Polycyclic aromatic sulfonium compounds

Abstract

This invention provides compounds that can be applied to various coupling reactions while improving the low solubility of naphthalenes, binaphthalenes, and polycyclic aromatic hydrocarbon compounds (PAHs). [Solution] General formula (1): TIFF2026145050000070.tif23170[where, Ar 1 R represents a naphthalene ring, binaphthalene ring, or polycyclic aromatic hydrocarbon ring, which may have substituents. 1 and R 2 This represents an aryl group that may have one or two substituents, and may be identical or different. A polycyclic aromatic sulfonium compound having a cation represented by .

Description

[Technical Field]

[0001] This invention relates to polycyclic aromatic sulfonium compounds. [Background technology]

[0002] Thiantreniumization of aromatic rings using thiantrene S-oxide has recently been developed, primarily by Ritter et al., as a new method for functionalizing aromatic rings (see, for example, Non-Patent Literature 1). Non-Patent Literature 1 states that by thiantreniumizing a benzene ring, various functional groups can be introduced to the thiantreniumized site.

[0003] However, Non-Patent Literature 1 shows that functionalization is almost exclusively limited to compounds without fused ring structures, and there are no examples of its application to naphthalene, binaphthalene, or polycyclic aromatic hydrocarbon compounds (PAHs) in which three or more benzene rings are fused. Regarding the functionalization of aromatic rings with fused ring structures, recent work has been limited to Dumele et al. thianthriniumizing relatively small polycyclic aromatic hydrocarbon compounds (PAHs) (see, for example, Non-Patent Literature 2). [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] Nature 2019, 567, 223-228. [Non-Patent Document 2] ChemRxiv, 2024, DOI: 10.26434 / chemrxiv-2024-4nh7w-v2 [Overview of the project] [Problems that the invention aims to solve]

[0005] Polycyclic aromatic hydrocarbons (PAHs) have low solubility in organic solvents and are naturally insoluble in water. However, even when thianthreniumization is performed on PAHs using thianthrene S-oxide, the solubility of the resulting PAH-thianthrenium salt does not significantly improve. Due to this low solubility, the application of the above-mentioned thianthreniumization functionalization method to PAHs is generally avoided.

[0006] Since thianthreniumized naphthalenes, binaphthalenes, and polycyclic aromatic hydrocarbon compounds (PAHs) are expected to be further functionalized by cross-coupling reactions and the like, the present invention aims to provide compounds that can be applied to various coupling reactions while improving the low solubility of naphthalenes, binaphthalenes, and polycyclic aromatic hydrocarbon compounds (PAHs). [Means for solving the problem]

[0007] In light of the above objectives, and after diligent research, the present inventors have found that by sulfonizing specific skeletons of naphthalene, binaphthalene, and polycyclic aromatic hydrocarbon compounds (PAHs), it is possible to solve the above problems and functionalize polycyclic aromatic hydrocarbon compounds (PAHs) while improving their low solubility. In other words, the present invention encompasses the following configuration.

[0008] Term 1. General formula (1):

[0009] [ka]

[0010] [In the formula, Ar 1 R represents a naphthalene ring, binaphthalene ring, or polycyclic aromatic hydrocarbon ring, which may have substituents. 1 and R 2 This represents an aryl group that may have one or two substituents, and may be identical or different. A polycyclic aromatic sulfonium compound having a cation represented by

[0011] Item 2. The R 1 and R 2 is an optionally substituted phenyl group, the polycyclic aromatic sulfonium compound according to Item 1.

[0012] Item 3. The R 1 and R 2 is a substituted phenyl group, the polycyclic aromatic sulfonium compound according to Item 1 or 2.

[0013] Item 4. The R 1 and R 2 wherein the substituent in is a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted glycol group, or an optionally substituted dialkylamino group, the polycyclic aromatic sulfonium compound according to any one of Items 1 to 3.

[0014] Item 5. The polycyclic aromatic sulfonium compound according to any one of Items 1 to 4, further comprising a counter anion.

[0015] Item 6. A fluorescent dye comprising the polycyclic aromatic sulfonium compound according to any one of Items 1 to 5.

[0016] Item 7. An organelle staining agent for intracellular use comprising the fluorescent dye according to Item 6.

[0017] Item 8. A method for producing the polycyclic aromatic sulfonium compound according to any one of Items 1 to 5, comprising: in the presence of a strong acid and a strong acid anhydride, naphthalene, binaphthalene or a polycyclic aromatic hydrocarbon compound (Ar 1 ; Ar 1 is as defined above) and General Formula (2):

[0018]

Chemical Formula

[0019] [In the formula, R 1 and R 2 This is the same as above. A step of reacting with a sulfinyl compound represented by A manufacturing method that includes the following features.

[0020] Section 9. General formula (3A):

[0021] [ka]

[0022] [In the formula, Ar 1 The same applies as above. R 3a [where n1 represents a halogen atom or a cyano group, and n1 represents 1 or 2] A method for producing polycyclic aromatic compounds represented by, In the presence of a ruthenium catalyst and a copper compound, A step of reacting a polycyclic aromatic sulfonium compound described in any one of items 1 to 5 with a compound having a halogen atom or a cyano group. A manufacturing method that includes the following features.

[0023] Section 10. General formula (3B):

[0024] [ka]

[0025] [In the formula, Ar 1 The same applies as above. R 3b n2 represents an optionally substituted alkenyl group or an optionally substituted alkynyl group. n2 represents 1 or 2. A method for producing polycyclic aromatic compounds represented by, In the presence of a palladium catalyst and a copper compound, A step of reacting a polycyclic aromatic sulfonium compound described in any one of items 1 to 5 with a compound having an alkenyl group or an alkynyl group. A manufacturing method that includes the following features.

[0026] Item 11. General formula (3C):

[0027] [ka]

[0028] [In the formula, Ar 1 The same applies as above. R 3c [where n3 represents an aryl group which may have substituents. n3 represents 1 or 2.] A method for producing polycyclic aromatic compounds represented by, In the presence of a palladium catalyst, A step of reacting a polycyclic aromatic sulfonium compound described in any one of items 1 to 5 with a compound having an aryl group. A manufacturing method that includes the following features.

[0029] Item 12. Method for producing extended polycyclic aromatic hydrocarbon compounds, A step of subjecting a polycyclic aromatic compound represented by general formula (3C), obtained by the manufacturing method described in item 11, to a ring fusion reaction. A manufacturing method that includes the following features.

[0030] Item 13. A method for increasing the fluorescence maximum wavelength of naphthalene, binaphthalene, or polycyclic aromatic hydrocarbon compounds, In the presence of strong acids and strong acid anhydrides, The naphthalene, binaphthalene, or polycyclic aromatic hydrocarbon compound, General formula (2):

[0031] [ka]

[0032] [In the formula, R 1 and R 2 This represents a (hetero)aryl group which may have one or two substituents, either identical or different. A step of reacting with a sulfinyl compound represented by A method that includes [something].

[0033] Item 14. Solubilizers for naphthalene, binaphthalene, or polycyclic aromatic hydrocarbon compounds, General formula (2):

[0034] [ka]

[0035] [In the formula, R 1 and R 2 This represents a (hetero)aryl group which may have one or two substituents, either identical or different. A solubilizer for naphthalene, binaphthalene, or polycyclic aromatic hydrocarbon compounds, comprising a sulfinyl compound represented by , a strong acid, and a strong acid anhydride.

[0036] Section 15. General formula (2A):

[0037] [ka]

[0038] [In the formula, R 4 and R 5 These represent identical or distinct alkoxy groups or glycol groups having 6 to 20 carbon atoms. A compound represented by the formula. [Effects of the Invention]

[0039] According to the present invention, it is possible to provide compounds that can be applied to various coupling reactions while improving the low solubility of naphthalene, binaphthalene, and polycyclic aromatic hydrocarbon compounds (PAHs). [Brief explanation of the drawing]

[0040] [Figure 1] Examples 5 to 13 demonstrate the substrate adaptability of polycyclic aromatic hydrocarbon compounds. [Figure 2] The absorption spectrum of 2,5,12,15-tetrakis(tert-butyl)quaterylene (21) obtained in Example 17 is shown. [Figure 3] The ORTEP diagram for 2,5,12,15-tetrakis(tert-butyl)quaterylene(21) (CCDC: 2397243) obtained in Example 17 with a thermal elliptic of 50% is shown. Counteranions and solvents have been omitted for clarity. [Figure 4] The results of single-crystal X-ray structural analysis of 5,12-bis(3,5-di-tert-butylphenyl)rubicene (23b) obtained in Example 19 are shown below. [Figure 5] The results of the photochemical properties of Test Example 2 are shown. [Figure 6] The results of imaging HeLa cells using bis(4-(2-(2-(2-2-methoxyethoxy)ethoxy)ethoxy)phenyl)(perylene-3-yl)sulfonium tetrafluoroborate (14d), obtained in Example 8 of Test Example 3, are shown. (A) Fluorescence of compound 14d. (B) Mitochondrial marker. (C) Differential interference contrast (DLC). (D) Merged image of A, B, and C. [Figure 7] The cell viability in DMS in Test Example 3 and when using 2,5,12,15-tetrakis(tert-butyl)quaterylene (21) obtained in Example 17 is shown. [Modes for carrying out the invention]

[0041] In this specification, "contains" is a concept that encompasses all of the following: "contains," "consist essentially of," and "consist of."

[0042] Furthermore, in this specification, when a numerical range is indicated as "A to B", it means A or greater and B or less.

[0043] Furthermore, in this specification, polycyclic aromatic hydrocarbon compounds (PAHs) mean compounds having a structure in which three or more benzene rings are fused together.

[0044] 1. Polycyclic aromatic sulfonium compounds The polycyclic aromatic sulfonium compound of the present invention has general formula (1):

[0045] [ka]

[0046] [In the formula, Ar 1 R represents a naphthalene ring, binaphthalene ring, or polycyclic aromatic hydrocarbon ring, which may have substituents. 1 and R 2 This represents an aryl group that may have one or two substituents, and may be identical or different. It has a cation represented by . The polycyclic aromatic sulfonium compound of the present invention can solubilize polycyclic aromatic hydrocarbon compounds (PAHs), which are conventionally insoluble in water and poorly soluble in organic solvents, and it is possible to introduce various functional groups. This not only enables further organic conversion of polycyclic aromatic hydrocarbon compounds (PAHs), but also functions as a staining agent for intracellular organelles.

[0047] Furthermore, the polycyclic aromatic sulfonium compound of the present invention is composed of a polycyclic aromatic hydrocarbon (PAH) moiety that is hydrophobic and has a broad π-plane, and a hydrophilic, cationic sulfonium moiety, and has the property of emitting fluorescence derived from the polycyclic aromatic hydrocarbon (PAH), so it can be expected to have biological applications such as selective fluorescence imaging in cells and nuclei, and as a material for transporting substances (e.g., nucleic acids) into cells and nuclei.

[0048] The polycyclic aromatic sulfonium compound of the present invention comprises a naphthalene ring, a binaphthalene ring, or a polycyclic aromatic hydrocarbon ring, that is, Ar in general formula (1). 1There are no particular restrictions on the number of rings in the naphthalene ring, binaphthalene ring, or polycyclic aromatic hydrocarbon ring represented by , but from the viewpoint of ease of precise synthesis, ease of solubilization of polycyclic aromatic hydrocarbon compounds, ease of subsequent functionalization, and ease of introduction into living organisms, 2 to 20 is preferred, 3 to 18 is more preferred, and 4 to 15 is even more preferred.

