group, a carbonate group, a carbamate group, a urea group, a siloxane group, an alkoxysilane group, or a polysiloxane group;

[0185] The two R 1 Group or two R 2 The groups can be linked to form rings;

[0186] R 3 is selected from substituted or unsubstituted 2-pyridyl or substituted or unsubstituted 2-quinolyl;

[0187] wherein the pyridyl and quinolyl substituents are selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, halogen, amino, ester, carboxylate, or hydroxyl; and

[0188] R 4 is selected from hydrogen, substituted or unsubstituted alkyl, alkoxymethyl, substituted or unsubstituted silyl, or acyl; and

[0189] The method comprises cyclizing a phenylnaphthol compound as described in any one of clauses 1 to 12 in the presence of a catalyst.

[0190] Clause 14. The method of Clause 13, wherein the catalyst is a transition metal catalyst.

[0191] Clause 15. The method of Clause 13 or 14, wherein the catalyst comprises copper, zinc, palladium, platinum, rhodium or iridium.

[0192] Clause 16. The method of any one of Clauses 13 to 15, wherein the catalyst comprises copper.

[0193] Clause 17. The method according to any one of clauses 13 to 16, further comprising alkylation or arylation to produce an indole naphthol compound comprising a core skeleton structure represented by formula (III):

[0194]

[0195] Where R 5 is selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or acyl.

[0196] Clause 18. The method of clause 17, wherein R 5 It is an alkyl group.

[0197] Item 19. The process according to Item 17 or 18, comprising alkylation by reaction with an alkyl halide, triflate or tosylate in the presence of a base.

[0198] Item 20. The method of Item 19, comprising deprotonating the indole with a base and reacting the resulting anion with the alkyl halide, triflate or tosylate.

[0199] Clause 21. The method of clause 17, wherein R 5 is a substituted or unsubstituted phenyl group.

[0200] Item 22. The method according to Item 17 or 21, comprising arylation by a cross-coupling reaction with a transition metal catalyst and an aryl halide.

[0201] Item 23. The method of Item 22, wherein the cross-coupling reaction is an Ullmann coupling reaction with a copper catalyst.

[0202] Item 24. The method of Item 17 or 21, comprising arylation by nucleophilic aromatic substitution reaction with an aryl fluoride.

[0203] Clause 25. The method according to any one of clauses 13 to 24, further comprising: 4 When R is a substituted or unsubstituted alkyl group, an alkoxymethyl group, a substituted or unsubstituted silyl group, or an acyl group, 4 Deprotection to generate the hydroxyl group.

[0204] Item 26. The method according to Item 25, wherein the deprotection is carried out under palladium hydrogenation conditions or with a strong acid.

[0205] Item 27. The method according to Item 26, wherein the deprotection is carried out under palladium on carbon.

[0206] Clause 28. The method of any one of clauses 13 to 27, further comprising reacting with a diaryl propargyl alcohol to form an indole naphthopyran compound comprising a core skeleton structure represented by formula (IV):

[0207]

[0208] wherein B and B' are each independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0209] Item 29. The process according to Item 28, wherein the reaction with the diaryl propargyl alcohol is carried out under acidic conditions.

[0210] Clause 30. The method of Clause 28 or 29, wherein B and B' are each independently substituted or unsubstituted phenyl.

[0211] Clause 31. The method of Clause 30, wherein each phenyl substituent is independently at each occurrence alkoxy, halogen, alkyl, or aryloxy.

[0212] The present invention has been described with reference to specific details of particular embodiments thereof. It is not intended that these details be considered limitations on the scope of the invention except to the extent they are included in the appended claims.

Claims

1. A phenylnaphthol compound having a structure represented by formula (I): in, m is 0 to 4, and n is 0 to 4; Independent of each m's R 1 and R is independent of each n 2 Each independently selected from: i. a halo group selected from fluorine, chlorine, bromine or iodine; ii. unsubstituted straight chain or branched C1-C6 alkyl; iii. an unsubstituted heteroaryl selected from the group consisting of furanyl, pyranyl, pyridinyl, isoquinolinyl and pyrimidinyl; iv. unsubstituted linear or branched C1-C6 alkoxy or unsubstituted phenoxy; v. unsubstituted linear or branched C1-C6 alkylthio, unsubstituted phenylthio, or linear or branched C1-C6 substituted phenylthio; R 3 is selected from unsubstituted 2-pyridyl or unsubstituted 2-quinolyl, and R 4 Selected from hydrogen, unsubstituted straight chain or branched C1-C6 alkyl, phenyl-substituted straight chain or branched C1-C6 alkyl, or straight chain or branched C1-C6 alkoxymethyl.

2. The phenylnaphthol compound according to claim 1, wherein R 1 or R 2 It is a straight chain or branched C1-C6 alkoxy group.

3. The phenylnaphthol compound according to claim 1, wherein R 3 It is 2-pyridyl.

4. The phenylnaphthol compound according to claim 1, wherein R 4 It's benzyl.

5. A method for producing an indole naphthol compound having a structure represented by formula (II): Where m, n, R 1 , R 2 and R 4 As defined by formula (I) in claim 1, and The method comprises cyclizing the phenylnaphthol compound as claimed in claim 1 in the presence of a transition metal catalyst, wherein the transition metal catalyst comprises copper, zinc, palladium, platinum, rhodium or iridium.

6. The method of claim 5, further comprising alkylation or arylation to produce an indole naphthol compound having a structure represented by formula (III): Where R 5 Selected from unsubstituted straight or branched C1-C6 alkyl, or unsubstituted phenyl.

7. The method of claim 6, further comprising: When R 4 When R is an unsubstituted straight or branched C1-C6 alkyl group, or a straight or branched C1-C6 alkoxymethyl group, 4 Deprotection to generate the hydroxyl group, and Reaction with a diaryl propargyl alcohol to form an indole naphthopyran compound having a structure represented by formula (IV): wherein B and B' are each independently an unsubstituted phenyl group, or a phenyl group substituted by at least one of a linear or branched C1-C6 alkoxy group, a halogen group selected from F, Br and Cl, a linear or branched C1-C6 alkyl group, or a phenoxy group.

8. The method of claim 5, wherein: The transition metal catalyst includes copper.

9. The process of claim 6, comprising alkylation by reaction with an alkyl halide, triflate or tosylate in the presence of a base.

10. The method of claim 6, comprising arylation by a cross-coupling reaction with a transition metal catalyst and an aryl halide, wherein the transition metal catalyst comprises copper.

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