[0049] The naphthalene ring, binaphthalene ring, or polycyclic aromatic hydrocarbon ring constituting the polycyclic aromatic sulfonium compound of the present invention is not particularly limited, and examples include naphthalene ring, binaphthalene ring, pentalene ring, indene ring, anthracene ring, phenanthrene ring, tetracene ring, pyrene ring, chrysene ring, triphenylene ring, fluorantene ring, dibenzopentalene ring, pentacene ring, perylene ring, benzopyrene ring, dibenzochrysene ring, cornulene ring, rubicene ring, terylene ring, quaterylene ring, quinterylene ring, hexabenzocoronene ring, hexabenzotetracene ring, and the like.

[0050] The polycyclic aromatic sulfonium compound of the present invention comprises a naphthalene ring, a binaphthalene ring, or a polycyclic aromatic hydrocarbon ring, that is, Ar in general formula (1). 1 The naphthalene ring, binaphthalene ring, or polycyclic aromatic hydrocarbon ring represented by may have substituents. There are no particular restrictions on substituents, and examples include hydroxyl groups, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.), alkyl groups described below, alkoxy groups described below, aryl groups described below, alkoxycarbonyl groups (methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, n-butyloxycarbonyl group, etc.), dialkylamino groups (amino groups substituted with alkyl groups described below), diarylamino groups (amino groups substituted with aryl groups described below), trialkylammonio groups (ammonio groups substituted with alkyl groups described below), etc. These substituents can be used individually or in combination.

[0051] The polycyclic aromatic sulfonium compounds of the present invention, considering their use as intracellular organelle staining agents, i.e., in vivo, preferably employ substituents that easily improve solubility in physiological buffers, i.e., substituents that easily improve water solubility. From this viewpoint, the Ar in general formula (1) 1 The substituents on the naphthalene ring, binaphthalene ring, or polycyclic aromatic hydrocarbon ring represented by are preferably hydroxyl groups, alkoxy groups, alkoxycarbonyl groups, dialkylamino groups (amino groups substituted with the alkyl group described below), diarylamino groups (amino groups substituted with the aryl group described below), trialkylammonio groups (ammonio groups substituted with the alkyl group described below), more preferably hydroxyl groups and alkoxycarbonyl groups, and even more preferably alkoxycarbonyl groups.

[0052] The number of substituents in the case of these substituents is not particularly limited, but from the viewpoint of facilitating precise synthesis and facilitating the solubilization of polycyclic aromatic hydrocarbon compounds, 1 to 10 substituents are preferred, 1 to 8 substituents are more preferred, and 1 to 6 substituents are even more preferred.

[0053] Furthermore, as substituents, sulfonium groups are particularly important, as shown in general formula (4):

[0054] [ka]

[0055] [In the formula, R 1 and R 2 This is the same as above. It is also possible to adopt a base represented by .

[0056] In other words, the polycyclic aromatic sulfonium compound of the present invention may have multiple groups represented by general formula (4). The number of groups represented by general formula (4) in the polycyclic aromatic sulfonium compound of the present invention is not particularly limited, but from the viewpoint of ease of precise synthesis, ease of solubilization of polycyclic aromatic hydrocarbon compounds, ease of subsequent functionalization, and ease of introduction into living organisms, it is usually preferable to have 1 to 3 groups, and more preferably 1 to 2 groups.

[0057] In general formula (1), R 1 and R 2 The aryl group represented by is not particularly limited, but can be monocyclic or polycyclic (e.g., bicyclic, tricyclic, etc.), but is preferably monocyclic. Specific examples of the aryl group include phenyl, naphthyl, biphenyl, pentarenyl, indenyl, anthracenyl, phenantrenyl, and fluorenyl groups. Among these, the phenyl group is preferred from the viewpoint of being easy to synthesize precisely, easy to solubilize polycyclic aromatic hydrocarbon compounds, and easy to introduce into living organisms.

[0058] The polycyclic aromatic sulfonium compounds of the present invention, considering their use as intracellular organelle staining agents, i.e., in vivo, preferably employ substituents that easily improve solubility in physiological buffers, i.e., substituents that easily improve water solubility. From this viewpoint, R in general formula (1) 1 and R 2 Preferred substituents on the aryl group represented by are halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.), alkyl groups, alkoxy groups, glycol groups, dialkylamino groups (amino groups substituted with alkyl groups, as described later).

[0059] Note that R in general formula (1) 1 and R 2 The number of substituents on the aryl group represented by is such that if there are too many substituents, the polycyclic aromatic sulfonium compound of the present invention cannot be obtained. Therefore, even when substituents are present, the number of substituents is 1 to 2, preferably 1. 1 and R 2 When the aryl group represented by is a phenyl group, there are no particular restrictions on the substitution site if substituents are present, but from the viewpoint of facilitating precise synthesis and facilitating the solubilization of polycyclic aromatic hydrocarbon compounds, substitution at the para position is preferable.

[0060] R in general formula (1) 1 and R 2The alkyl group as a substituent of the aryl group represented by can be linear or branched (preferably linear), but linear alkyl groups are preferred from the viewpoint of ease of precise synthesis and ease of solubilizing polycyclic aromatic hydrocarbon compounds. The number of carbon atoms in the alkyl group is not particularly limited, for example, 1 to 20 is preferred, and 1 to 15 is more preferred. Specific examples of the alkyl group include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, etc.

[0061] R in general formula (1) 1 and R 2 The alkyl group, which is a substituent on the aryl group represented by , may have substituents. There are no particular restrictions on substituents, and examples include hydroxyl groups, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.), alkoxy groups described later, glycol groups described later, etc. When these substituents are present, there are no particular restrictions on the number of substituents, but from the viewpoint of facilitating precise synthesis, facilitating solubilization of polycyclic aromatic hydrocarbon compounds, facilitating subsequent functionalization, and facilitating introduction into living organisms, 1 to 10 substituents are preferred, 1 to 8 substituents are more preferred, and 1 to 6 substituents are even more preferred.

[0062] R in general formula (1) 1 and R 2The alkoxy group as a substituent on the aryl group represented by can be linear or branched (preferably linear), but a linear alkoxy group is preferred from the viewpoint of ease of precise synthesis and ease of solubilizing polycyclic aromatic hydrocarbon compounds. The number of carbon atoms in the alkoxy group is not particularly limited, for example, 1 to 20 is preferred, and 1 to 15 is more preferred. Specific examples of the alkoxy group include, for example, a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a tert-butyloxy group, a sec-butyloxy group, an n-pentyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, an n-nonyloxy group, an n-decyloxy group, an n-undecyloxy group, and an n-dodecyloxy group.

[0063] R in general formula (1) 1 and R 2 The alkoxy group, which is a substituent on the aryl group represented by , may have substituents. There are no particular restrictions on substituents, and examples include hydroxyl groups, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.), the above-mentioned alkoxy group, and the glycol group described later. The number of substituents when these substituents are present is not particularly limited, but from the viewpoint of facilitating precise synthesis, facilitating solubilization of polycyclic aromatic hydrocarbon compounds, facilitating subsequent functionalization, and facilitating introduction into living organisms, 1 to 10 substituents are preferred, 1 to 8 substituents are more preferred, and 1 to 6 substituents are even more preferred.

[0064] R in general formula (1) 1 and R 2 The glycol group that can be a substituent on the aryl group shown is not particularly limited, but examples include -O(CH2CH2O)2H, -O(CH2CH2O)2CH3, -O(CH2CH2O)3H, -O(CH2CH2O)3CH3, -O(CH2CH2O)4H, -O(CH2CH2O)4CH3, etc.

[0065] R in general formula (1) 1 and R 2The glycol group, which is a substituent on the aryl group represented by , may have substituents. There are no particular restrictions on substituents, and examples include hydroxyl groups, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.), the alkyl groups mentioned above, the alkoxy groups mentioned above, and the glycol groups mentioned above. The number of substituents when these substituents are present is not particularly limited, but from the viewpoint of facilitating precise synthesis, facilitating solubilization of polycyclic aromatic hydrocarbon compounds, facilitating subsequent functionalization, and facilitating introduction into living organisms, 1 to 10 substituents are preferred, 1 to 8 substituents are more preferred, and 1 to 6 substituents are even more preferred.

[0066] Therefore, the polycyclic aromatic sulfonium compound of the present invention has the general formula (1A):

[0067] [ka]

[0068] [In the formula, Ar 1 The same applies as above. R 1a and R 2a These terms, whether identical or distinct, represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted glycol group. Compounds represented by are preferred.

[0069] In this invention, a naphthalene ring, a binaphthalene ring, or a polycyclic aromatic hydrocarbon ring (Ar 1 The site to which the sulfonium group (general formula (4)) is attached in the compound is not particularly limited. However, according to the manufacturing method of the present invention described later, the sulfonium group (general formula (4)) is introduced to some extent selectively, so the position of the sulfonium group (general formula (4)) in the polycyclic aromatic sulfonium compound of the present invention is also determined to some extent. For example, as follows, if the compound has a naphthalene skeleton, the sulfonium group (general formula (4)) is likely to be at position 1; if the compound has a triphenylene skeleton, the sulfonium group (general formula (4)) is likely to be at the carbon atom adjacent to position 1; and if the compound has a rubicene skeleton, the sulfonium group (general formula (4)) is likely to be at position 5.

[0070] [ka]

[0071] In the formula, R 1 and R 2 The same applies as above.

[0072] Furthermore, the polycyclic aromatic sulfonium compounds of the present invention may also have a counteranion corresponding to the sulfonium group which is the cationic moiety. Examples of possible counteranions include halogen ions (fluoride ions, chloride ions, bromide ions, iodide ions) and hexafluorophosphate anions (PF6). - ), tetrafluoroborate anion (BF4 - Examples include the following. The number of counter anions can be adjusted so that the valency is suitable according to the number of sulfonium groups in the polycyclic aromatic sulfonium compound of the present invention.

[0073] The polycyclic aromatic sulfonium compounds of the present invention that satisfy the above conditions are, for example,

[0074] [ka]

[0075] [ka]

[0076] [ka]

[0077] [ka]

[0078] [ka]

[0079] These are some examples.

[0080] 2. Fluorescent dyes and intracellular organelle stains The fluorescent dye of the present invention contains the polycyclic aromatic sulfonium compound of the present invention described above.

[0081] Furthermore, the fluorescent dyes of the present invention containing the polycyclic aromatic sulfonium compound of the present invention can stain intracellular organelles depending on the structure adopted. For example, in general formula (1A), R 1a and R 2a When the compound is a glycol group, it is easier to selectively stain mitochondria. Furthermore, by adjusting the structure, it is expected that other intracellular organelles can also be stained. For this reason, the fluorescent dye of the present invention, which uses the polycyclic aromatic sulfonium compound of the present invention as described above, is useful in that it can be used as an intracellular organelle staining agent (mitochondrial staining agent, lipid droplet staining agent, lysosome staining agent, endoplasmic reticulum staining agent, cell membrane staining agent, etc.).

[0082] The fluorescent dye of the present invention contains the polycyclic aromatic sulfonium compound of the present invention described above. There are no particular restrictions on its form of use; for example, it can be dissolved in an organic solvent to form a solution. In this case, the content of the polycyclic aromatic sulfonium compound of the present invention described above can be adjusted as appropriate, from the viewpoint of easily detecting (staining) even small intracellular organelles with high sensitivity, easily suppressing fluorescence of tissues other than oil droplets and intracellular organelles, and easily identifying intracellular organelles.

[0083] When the fluorescent dye (intracellular organelle staining agent) of the present invention is a solution containing the polycyclic aromatic sulfonium compound of the present invention as described above, preferred organic solvents that can be used are, from the viewpoint of easily dissolving the polycyclic aromatic sulfonium compound of the present invention and easily fluorescing intracellular organelles with high sensitivity, water; aliphatic halogenated hydrocarbons such as chloroform, dichloromethane, and dichloroethane; aliphatic saturated hydrocarbons such as pentane, hexane, and heptane; ethers such as tetrahydrofuran, 1,4-dioxane, and diethyl ether; ketones such as acetone; esters such as ethyl acetate; nitriles such as acetonitrile; and dimethyl sulfoxides.

[0084] When the fluorescent dye (intracellular organelle staining agent) of the present invention is in solution form, a pH of approximately 5 to 11 is preferred, and more preferably approximately 6.5 to 7.5, from the viewpoint of ease of use in living cells and ease of highly sensitive detection of intracellular organelles even at small sizes. Buffers (such as HEPES buffer, Tris buffer, Trisine-sodium hydroxide buffer, phosphate-based buffer, phosphate-buffered saline, etc.) can also be used to adjust the pH of the fluorescent dye (intracellular organelle staining agent) of the present invention.

[0085] 3. Method for producing polycyclic aromatic sulfonium compounds The method for producing the polycyclic aromatic sulfonium compound of the present invention described above is not particularly limited, In the presence of strong acids and strong acid anhydrides, Naphthalene, binaphthalene, or polycyclic aromatic hydrocarbon compounds (Ar 1 ;Ar 1 (This is the same as above) General formula (2):

[0086] [ka]

[0087] [In the formula, R 1 and R 2 This is the same as above. It can be produced by reacting it with a sulfinyl compound represented by .

[0088] This allows for the solubilization of insoluble naphthalene, binaphthalene, or polycyclic aromatic hydrocarbon compounds. In other words, a composition containing a sulfinyl compound represented by general formula (2), a strong acid, and a strong acid anhydride can be used as a solubilizer for naphthalene, binaphthalene, or polycyclic aromatic hydrocarbon compounds.

[0089] Furthermore, in the presence of strong acids and strong acid anhydrides, Naphthalene, binaphthalene, or polycyclic aromatic hydrocarbon compounds (Ar 1 ;Ar 1 (This is the same as above) General formula (2):

[0090] [ka]

[0091] [In the formula, R 1 and R 2 This is the same as above. By reacting it with a sulfinyl compound represented by [formula], the fluorescence maximum wavelength of an aromatic hydrocarbon compound can be increased.

[0092] In addition, in the sulfinyl compound represented by general formula (2), R 1 and R 2 It is important that it is easy to move, R 1 and R 2 When the molecules come together to form a ring, the reaction is less likely to proceed.

[0093] The substrate used is naphthalene, binaphthalene, or a polycyclic aromatic hydrocarbon compound, as described above. 1 The naphthalene ring, binaphthalene ring, or polycyclic aromatic hydrocarbon ring described above can be used as a compound as is.

[0094] While there are no particular restrictions on what constitutes a strong acid, examples include sulfuric acid, hydrochloric acid, trifluoroacetic acid, and trifluoromethanesulfonic acid. These strong acids can be used individually or in combination of two or more.

[0095] While there are no particular restrictions on the amount of strong acid used, from the viewpoint of conversion rate, selectivity, yield, etc., 0.5 to 5.0 moles, and more preferably 1.0 to 3.0 moles, are preferred per mole of the polycyclic aromatic hydrocarbon substrate. If multiple strong acids are used, their total amount can be adjusted to fall within the above range.

[0096] Furthermore, by using strong acid anhydrides, it is possible to remove an oxygen atom from the sulfinyl compound represented by general formula (2) and facilitate the reaction. Examples of such strong acid anhydrides include trifluoromethanesulfonic acid anhydride (Tf2O) and trifluoroacetic acid anhydride. These strong acid anhydrides can be used individually or in combination of two or more types.

[0097] While there are no particular restrictions on the amount of strong acid anhydride used, from the viewpoint of conversion rate, selectivity, yield, etc., 1.5 to 10.0 moles, and more preferably 2.0 to 5.0 moles, are preferred per mole of the substrate naphthalene, binaphthalene, or polycyclic aromatic hydrocarbon compound. When using multiple strong acid anhydrides, their total amount can be adjusted to fall within the above range.

[0098] Sulfinyl compounds represented by general formula (2) are general formula (2A):

[0099] [ka]

[0100] [In the formula, R 1a and R 2a This is the same as above. Compounds represented by this formula (2A) are preferred. This compound represented by this general formula (2A) is a novel compound not described in the literature.

[0101] In this invention, naphthalene, binaphthalene, or polycyclic aromatic hydrocarbon compounds (Ar 1 The site to which the sulfonium group (general formula (4)) is attached in ) is not particularly limited, but the sulfonium group (general formula (4)) is introduced to some extent selectively. For example, as shown below, naphthalene, binaphthalene or polycyclic aromatic hydrocarbon compounds (Ar 1 If the carbon atom has a naphthalene skeleton, a sulfonium group (general formula (4)) is likely to be introduced at position 1; if it has a triphenylene skeleton, a sulfonium group (general formula (4)) is likely to be introduced to the carbon atom adjacent to position 1; and if it has a rubicene skeleton, a sulfonium group (general formula (4)) is likely to be introduced at position 5.

[0102] [ka]

[0103] In the formula, R 1 and R 2 The same applies as above.

[0104] A sulfinyl compound represented by general formula (2) that satisfies the above conditions is, for example,

[0105] [ka]

[0106] These are some examples.

[0107] The amount of sulfinyl compound represented by general formula (2) used is not particularly limited, but from the viewpoint of conversion rate, selectivity, yield, etc., 0.3 to 3.0 moles and more preferably 0.5 to 1.5 moles per mole of the substrate naphthalene, binaphthalene, or polycyclic aromatic hydrocarbon compound is preferred.

[0108] The reaction can usually be carried out in the presence of a solvent. While there are no particular restrictions on the solvents that can be used, examples include aliphatic halogenated hydrocarbons such as dichloromethane and dichloroethane; aromatic halogenated hydrocarbons such as chlorobenzene; nitriles such as acetonitrile; and carbon disulfide. These solvents can be used individually or in combination of two or more.

[0109] The reaction atmosphere can be an inert atmosphere such as a nitrogen gas atmosphere or an argon gas atmosphere.

[0110] The reaction temperature is not particularly limited, but from the viewpoint of conversion rate, selectivity, yield, etc., it can usually be set to around 0-50°C, and especially around 10-40°C. The reaction time should be set to a time when the reaction is sufficiently completed.

[0111] After the reaction is complete, the compound can be purified by conventional methods as needed to obtain the polycyclic aromatic sulfonium compound of the present invention.

[0112] 4. Functionalization of polycyclic aromatic sulfonium compounds (Part 1) The polycyclic aromatic sulfonium compounds of the present invention can subsequently be given various properties by introducing various functional groups to the sulfonium group moiety.

[0113] For example, general formula (3A):

[0114] [ka]

[0115] [In the formula, Ar 1 The same applies as above. R 3a [where n1 represents a halogen atom or a cyano group, and n1 represents 1 or 2] A method for producing polycyclic aromatic compounds represented by, In the presence of a ruthenium catalyst and a copper compound, This can be obtained by reacting the polycyclic aromatic sulfonium compound of the present invention with a compound having a halogen atom or a cyano group.

[0116] In general formula (3A), R 3a Examples of halogen atoms represented by include fluorine, chlorine, bromine, and iodine atoms.

[0117] Furthermore, in the general formula (3A), R 3a The number n1 is either 1 or 2.

[0118] Therefore, the target product, a polycyclic aromatic compound represented by general formula (3A), is, for example,

[0119] [ka]

[0120] [ka]

[0121] These are some examples.

[0122] While there are no particular restrictions on ruthenium catalysts, examples include dichlorotris(2,2'-bipyridyl)ruthenium(II) (RuCl2(bpy)3), dichlorotris(triphenylphosphino)ruthenium(II) (RuCl2(PPh3)3), RuCl3, RuBr3, RuI3, dichlorotetrakis(dimethyl sulfoxide)ruthenium(II) (RuCl2(DMSO)4), and dichloro(1,5-cyclooctadiene)ruthenium(II) polymer ([Ru(cod)Cl2] nExamples include dibromotris(triphenylphosphino)ruthenium(II) (RuBr2(PPh3)3), diiodotris(triphenylphosphino)ruthenium(II) (RuI2(PPh3)3), RuH4(PPh3)3, RuH(OAc)(PPh3)3, RuH2(PPh3)4, etc. (In the examples, DMSO represents dimethyl sulfoxide, cod represents 1,5-cyclooctadiene, Ph represents a phenyl group, and Ac represents an acetyl group. The same applies hereafter.) Among these, dichlorotris(2,2'-bipyridyl)ruthenium(II) (RuCl2(bpy)3) is preferred from the viewpoint of reactivity (yield, selectivity, etc.). Hydrates of these ruthenium catalysts can also be used. Furthermore, these ruthenium catalysts can be used individually or in combination of two or more types.

[0123] While there are no particular restrictions on the amount of ruthenium catalyst used, from the viewpoint of conversion rate, selectivity, yield, etc., 0.01 to 0.10 moles, and more preferably 0.02 to 0.05 moles, are preferred per mole of the polycyclic aromatic sulfonium compound of the present invention, which is the substrate. When using multiple ruthenium catalysts, their total amount can be adjusted to fall within the above range.

[0124] Furthermore, while there are no particular limitations on the copper compound, monovalent or divalent copper compounds can be used, with monovalent copper compounds being preferred. Examples of monovalent copper compounds include CuI, CuBr, CuCl, copper(I) acetate (CuOAc), tetrakis(acetonitrile)copper(I) tetrafluoroborate (CuBF4(MeCN)4), and tetrakis(acetonitrile)copper(I) hexafluorophosphate (CuPF6(MeCN)4). Examples of divalent copper compounds include CuCl2, CuBr2, CuF2, and copper(II) acetate (Cu(OAc)2). These copper compounds can be used individually or in combination of two or more.

[0125] While there are no particular restrictions on the amount of copper compound used, from the viewpoint of conversion rate, selectivity, yield, etc., 0.3 to 3.0 moles, and more preferably 0.5 to 2.0 moles, are preferred per mole of the polycyclic aromatic sulfonium compound of the present invention, which is the substrate. When using multiple copper compounds, their total amount can be adjusted to fall within the above range.

[0126] Compounds having a halogen atom or a cyano group are not particularly limited as long as they have a halogen atom or a cyano group, since they are compounds for introducing a halogen atom or a cyano group to the sulfonium group portion of the polycyclic aromatic sulfonium compound of the present invention. Examples include lithium halides such as LiF, LiCl, LiBr, and LiI; and tetraalkylammonium cyanides such as tetraethylammonium cyanide and tetra-n-butylammonium cyanide.

[0127] The amount of compound having a halogen atom or cyano group used is not particularly limited, but from the viewpoint of conversion rate, selectivity, yield, etc., 1 to 20 moles and more preferably 2 to 15 moles per mole of the polycyclic aromatic sulfonium compound of the present invention, which is the substrate, is preferred. When using multiple compounds having halogen atoms or cyano groups, the total amount can be adjusted so that it falls within the above range.

[0128] The reaction can usually be carried out in the presence of a solvent. While there are no particular restrictions on the solvents that can be used, examples include halogenated aliphatic hydrocarbons such as chloroform and dichloromethane; aromatic hydrocarbons such as toluene and xylene; nitrile compounds such as acetonitrile; and dimethyl sulfoxide. These solvents can be used individually or in combination of two or more.

[0129] The reaction atmosphere can be an inert atmosphere such as a nitrogen gas atmosphere or an argon gas atmosphere.

[0130] The reaction temperature is not particularly limited, but from the viewpoints of conversion rate, selectivity, yield and the like, it can usually be about 0 to 50°C, particularly about 10 to 40°C. Further, the reaction time can be set to a time sufficient for the reaction to be completed.

[0131] After completion of the reaction, purification can be performed by a conventional method as necessary to obtain a polycyclic aromatic compound represented by general formula (3A).

[0132] 5. Functionalization of polycyclic aromatic sulfonium compounds (Part 2) The polycyclic aromatic sulfonium compound of the present invention can subsequently be imparted with various properties by introducing various functional groups into the sulfonium group site.

[0133] For example, general formula (3B):

[0134]

Chemical Formula

[0135] [In the formula, Ar 1 is as defined above. R 3b represents an optionally substituted alkenyl group or an optionally substituted alkynyl group. n2 represents 1 or 2.] which is a method for producing a polycyclic aromatic compound represented by in the presence of a palladium catalyst and a copper compound, it can be obtained by reacting the polycyclic aromatic sulfonium compound of the present invention with a compound having an alkenyl group or an alkynyl group.

[0136] In general formula (3B), as the alkenyl group represented by R 3b preferred are alkenyl groups having 2 to 6 carbon atoms (particularly 2 to 4 carbon atoms), and examples thereof include a vinyl group, a 1-butenyl group, and a 2-butenyl group.

[0137] R 3bExamples of the substituent which may be optionally possessed by the alkenyl group represented by include a hydroxyl group, the above-mentioned halogen atom, the above-mentioned alkyl group, the above-mentioned alkoxy group, the above-mentioned alkenyl group, an alkynyl group described below, the above-mentioned aryl group, a carboxy group, an amide group (a dimethylamide group, a diethylamide group, an acetamido group, etc.), an alkoxycarbonyl group (a methoxycarbonyl group, an ethoxycarbonyl group, etc.), and the like. There is no particular limitation on the number of substituents when the alkenyl group has one or more substituents; 1 to 6 substituents are preferred, and 1 to 3 substituents are more preferred.

[0138] In general formula (3), R 3b As the alkynyl group represented by , an alkynyl group having 2 to 6 carbon atoms (particularly 2 to 4 carbon atoms) is preferred, and examples thereof include an ethynyl group, a 1-propynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, and the like.

[0139] R 3b Examples of the substituent which may be optionally possessed by the alkynyl group represented by include a hydroxyl group, the above-mentioned halogen atom, the above-mentioned alkyl group, the above-mentioned alkoxy group, the above-mentioned alkenyl group, the above-mentioned alkynyl group, the above-mentioned aryl group, a carboxy group, an amide group (a dimethylamide group, a diethylamide group, an acetamido group, etc.), an alkoxycarbonyl group (a methoxycarbonyl group, an ethoxycarbonyl group, etc.), and the like. There is no particular limitation on the number of substituents when the alkynyl group has one or more substituents; 1 to 6 substituents are preferred, and 1 to 3 substituents are more preferred.

[0140] Further, in general formula (3B), R 3b n2, which is the number of , is 1 or 2.

[0141] Accordingly, the target polycyclic aromatic compound represented by general formula (3B) is, for example,

[0142]

Chemical Formula

[0143]

Chemical Formula

[0144] These are some examples.

[0145] Examples of palladium catalysts include palladium compounds known as catalysts for the synthesis of organic compounds (including polymer compounds), such as tetrakis(triphenylphosphine)palladium(O)(Pd(PPh3)4), dichlorobis(triphenylphosphine)palladium(II)(PdCl2(PPh3)2), palladium(II) acetate(Pd(OAc)2), tris(dibenzylideneacetone)dipalladium(O)(Pd2(dba)3), tris(dibenzylideneacetone)dipalladium(O) chloroform complex, bis(dibenzylideneacetone)palladium(O), bis(tritert-butylphosphino)palladium(O), and (1,1'-bis(diphenylphosphino)ferrocene)dichloropalladium(II)(PdCl2(dppf)). In this process, (1,1'-bis(diphenylphosphino)ferrocene)dichloropalladium(II)(PdCl2(dppf)) is preferred from the viewpoint of ease of synthesis and yield. These palladium catalysts can be used individually or in combination of two or more types.

[0146] While there are no particular restrictions on the amount of palladium catalyst used, from the viewpoint of conversion rate, selectivity, yield, etc., 0.01 to 0.10 moles, and more preferably 0.02 to 0.05 moles, are preferred per mole of the polycyclic aromatic sulfonium compound of the present invention, which is the substrate. When using multiple palladium catalysts, their total amount can be adjusted to fall within the above range.

[0147] Furthermore, while there are no particular limitations on the copper compound, monovalent or divalent copper compounds can be used, with monovalent copper compounds being preferred. Examples of monovalent copper compounds include CuI, CuBr, CuCl, copper(I) acetate (CuOAc), tetrakis(acetonitrile)copper(I) tetrafluoroborate (CuBF4(MeCN)4), and tetrakis(acetonitrile)copper(I) hexafluorophosphate (CuPF6(MeCN)4). Examples of divalent copper compounds include CuCl2, CuBr2, CuF2, and copper(II) acetate (Cu(OAc)2). These copper compounds can be used individually or in combination of two or more.

[0148] While there are no particular restrictions on the amount of copper compound used, from the viewpoint of conversion rate, selectivity, yield, etc., 0.05 to 0.5 moles, and more preferably 0.1 to 0.3 moles, of copper compound per mole of the polycyclic aromatic sulfonium compound of the present invention, which is the substrate, is preferred. When using multiple copper compounds, their total amount can be adjusted to fall within the above range.

[0149] The compounds having an alkenyl group or alkynyl group are not particularly limited as long as they have an alkenyl group or alkynyl group, since they are compounds for introducing an alkenyl group or alkynyl group to the sulfonium group portion of the polycyclic aromatic sulfonium compound of the present invention. Examples include alkenylbenzenes such as ethenylbenzene and alkynylbenzenes such as ethynylbenzene.

[0150] The amount of compound having an alkenyl group or alkynyl group used is not particularly limited, but from the viewpoint of conversion rate, selectivity, yield, etc., 0.5 to 5 moles and more preferably 1 to 3 moles per mole of the polycyclic aromatic sulfonium compound of the present invention, which is the substrate, is preferred.

[0151] In this process, bases can also be used. Examples of usable bases include alkyllithiums such as methyllithium, ethyllithium, n-butyllithium, isobutyllithium, sec-butyllithium, and tert-butyllithium; aryllithiums such as phenyllithium; Grignard reagents; and amine compounds such as diisopropylethylamine, tributylamine, morpholine, and N-methylmorpholine. From the viewpoint of conversion rate, selectivity, and yield, amine compounds are preferred, and morpholine and N-methylmorpholine are more preferred. These bases can be used individually or in combination of two or more.

[0152] While there are no particular restrictions on the amount of base used, from the viewpoint of conversion rate, selectivity, yield, etc., 1.0 to 5.0 moles, and more preferably 1.5 to 3.0 moles, of base per mole of the polycyclic aromatic sulfonium compound of the present invention, which is the substrate, is preferred. If multiple bases are used, their total amount can be adjusted to fall within the above range.

[0153] The reaction can usually be carried out in the presence of a solvent. While there are no particular restrictions on the solvents that can be used, examples include amide compounds such as N,N-dimethylformamide; ether compounds such as tetrahydrofuran and 1,4-dioxane; halogenated aliphatic hydrocarbon compounds such as chloroform and dichloromethane; and aromatic hydrocarbon compounds such as toluene and xylene. These solvents can be used individually or in combination of two or more.

[0154] The reaction atmosphere can be an inert atmosphere such as a nitrogen gas atmosphere or an argon gas atmosphere.

[0155] While there are no particular restrictions on the reaction temperature, it is generally suitable for temperatures ranging from 20 to 80°C, and especially from 30 to 60°C, from the viewpoint of conversion rate, selectivity, and yield. The reaction time should be sufficient for the reaction to be fully completed.

[0156] After completion of the reaction, the polycyclic aromatic compound represented by general formula (3B) can be obtained by purification according to a conventional method as necessary.

[0157] 6. Functionalization of polycyclic aromatic sulfonium compounds (Part 3) The polycyclic aromatic sulfonium compound of the present invention can be imparted with various properties by subsequently introducing various functional groups into the sulfonium group site.

[0158] For example, general formula (3C):

[0159]

Chemical Formula

[0160] [wherein Ar 1 is the same as defined above. R 3c represents an aryl group which may have a substituent. n3 represents 1 or 2.] which is a method for producing a polycyclic aromatic compound represented by in the presence of a palladium catalyst, it can be obtained by reacting the polycyclic aromatic sulfonium compound of the present invention with a compound having an aryl group.

[0161] In general formula (3C), R 3c as the aryl group represented by, those described above can be employed. The same applies to the types and number of substituents.

[0162] Further, in general formula (3C), n3, which is the number of R 3c groups, is 1 or 2.

[0163] Therefore, the target polycyclic aromatic compound represented by general formula (3C) is, for example,

[0164]

Chemical Formula

[0165]

Chemical Formula

[0166] [ka]

[0167] These are some examples.

[0168] Examples of palladium catalysts include palladium compounds known as catalysts for the synthesis of organic compounds (including polymer compounds), such as tetrakis(triphenylphosphine)palladium(O)(Pd(PPh3)4), dichlorobis(triphenylphosphine)palladium(II)(PdCl2(PPh3)2), palladium(II) acetate(Pd(OAc)2), tris(dibenzylideneacetone)dipalladium(O)(Pd2(dba)3), tris(dibenzylideneacetone)dipalladium(O) chloroform complex, bis(dibenzylideneacetone)palladium(O), bis(tritert-butylphosphino)palladium(O), and (1,1'-bis(diphenylphosphino)ferrocene)dichloropalladium(II)(PdCl2(dppf)). In this process, (1,1'-bis(diphenylphosphino)ferrocene)dichloropalladium(II) (PdCl2(dppf)) is preferred from the viewpoint of ease of synthesis and yield. These palladium catalysts can be used individually or in combination of two or more types.

[0169] While there are no particular restrictions on the amount of palladium catalyst used, from the viewpoint of conversion rate, selectivity, yield, etc., 0.005 to 0.10 moles, and more preferably 0.01 to 0.05 moles, are preferred per mole of the polycyclic aromatic sulfonium compound of the present invention, which is the substrate. When using multiple palladium catalysts, their total amount can be adjusted to fall within the above range.

[0170] As for compounds having an aryl group, since they are compounds for introducing an aryl group to the sulfonium group of the polycyclic aromatic sulfonium compound of the present invention, they are not particularly limited as long as they have an aryl group, but general formula (4): YR 3c (4) [In the formula, R 3c The same applies as described above. Y represents a boronic acid or its ester group. Compounds represented by are preferred.

[0171] In general formula (4), the boronic acid represented by Y or its ester group is:

[0172] [ka]

[0173] [In the formula, two R 4 These are identical or different, representing a hydrogen atom or an alkyl group. Two R 4 These elements may come together to form a ring with adjacent -OBO- elements. A base represented by is preferred.

[0174] The above boronic acid or its ester group R 4 is a hydrogen atom or an alkyl group.

[0175] The alkyl groups described above can be used, and the types and number of substituents are also the same.

[0176] Also, R 4 If R is an alkyl group, 4 These may come together to form a ring with adjacent -OBO- groups. In this case, the two oxygen atoms will be bonded via an alkylene group (such as a methylene group, ethylene group, trimethylene group, tetramethylene group, or other alkylene groups with 1 to 10 carbon atoms).

[0177] Examples of such boronic acids or their ester groups include:

[0178] [ka]

[0179] [In the above formula, R 5 and R 6 These are identical or different, representing a hydrogen atom or an alkyl group. Examples of groups represented by the following are given.

[0180] The above R 5 and R 6 is a hydrogen atom or an alkyl group.

[0181] The alkyl groups described above can be used, and the types and number of substituents are also the same.

[0182] Boronic acid or its ester group may have substituents. Examples of substituents when boronic acid or its ester group is substituted include halogen atoms (fluorine, chlorine, bromine, iodine, etc.), the alkoxy groups mentioned above, the aryl groups mentioned above, the boronic acid or its ester group mentioned above, cyano groups, etc. When these substituents are present, the number of substituents can be, for example, 1 to 5.

[0183] Examples of compounds represented by such general formula (4) include:

[0184] [ka]

[0185] [In the above formula, R 5 and R 6 This is the same as above. The like are preferable.

[0186] While there are no particular restrictions on the amount of compound having an aryl group used, from the viewpoint of conversion rate, selectivity, yield, etc., 0.005 to 0.10 moles, and more preferably 0.01 to 0.05 moles, are preferred per mole of the polycyclic aromatic sulfonium compound of the present invention, which is the substrate. When using multiple compounds having aryl groups, their total amount can be adjusted to fall within the above range.

[0187] In this process, bases can also be used. Preferred bases include, for example, alkali metal carbonates, alkali metal fluoride salts, and alkali metal phosphates. Examples of such bases include alkali metal phosphates such as sodium phosphate and potassium phosphate; alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate; alkali metal fluoride salts such as sodium fluoride, potassium fluoride, and cesium fluoride; alkali metal alkoxy salts such as lithium tert-butoxide, sodium tert-butoxide, and potassium tert-butoxide; and alkali metal amide salts such as lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, and potassium bis(trimethylsilyl)amide. These can be used individually or in combination of two or more types.

[0188] When using a base, the amount of base used is not particularly limited, but from the viewpoint of conversion rate, selectivity, yield, etc., 1.0 to 10.0 moles, and more preferably 1.5 to 5.0 moles, of base per mole of the polycyclic aromatic sulfonium compound of the present invention, which is the substrate, is preferred. When using multiple bases, the total amount can be adjusted so that it falls within the above range.

[0189] The reaction can usually be carried out in the presence of a solvent. While there are no particular restrictions on the solvents that can be used, examples include alcohol compounds such as ethanol and n-propyl alcohol; amide compounds such as N,N-dimethylformamide; ether compounds such as tetrahydrofuran and 1,4-dioxane; halogenated aliphatic hydrocarbon compounds such as chloroform and dichloromethane; and aromatic hydrocarbon compounds such as toluene and xylene. These solvents can be used individually or in combination of two or more.

[0190] The reaction atmosphere can be an inert atmosphere such as a nitrogen gas atmosphere or an argon gas atmosphere.

[0191] While there are no particular restrictions on the reaction temperature, it is generally suitable for temperatures ranging from 20 to 80°C, and especially from 30 to 60°C, from the viewpoint of conversion rate, selectivity, and yield. The reaction time should be sufficient for the reaction to be fully completed.

[0192] After the reaction is complete, the product can be purified by conventional methods as needed to obtain a polycyclic aromatic compound represented by the general formula (3C).

[0193] 7. Method for producing extended polycyclic aromatic hydrocarbon compounds After obtaining a polycyclic aromatic compound represented by the general formula (3C) as described above, an extended polycyclic aromatic hydrocarbon compound with an expanded π-plane can be produced by subjecting it to a ring fusion reaction.

[0194] The ring fusion reaction is not particularly limited and may be a general oxidation reaction or a Scholl reaction (dehydrogenation cyclization reaction). Furthermore, it may not be limited to oxidation reactions but may also be reductive reactions. In this case, oxidation reactions using antimony pentachloride, aluminum chloride, aluminum bromide, titanium tetrachloride, tin tetrachloride, zinc chloride, copper chloride, iron chloride (FeCl3), boron trifluoride, phosphorus pentoxide, manganese dioxide, selenium oxide, iodine, etc. may be carried out, or a reductive reaction using potassium may be carried out. In the present invention, a Scholl reaction using FeCl3 or a reductive reaction using potassium is preferred.

[0195] The solvent used in this process may be a nonpolar or polar solvent. Examples include alkane compounds such as hexane, heptane, and octane; haloalkane compounds such as dichloromethane, chloroform, carbon tetrachloride, and ethylene chloride; aromatic hydrocarbon compounds such as benzene, toluene, xylene, mesitylene, and pentamethylbenzene; halobenzene compounds such as chlorobenzene and bromobenzene; ether compounds such as diethyl ether and anisole; methyl nitrate; dimethyl sulfoxide; and nitromethane. These solvents can be used individually or in combination of two or more.

[0196] The reaction temperature for a ring fusion reaction is usually selected from the range of 0°C to the boiling point of the solvent. The reaction pressure for a ring fusion reaction is usually selected from the range of atmospheric pressure. Furthermore, the reaction time for a ring fusion reaction is usually the time it takes for the reaction to proceed.

[0197] Furthermore, the reaction atmosphere is not particularly limited, but is preferably an inert gas atmosphere, and can be an argon gas atmosphere, a nitrogen gas atmosphere, etc. An air atmosphere can also be used.

[0198] After the reaction is complete, the desired extended polycyclic aromatic hydrocarbon compound can be obtained by following the usual isolation and purification steps, if necessary. [Examples]

[0199] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0200] Unless otherwise specified, all reactions were carried out in oven-dried or flame-dried glassware under a nitrogen atmosphere. Before setting up the reaction, the glassware was evacuated and filled with nitrogen three times. Unless otherwise specified, all preparation and purification were carried out under air using reagent-grade solvents. rt (room temperature) in this example refers to 23–26°C.

[0201] Chromatography and solvents: Analytical thin-layer chromatography (TLC) was performed using E. Merck silica gel 60 F254 pre-coated plates (0.25 mm). Developed chromatograms were analyzed under a UV lamp (254 or 365 nm) or stained with KMnO4 solution. Flash column chromatography was performed using a Biotage Isolera® equipped with a Biotage SNAP Cartridge KP-Sil column or a KANTO Silica Gel 60N (spherical, neutral, 40-100 μm) column. Toluene, tetrahydrofuran (THF), and diethyl ether (Et2O) used in the reaction were purified through a solvent purification system (Glass Contour).

[0202] NMR and deuterated solvents: Unless otherwise specified, NMR spectra are from JEOL ECS-600. 1 H 600 MHz, 13 Recorded at room temperature using a 150 MHz C spectrometer. Chemical shift (δ) is shown in downfield ppm for tetramethylsilane. The residual solvent signal is: 1 H and 13 Used as a reference for the 13C NMR spectrum (with tetramethylsilane at 0.0 ppm, CDCl3:δ H = 7.26 ppm, δ C = 77.16 ppm; C2D2Cl4:δ H = 6.0 ppm, δ C = 73.78 ppm; CD2Cl2:δ H = 5.32 ppm, δ C (= 54.00 ppm). 19The 1F NMR spectra were not calibrated using an internal standard. All signal multiplicity was expressed using standard abbreviations: s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, h = sextet, hept = heptet, m = multiplet, br = broad signal. All NMR data were processed using Mestrenova 14 with standard phase and baseline corrections. Coupling constants (J) are in Hz. Crude yields were calculated using CH2Br2 as the internal standard. 1 This was determined by 1H NMR. 13 In 13C NMR, peak overlap of assigned peaks is reported based on the degree of overlap of carbon signals.

[0203] HRMS: High-resolution mass spectra (HRMS) were obtained using Thermo Fisher Scientific Exactive (ESI-MS), JEOL JMS-T100TD (Direct Analysis in Real Time, DART), or Bruker ultrafleXtreme (MALDI-TOF MS).

[0204] Chemicals: Unless otherwise specified, all reactants or reagents, including dry solvents, were obtained from commercial suppliers and used as is. Thianthrene, trifluoromethanesulfonic acid (TfOH), trifluoromethanesulfonic anhydride (Tf2O), 4,4'-thiodiphenol, and 1-bromo-2-(2-(2-methoxyethoxy)ethoxy)ethane were purchased from Tokyo Chemical Industries, Ltd. (TCI), and p-tolylsulfoxide (9b) was purchased from Fujifilm Wako Pure Chemical Industries, Ltd. H2SO4 was purchased from Kanto Chemical Co., Ltd.

[0205] Synthesis Examples 1-4: Synthesis of Diaryl Sulfoxide Compounds

[0206] [ka]

[0207] [Synthesis Examples 1-2: Compounds 9a and 9c] 2,2'-Sulfinylbis(1,3,5-trimethylbenzene)(9a) was synthesized according to the reference (X. Li, Y. Sun, X. Huang, L. Zhang, L. Kong, B. Peng, Org. Lett. 2017, 19, 838-841). 4,4'-Sulfinylbis(methoxybenzene)(9c) was synthesized according to the reference (GA Olah, ER Marinez, GKS Prakash, Synlett 1999, 1999, 1397-1398).

[0208] [Synthesis Example 3: 4,4'-Sulfinylbis((dodecyloxy)benzene) (Compound 9d)]

[0209] [ka]

[0210] Compound 9d was synthesized in two steps. 4,4'-sulfinyldiphenol was prepared according to the literature procedure (L. Engman, J. Lind, G. Merenyi, J. Phys. Chem. 1994, 98, 3174-3182.), recrystallized from methanol (small amount), hexane (small amount), and CH2Cl2, and then purified by washing the crystalline solid with CH2Cl2. Following the modified literature procedure (JW Thackeray, SM Coley, JF Cameron, PJ Labeaume, AE Madkour, O. Ongayi, V. Jain, US2012141939A1, 2012), 4,4'-sulfinyldiphenol (468.5 mg, 2.00 mmol, 1.00 equivalent), K2CO3 (624.7 mg, 4.52 mmol, 2.26 equivalents), tetramethylethylenediamine (TMEDA; 15 μL, 0.10 mmol, 5 mol%), and dimethyl sulfoxide (DMSO; 2.5 mL) were added to a J.-Young Schlenk tube equipped with a polytetrafluoroethylene-coated stirring bar. Next, 1-bromododecane (1.00 mL, 4.2 mmol, 2.1 equivalents) was added, and the resulting mixture was stirred under nitrogen at 90°C for 18 hours. After cooling to room temperature (rt), the reaction mixture was diluted with ethyl acetate and washed three times with distilled water. After washing three times with H2O, the organic layer was dried over Na2SO4, filtered, and concentrated under vacuum. The target compound, 4,4'-sulfinylbis((dodecyloxy)benzene) (compound 9d), was obtained as a colorless solid by silica gel flash column chromatography (hexane / ethyl acetate = 75:25) (800.9 mg, 1.40 mmol, 70%). R f (Hexane / ethyl acetate = 80 : 20) : 0.3. 1H NMR (600 MHz, CDCl3) δ 7.51 (d, J = 8.9 Hz, 4H), 6.93 (d, J = 8.3 Hz, 4H), 3.94 (t, J = 6.5 Hz, 4H), 1.80-1.72 (m, 4H), 1.46-1.38 (m, 4H), 1.38-1.18 (m, 32H), 0.87 (t, J = 7.0 Hz, 6H). 13 C NMR (151 MHz, CDCl3) δ 161.5, 136.8, 127.0, 115.3, 68.4, 32.0, 29.8, 29.7, 29.7, 29.7, 29.5 (2C), 29.2, 26.1, 22.8, 14.2. ESI-HRMS calcd for C 36 H 58 O3SNa [M+Na] + : 593.4004; observed 593.3999.

[0211] [Synthesis Example 4: 4,4'-Sulfinylbis((2-(2-(2-methoxyethoxy)ethoxy)ethoxy)benzene)(Compound 9e)]

[0212] [ka]

[0213] Compound 9e was synthesized in two steps. 4,4'-sulfinyldiphenol was prepared according to the literature procedure (L. Engman, J. Lind, G. Merenyi, J. Phys. Chem. 1994, 98, 3174-3182.), recrystallized from methanol (small amount), hexane (small amount), and CH2Cl2, and then purified by washing the crystalline solid with CH2Cl2. Following the modified literature procedure (JW Thackeray, SM Coley, JF Cameron, PJ Labeaume, AE Madkour, O. Ongayi, V. Jain, US2012141939A1, 2012), 4,4'-sulfinyldiphenol (1.17 g, 5.00 mmol, 1.00 equivalent), K2CO3 (1.56 g, 11.3 mmol, 2.26 equivalents), tetramethylethylenediamine (TMEDA; 37.5 μL, 0.25 mmol, 5 mol%), and dimethyl sulfoxide (DMSO; 6.25 mL) were added to a J.-Young Schlenk tube equipped with a polytetrafluoroethylene-coated stirring bar. Next, 1-bromo-2-(2-(2-methoxyethoxy)ethoxy)ethane (1.82 mL, 10.5 mmol, 2.1 equivalents) was added, and the resulting mixture was stirred under nitrogen at 90°C for 18 hours. After cooling to room temperature (rt), the reaction mixture was diluted with ethyl acetate and washed three times with distilled water. After washing three times with H2O, the organic layer was dried over Na2SO4, filtered, and concentrated under vacuum. The target compound, 4,4'-sulfinylbis((2-(2-(2-methoxyethoxy)ethoxy)ethoxy)benzene) (compound 9e), was obtained as a colorless oil by silica gel flash column chromatography (ethyl acetate / methanol = 95:5) (1.98 g, 3.76 mmol, 75%). R f (Ethyl acetate / methanol = 95 : 5) : 0.3. 1¹H NMR (600 MHz, CDCl₃) δ 7.54-7.48 (m, 4H), 6.96 (d, J = 8.7 Hz, 4H), 4.16-4.09 (m, 4H), 3.87-3.82 (m, 4H), 3.71 (dd, J = 6.1, 3.5 Hz, 4H), 3.66 (dd, J = 5.9, 3.6 Hz, 4H), 3.63 (dd, J = 5.6, 3.6 Hz, 4H), 3.53 (dd, J = 5.5, 3.3 Hz, 4H), 3.36 (s, 6H). 13 ¹³C NMR (151 MHz, CDCl₃) δ 161.1, 137.2, 127.0, 115.4, 72.0, 71.0, 70.8, 70.7, 69.6, 67.8, 59.2. ESI-HRMS calcd for C 26 H 38 O₉SNa [M+Na] + : 549.2134; observed: 549.2129.

[0214] Synthesis Examples 5-6: Synthesis of Thianthrene 5-Oxide Compounds [Synthesis Example 5: 2,3,7,8-tetramethoxythianthrene 5-oxide (2c)]

[0215] [Chemical Formula]

[0216] Compound 2c was synthesized in three steps. Following the literature procedure, 1,2-diiodo-4,5-dimethoxybenzene (J. Lacour, D. Monchaud, G. Bernardinelli, F. Favarger, Org. Lett. 2001, 3, 1407-1410.) and 2,3,7,8-tetramethoxythiantrene (J. Yuan, Y. Song, X. Li, J. Xie, S. Dong, K. Zhu, Org. Lett. 2021, 23, 9554-9558.) were synthesized. Oxidation of 2,3,7,8-tetramethoxythiantrene (168 mg, 0.50 mmol, 1.0 equivalent) was carried out according to Ritter's method (F. Berger, MB Plutschack, J. Riegger, W. Yu, S. Speicher, M. Ho, N. Frank, T. Ritter, Nature 2019, 567, 223-228). Purification by silica gel flash column chromatography (hexane / ethyl acetate = 100:0 - 30:70) yielded the target compound, 2,3,7,8-tetramethoxythiantrene 5-oxide (2c), as a yellow solid (146 mg, 0.41 mmol, 83%). R f (Hexane / ethyl acetate = 30 : 70) : 0.3. 1 H NMR (600 MHz, CDCl3) δ 7.37 (s, 3H), 7.10 (s, 2H), 3.97 (s, 6H), 3.91 (s, 6H). 13 C NMR (151 MHz, CDCl3) δ 150.3, 150.0, 133.4, 120.7, 111.9, 106.9, 56.5. ESI-HRMS calcd for C 16 H 16 O5S2Na [M+Na] + : 375.0337; found: 375.0334.

[0217] [Synthesis Example 6: 2,3,7,8-Tetrakis[4-(tert-butyl)phenyl]thiantrene 5-oxide(2d)]

[0218] [ka]

[0219] Compound 2d was synthesized in three steps. First, 2,3,7,8-tetrabromothinrene was synthesized according to the literature (T.-Z. Xie, J.-Y. Li, Z. Guo, JM Ludlow, X. Lu, CN Moorefield, C. Wesdemiotis, GR Newkome, Eur. J. Inorg. Chem. 2016, 2016, 1671-1677). 2,3,7,8-tetrabromothinrene (531.9 mg, 1.0 mmol, 1.0 equivalent), (4-(tert-butyl)phenyl)boronic acid (1.07 g, 6.0 mmol, 6.0 equivalent), and Na2CO3 (2.65 g, 25 mmol, 25 equivalents) were placed in a J.-Young Schlenk tube. Distilled H2O (75 mL), toluene (125 mL), and ethanol (50 mL) were added, and the mixture was purged with nitrogen for an extended period. Dichlorobis(triphenylphosphine)palladium(II) (PdCl2(PPh3)2; 123 mg, 0.0175 mmol, 1.75 mol%) was added, and the mixture was stirred under reflux for 72 hours. After the reaction mixture was cooled to room temperature, the layers were separated, and the aqueous layer was extracted with CH2Cl2 (3 x 100 mL). The organic layer was dried over Na2SO4, filtered, and concentrated under vacuum. Silica gel flash column chromatography (hexane / CH2Cl2 = 100 : 0 - 90 : 10) yielded 2,3,7,8-tetrakis(4-(tert-butyl)phenyl)thiantrene (633.1 mg, 0.85 mmol, 85%) as a colorless solid. Oxidation of 2,3,7,8-tetrakis(4-(tert-butyl)phenyl)thiantrene (590.4 mg, 0.79 mmol, 1.0 equivalent) was carried out according to Ritter's method. Purification by silica gel flash column chromatography (hexane / ethyl acetate = 100:0 - 90:10) yielded the target compound, 2,3,7,8-tetrakis[4-(tert-butyl)phenyl]thiantrene 5-oxide (2d), as a colorless solid (211.2 mg, 0.28 mmol, 35%). R f (Hexane): 0.4. 1 H NMR (600 MHz, CDCl3) δ 7.99 (s, 2H), 7.70 (s, 2H), 7.26-7.20 (m, 8H), 7.08-7.05 (m, 8H), 1.29 (s, 36H). 13 C NMR (151 MHz, CDCl3) δ 150.4, 150.2, 142.7, 141.3, 139.8, 137.0, 136.8, 131.2, 129.5, 129.5, 127.2, 126.9, 125.1, 125.0, 34.6, 31.4. MALDI-TOF MS calcd for C 52 H 56 OS2Na [M+Na] + : 783.3665; found: 783.3661.

[0220] Synthesis Examples 7-9: Synthesis of Dibenzothiophene Compounds

[0221]

change

[0222] [Synthetic Examples 7~8: Compounds 15a and 15b] Dibenzothiophene oxide (15a) was synthesized according to the literature (P. Xu, Da Zhao, F. Berger, A. Hamad, J. Rickmeier, R. Petzold, M. Kondratiuk, K. Bohdan, T. Ritter, Angew. Chem. Int. Ed. 2020, 132, 1972-1976). 2,8-Dimethoxydibenzo[b,d]thiophene 5-oxide (15b) was synthesized from 2,8-dimethoxydibenzo[b,d]thiophene (S.-I. Kawano, T. Hamazaki, A. Suzuki, K. Kurahashi, K. Tanaka, Chem. Eur. J. 2016, 22, 15674-15683) according to the literature (P. Xu, Da Zhao, F. Berger, A. Hamad, J. Rickmeier, R. Petzold, M. Kondratiuk, K. Bohdan, T. Ritter, Angew. Chem. Int. Ed. 2020, 132, 1972-1976).

[0223] [Synthesis Example 9: 2,8-Bis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)dibenzo[b,d]thiophene 5-oxide(15c)]

[0224] [ka]

[0225] Compound 15c was synthesized in three steps. First, 2,8-dihydroxydibenzo[b,d]thiophene was synthesized according to the literature procedure (S.-I. Kawano, T. Hamazaki, A. Suzuki, K. Kurahashi, K. Tanaka, Chem. Eur. J. 2016, 22, 15674-15683). Next, 2,8-bis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)dibenzo[b,d]thiophene was synthesized according to a modified literature procedure (JW Thackeray, SM Coley, JF Cameron, PJ Labeaume, AE Madkour, O. Ongayi, V. Jain, US2012141939A1, 2012). In a J.-Young Schlenk tube equipped with a polytetrafluoroethylene-coated stirring rod, 2,8-dihydroxydibenzo[b,d]thiophene (432.5 mg, 2.00 mmol, 1.00 equivalent), K2CO3 (624.7 mg, 4.52 mmol, 2.26 equivalents), tetramethylethylenediamine (TMEDA; 15 μL, 0.10 mmol, 5 mol%), and dimethyl sulfoxide (2.5 mL) were added. Next, 1-bromo-2-(2-(2-methoxyethoxy)ethoxy)ethane (0.73 mL, 4.20 mmol, 2.1 equivalents) was added, and the resulting mixture was stirred under nitrogen at 90°C for 18 hours. After cooling to room temperature, the reaction mixture was diluted with ethyl acetate, washed three times with distilled water, the organic layer was dried over Na2SO4, filtered, and concentrated under vacuum. 2,8-bis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)dibenzo[b,d]thiophene (792.9 mg, 1.56 mmol, 78%) was obtained as a yellow solid by silica gel flash column chromatography (hexane / ethyl acetate = 66:33 - 0:100).Thirdly, the procedure described in the literature (P. Xu, Da Zhao, F. Berger, A. Hamad, J. Rickmeier, R. Petzold, M. Kondratiuk, K. Bohdan, T. Ritter, Angew. Chem. Int. Ed. 2020, 132, 1972-1976.) was modified to dissolve 2,8-bis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)dibenzo[b,d]thiophene (792.9 mg, 1.56 mmol, 1.0 equivalent) in trifluoroacetic acid (1.6 mL, 1 M), and the reaction mixture was cooled to 0°C. An aqueous H2O2 solution (35%, 167 μL, 1.72 mmol, 1.1 equivalent) was added dropwise over 1 minute, and the reaction mixture was stirred at 0°C for 1 hour. The reaction mixture was poured into a mixture of ice / Na2CO3 aqueous solution and CH2Cl2, the layers were separated, and the aqueous layer was extracted twice with CH2Cl2. The combined organic layers were dried over Na2SO4, filtered, and concentrated under vacuum. Silica gel flash column chromatography (ethyl acetate / methanol = 95:5) yielded the target compound, 2,8-bis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)dibenzo[b,d]thiophene 5-oxide (15c), as a colorless oil (787.4 mg, 1.50 mmol, 96%). R f (Ethyl acetate / methanol = 95 : 5) : 0.2. 1 H NMR (600 MHz, CD2Cl2) δ 7.82 (d, J = 8.5 Hz, 2H), 7.31 (d, J = 2.4 Hz, 2H), 7.02 (dd, J = 8.5, 2.4 Hz, 2H), 4.28-4.19 (m, 4H), 3.91-3.82 (m, 4H), 3.75-3.64 (m, 4H), 3.65-3.57 (m, 4H), 3.63-3.54 (m, 4H), 3.54-3.44 (m, 4H), 3.32 (s, 6H). 13C NMR (151 MHz, CD2Cl2) δ 162.8, 139.3, 138.6, 128.8, 116.1, 108.2, 72.2, 71.2, 70.9, 70.8, 69.8, 68.5, 59.0. ESI-HRMS calcd for C 26 H 36 O9S [M] + : 547.1978; found: 547.1976.

[0226] Examples 1-4 and Comparative Examples 1-6 [Screening of sulfonation agents]

[0227] [ka]

[0228] Comparative Example 1 is an example where the substrate used is compound 2c, Comparative Example 2 is an example where the substrate used is compound 2d, Comparative Example 3 is an example where the substrate used is compound 9a, Example 1 is an example where the substrate used is compound 9b, Example 2 is an example where the substrate used is compound 9c, Example 3 is an example where the substrate used is compound 9d, Example 4 is an example where the substrate used is compound 9e, Comparative Example 4 is an example where the substrate used is compound 15a, Comparative Example 5 is an example where the substrate used is compound 15b, and Comparative Example 6 is an example where the substrate used is compound 15c.

[0229] Sulfoxide (1.0 equivalent) and naphthalene (1.0 equivalent) were added to 30 mL or 50 mL glass vials equipped with a polytetrafluoroethylene-coated stirring rod under air. Dry CH2Cl2 (0.10 M relative to naphthalene) was added, and the solution was cooled to 0°C in an ice bath. Then, trifluoromethanesulfonic acid anhydride (Tf2O) (3.0 equivalents) and concentrated H2SO4 (1.5 equivalents) were added dropwise, respectively. The reaction mixture was heated to 26°C and stirred at that temperature for 5 hours. After completion, the reaction mixture was diluted with CH2Cl2, saturated NaHCO3 aqueous solution was added, and the mixture was stirred for 1 minute, after which the layers were separated. The organic layer was washed twice with saturated NaBF4 aqueous solution, dried with anhydrous Na2SO4, filtered, and concentrated under vacuum. Using CH2Br2 as an internal standard, a coarse solution was obtained. 1The 1H NMR yield was measured. 1 If the 1H NMR yield was high, purification was attempted by silica gel flash column chromatography (hexane / CH2Cl2 = 100 : 0 - 0 : 100; then CH2Cl2 / methanol) to obtain the sulfonium salt.

[0230] [General procedure for thianthreneation of polycyclic aromatic hydrocarbon compounds (GP-1)] Thianthrene 5-oxide (1.5 equivalents) and each polycyclic aromatic hydrocarbon compound (1.0 equivalent) were added to 30 mL or 50 mL glass vials equipped with polytetrafluoroethylene-coated stirring rods under air. Dry CH2Cl2 (0.025 M) was added, and the solution was cooled to 0°C in an ice bath. Then, trifluoromethanesulfonic anhydride (Tf2O; 3.0 equivalents) and concentrated H2SO4 (1.5 equivalents) were added dropwise, respectively. The reaction mixture was heated to 26°C and stirred at that temperature for 5 hours. After completion, the reaction mixture was diluted with CH2Cl2, saturated NaHCO3 aqueous solution was added, and the mixture was stirred for 1 minute, after which the layers were separated. The organic layer was washed with saturated NaBF4 aqueous solution (twice for small-scale reactions, three times for large-scale reactions), dried over anhydrous Na2SO4, filtered, and concentrated under vacuum. The thianthenium salt was obtained as a solid by silica gel flash column chromatography (hexane / CH2Cl2 = 100 : 0 - 0 : 100; then CH2Cl2 / methanol). After concentration by column chromatography, the isolated compound was dissolved in a small amount of CH2Cl2 and precipitated with diethyl ether. However, the reaction did not proceed well with large polycyclic aromatic hydrocarbon compounds such as pyrene, and it became clear that only small polycyclic aromatic hydrocarbon compounds are suitable as substrates for the thianthrening protocol.

[0231] [Isolation of polycyclic aromatic compound sulfonium salts] (Example 2: Bis(4-methoxyphenyl)(naphthalene-1-yl)sulfonium tetrafluoroborate (12a))

[0232] [ka]

[0233] Compound 12a was synthesized according to modified GP-1 using 4,4'-sulfinylbis(methoxybenzene) (52.5 mg, 0.2 mmol, 1.0 equivalent) and naphthalene (25.6 mg, 0.2 mmol, 1.0 equivalent). The compound was purified by silica gel flash column chromatography (hexane / CH2Cl2 = 100 : 0 - 0 : 100; then CH2Cl2 / methanol = 100 : 0 - 95 : 5), then concentrated, and precipitated with CH2Cl2 and diethyl ether to obtain the target compound, bis(4-methoxyphenyl)(naphthalene-1-yl)sulfonium tetrafluoroborate (12a), as a colorless solid (89.4 mg, 0.194 mmol, 97%). R f (CH2Cl2 / methanol = 95 : 5) : 0.3. 1 H NMR (600 MHz, CDCl3) δ 8.16 (d, J = 8.2 Hz, 2H), 7.98 (d, J = 8.2 Hz, 1H), 7.69-7.56 (m, 7H), 7.44 (d, J = 7.3 Hz, 1H), 7.16-7.10 (m, 4H), 3.82 (s, 6H). 13 C NMR (151 MHz, CDCl3) δ 164.6, 135.0, 134.3, 133.3, 130.6, 129.9, 129.8, 129.6, 128.3, 126.3, 122.3, 121.8, 117.4, 112.6, 56.1. 19 F NMR (376 MHz, CDCl3) δ -152.06. ESI-HRMS calcd for C 24 H 21 O2S [M-BF4] + : 373.1262; found: 373.1256.

[0234] Examples 4-12 As described below, the range of polycyclic aromatic hydrocarbon compounds was investigated using 4,4'-sulfinylbis((2-(2-(2-methoxyethoxy)ethoxy)ethoxy)benzene) (compound 9e) obtained in Synthesis Example 4 as a substrate. Various large polycyclic aromatic hydrocarbon compounds underwent CH sulfonation reactions, and sulfonium salts 14b-h were obtained in high yield. Notably, the sulfonium salts of this series of polycyclic aromatic hydrocarbon compounds showed outstanding solubility in methanol. For example, compound 14d had a solubility of 160 mg / mL or higher, and compound 14h had a solubility of 297 mg / mL or higher, showing more than 1000 times the solubility of the original perylene (0.16 mg / mL) and coronene (0.09 mg / mL) in methanol. Furthermore, compound 14d also dissolved in deionized water, with a solubility of 4.6 mg / mL. The solubility of other polycyclic aromatic hydrocarbon compounds was also uniformly improved. The results are shown in Figure 1.

[0235] [General Procedure 2 (GP-2) for Sulfonation of Large Polycyclic Aromatic Hydrocarbon Compounds with Tetraethylene Glycol-Diaryl Sulfoxide] 4,4'-Sulfinylbis((2-(2-methoxyethoxy)ethoxy)ethoxy)benzene (1.0 equivalent) and each polycyclic aromatic hydrocarbon compound (PAH; 1.0 equivalent) were added under nitrogen to a flame-dry J.-Young Schlenk tube (50 mL) equipped with a polytetrafluoroethylene-coated stirring bar. Dry 1,2-dichloroethane (0.0125 M relative to the polycyclic aromatic hydrocarbon compound) was added, and the mixture was stirred at 85°C until all solids were dissolved (usually 15-30 minutes). After the reaction mixture was cooled to 26°C, trifluoromethanesulfonic anhydride (Tf2O; 3.0 equivalents) and concentrated H2SO4 (1.5 equivalents) were added dropwise, respectively, under nitrogen. The reaction mixture was stirred at 26°C for 5 hours. After completion, the reaction mixture was diluted with CH2Cl2, saturated aqueous NaHCO3 was added, and the mixture was stirred for 1 minute, after which the layers were separated. The organic layer was washed twice with saturated NaBF4 aqueous solution, dried over anhydrous Na2SO4, filtered, and concentrated under vacuum. The sulfonium salt was obtained as a viscous oil by silica gel flash column chromatography (hexane / CH2Cl2 = 100 : 0 - 0 : 100, then CH2Cl2 / methanol = 100 : 0 - 97 : 3). Note 1: Separation between the saturated NaBF4 aqueous solution and the organic layer is poor, so separation takes approximately 10 minutes. Note 2: As the size of polycyclic aromatic hydrocarbon compounds increases, longer column chromatography needs to be considered (up to 40 column volumes at CH2Cl2 / methanol = 97:3).

[0236] [General Procedure 3 (GP-3) for Medium Polycyclic Aromatic Hydrocarbon Compounds] 4,4'-Sulfinylbis((2-(2-methoxyethoxy)ethoxy)ethoxy)benzene (1.0 equivalent) and each polycyclic aromatic hydrocarbon compound (1.0 equivalent) were added to a glass vial (30 mL or 50 mL) equipped with a polytetrafluoroethylene-coated stirring bar under air. Dry 1,2-dichloroethane (0.0125 M relative to the polycyclic aromatic hydrocarbon compound) was added, and the mixture was stirred at 26°C until all solids were dissolved. Next, trifluoromethanesulfonic anhydride (Tf2O; 3.0 equivalents) and concentrated H2SO4 (1.5 equivalents) were added dropwise under air. The reaction mixture was stirred at 26°C for 5 hours. After completion, the reaction mixture was diluted with CH2Cl2, saturated aqueous NaHCO3 was added, and the mixture was stirred for 1 minute, after which the layers were separated. The organic layer was washed twice with saturated aqueous NaBF4, dried with anhydrous Na2SO4, filtered, and concentrated under vacuum. The sulfonium salt was obtained as a sticky oil by silica gel flash column chromatography (hexane / CH2Cl2 = 100 : 0 - 0 : 100, followed by CH2Cl2 / methanol = 100 : 0 - 97 : 3).

[0237] (Example 4: Bis(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)(naphthalene-1-yl)sulfonium tetrafluoroborate (14a))

[0238] [ka]

[0239] Compound 14a was prepared according to modified GP-3 using 4,4'-sulfinylbis((2-(2-methoxyethoxy)ethoxy)ethoxy)benzene (105.3 mg, 0.2 mmol, 1.0 equivalent), naphthalene (25.6 mg, 0.2 mmol, 1.0 equivalent), and CH2Cl2 (0.1 M relative to naphthalene) instead of 1,2-dichloroethane. Under ice cooling, trifluoromethanesulfonic anhydride (Tf2O; 83.5 μL, 0.6 mmol, 3.0 equivalents) and H2SO4 (16 μL, 0.3 mmol, 1.5 equivalents) were added, and the reaction mixture was slowly heated to 26°C and stirred at that temperature for 5 hours. After completion, the reaction mixture was diluted with CH2Cl2, saturated aqueous NaHCO3 was added, and the mixture was stirred for 1 minute, after which the layers were separated. The organic layer was washed twice with saturated NaBF4 aqueous solution, dried over anhydrous Na2SO4, filtered, and concentrated under vacuum. Silica gel flash column chromatography (hexane / CH2Cl2 = 100 : 0 - 0 : 100; then CH2Cl2 / methanol = 100 : 0 - 97 : 3) yielded the target compound, bis(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)(naphthalene-1-yl)sulfonium tetrafluoroborate (14a), as a colorless oil (134.8 mg, 0.186 mmol, 93%). R f (CH2Cl2 / methanol = 95 : 5) : 0.2. 1 H NMR (600 MHz, CDCl3) δ 8.16-8.09 (m, 2H), 7.98-7.93 (m, 1H), 7.65-7.60 (m, 2H), 7.60-7.56 (m, 5H), 7.36 (dd, J = 7.6, 1.0 Hz, 1H), 7.16-7.11 (m, 4H), 4.16-4.12 (m, 4H), 3.82-3.77 (m, 4H), 3.67-3.62 (m, 4H), 3.61-3.58 (m, 4H), 3.58-3.55 (m, 4H), 3.50-3.44 (m, 4H), 3.28 (s, 6H). 13C NMR (151 MHz, CDCl3) δ 163.8, 135.0, 134.2, 133.1, 130.4, 129.8, 129.7, 129.4, 128.3, 126.1, 122.2, 121.6, 117.8, 112.5, 71.7, 70.6, 70.4, 70.4, 69.1, 68.2, 58.9. 19 F NMR (376 MHz, CDCl3) δ -152.16. ESI-HRMS calcd for C 36 H 45 O8S [M-BF4] + : 637.2835; found: 637.2832.

[0240] (Example 5: [1,1'-binaphthalene]-4-ylbis(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)sulfonium tetrafluoroborate (14b))

[0241] [ka]

[0242] Compound 14b was prepared according to GP-3 using 1,1'-binaphthalene (50.9 mg, 0.2 mmol, 1.0 equivalent). The target compound, [1,1'-binaphthalene]-4-ilbis(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)sulfonium tetrafluoroborate (14b), was obtained as a yellow oil (131.7 mg, 0.155 mmol, 77%) by silica gel flash column chromatography (hexane / CH2Cl2 = 100 : 0 - 0 : 100; then CH2Cl2 / methanol = 100 : 0 - 97 : 3). R f (CH2Cl2 / methanol = 95 : 5) : 0.2. 1H NMR (600 MHz, CDCl3) δ 8.33 (d, J = 8.6 Hz, 1H), 8.02 (d, J = 8.2 Hz, 1H), 7.98 (d, J = 8.1 Hz, 1H), 7.81 (d, J = 8.9 Hz, 2H), 7.77 (d, J = 8.9 Hz, 2H), 7.72-7.67 (m, 2H), 7.66-7.54 (m, 3H), 7.54-7.42 (m, 3H), 7.41-7.24 (m, 6H), 4.29-4.20 (m, 4H), 3.92-3.86 (m, 4H), 3.79-3.72 (m, 4H), 3.72-3.67 (m, 4H), 3.67-3.64 (m, 4H), 3.61-3.53 (m, 4H), 3.38 (s, 6H). 13 C NMR (151 MHz, CDCl3) δ 164.0, 163.9, 146.0, 135.7, 133.9, 133.4 (2C), 133.2, 131.9, 130.0, 129.9, 129.7, 129.1, 128.4, 128.3, 128.3, 128.0, 127.8, 126.7, 126.3, 125.7, 125.3, 122.6, 121.3, 118.0, 118.0, 112.8, 112.4, 71.8, 70.7, 70.5, 70.4, 69.1, 68.3, 59.0. 19 F NMR (471 MHz, CDCl3) δ -152.08. ESI-HRMS calcd for C 46 H 51 O8S [M-BF4] + : 763.3305, found: 763.3301.

[0243] (Example 6: Bis(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)(triphenylene-2-yl)sulfonium tetrafluoroborate(14c))

[0244] [ka]

[0245] Compound 14c was prepared according to GP-3 using triphenylene (45.7 mg, 0.2 mmol, 1.0 equivalent). The target compound, bis(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)(triphenylene-2-yl)sulfonium tetrafluoroborate (14c), was obtained as a yellow oil (141.7 mg, 0.172 mmol, 86%) by silica gel flash column chromatography (hexane / CH2Cl2 = 100 : 0 - 0 : 100; then CH2Cl2 / methanol = 100 : 0 - 0 : 100). R f (CH2Cl2 / methanol = 95 : 5) : 0.2. 1 H NMR (396 MHz, CDCl3) δ 8.81 (d, J = 2.3 Hz, 1H), 8.60 (d, J = 9.1 Hz, 1H), 8.32-8.24 (m, 4H), 7.70-7.63 (m, 4H), 7.59 (dd, J = 8.9, 2.1 Hz, 1H), 7.56-7.41 (m, 4H), 7.15-7.09 (m, 4H), 4.16-4.04 (m, 4H), 3.83-3.74 (m, 4H), 3.66-3.56 (m, 12H), 3.51-3.44 (m, 4H), 3.29 (s, 6H). 13 C NMR (100 MHz, CDCl3) δ 163.6, 133.4, 132.9, 131.1, 130.6, 129.9, 129.2, 128.7, 128.0, 127.7, 127.5, 127.4, 126.8 (2C), 126.0, 123.9 (2C), 123.5, 123.2, 123.1, 117.6, 114.8, 71.8, 70.7, 70.5, 70.4, 69.1, 68.2, 58.9. 19 F NMR (373 MHz, CDCl3) δ -151.15. ESI-HRMS calcd for C 44 H 49 O8S [M-BF4] + : 737.3148; found 737.3140.

[0246] (Example 7: Bis(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)(perylene-3-yl)sulfonium tetrafluoroborate (14d))

[0247] [ka]

[0248] Compound 14d was prepared using perylene (1.0 equivalent) according to the procedure described below. The target compound was obtained by silica gel flash column chromatography (hexane / CH2Cl2 = 100 : 0 - 0 : 100; then CH2Cl2 / methanol = 100 : 0 - 97 : 3) as a red viscous oil that appeared fluorescent yellow when diluted, in the isolation yields shown below. Isolation yield using GP-3 (0.2 mmol scale): 76.5 mg, 0.087 mmol, 44%. Isolation yield using GP-2 (0.2 mmol scale): 91.2 mg, 0.107 mmol, 54%. Isolation yield using GP-2 (0.5 mmol scale): 206.3 mg, 0.243 mmol, 49%. R f (CH2Cl2 / methanol = 95 : 5) : 0.3. 1H NMR (600 MHz, CDCl3) δ 7.95 (d, J = 8.2 Hz, 1H), 7.85 (d, J = 7.6 Hz, 1H), 7.82 (d, J = 7.6 Hz, 1H), 7.77 (dd, J = 14.1, 7.9 Hz, 2H), 7.68 (d, J = 8.9 Hz, 4H), 7.53 (d, J = 8.2 Hz, 1H), 7.49 (d, J = 8.0 Hz, 1H), 7.33 (t, J = 8.0 Hz, 1H), 7.27-7.20 (m, 3H), 7.18 (d, J = 9.0 Hz, 5H), 4.17 (dd, J = 6.2, 3.4 Hz, 4H), 3.85-3.80 (m, 4H), 3.69-3.66 (m, 4H), 3.63 (d, J = 4.9 Hz, 4H), 3.61-3.57 (m, 4H), 3.52-3.48 (m, 4H), 3.32 (s, 6H). 13 C NMR (151 MHz, CDCl3) δ 163.9, 137.6, 133.9, 133.3, 132.3, 131.4, 130.8, 130.6, 129.6, 129.2, 129.2, 129.0, 128.2, 127.5, 126.8, 126.6, 123.1, 121.9, 121.4, 121.2, 119.9, 118.6, 117.9, 113.2, 71.9, 70.8, 70.6, 70.6, 69.2, 68.3, 59.1. 19 F NMR (471 MHz, CDCl3) δ -151.70. ESI-HRMS calcd for C 46 H 49 O8S [M-BF4] + : 761.3148; found: 761.3137.

[0249] (Example 8: Perylene-3,10-diylbis(bis(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)sulfonium)ditetrafluoroborate(14d'))

[0250] [ka]

[0251] Perylene-bis-sulfonium salt (14d') was prepared according to modified GP-3 using 4,4'-sulfinylbis((2-(2-methoxyethoxy)ethoxy)ethoxy)benzene) (322.5 mg, 0.61 mmol, 3.0 equivalents) and perylene (51.4 mg, 0.20 mmol, 1.0 equivalent). Trifluoromethanesulfonic anhydride (Tf2O; 0.30 mL, 1.8 mmol, 9.0 equivalents) and concentrated H2SO4 (0.050 mL, 0.94 mmol, 4.6 equivalents) were added dropwise under air. The reaction mixture was stirred at room temperature (rt) for 5 hours. After completion, the reaction mixture was diluted with CH2Cl2, saturated NaHCO3 aqueous solution was added, and the mixture was stirred for a further 1 minute. Subsequently, the organic layer was separated, washed twice with saturated NaBF4 aqueous solution, dried over Na2SO4, filtered, and concentrated under vacuum. Silica gel flash column chromatography (hexane / CH2Cl2 = 100 : 0 - 0 : 100; then CH2Cl2 / methanol = 100 : 0 - 95 : 5 - 90 : 10) yielded the target compound, perylene-3,10-diylbis(bis(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)sulfonium) ditetrafluoroborate (14d'), as a red, sticky oil (100.4 mg, 0.20 mmol, 34%). R f (CH2Cl2 / methanol = 90 : 10) : 0.0 - 0.2 (broad). Note 1: Follow the above procedure for TfO - and BF4 - If anion exchange by NaBF4 is not completed, it is preferable to further wash with a saturated NaBF4 aqueous solution. 1H NMR (600 MHz, CDCl3) δ 8.07 (d, J = 8.2 Hz, 2H), 8.04 (d, J = 8.2 Hz, 2H), 7.76-7.72 (m, 10H), 7.47 (d, J = 8.2 Hz, 2H), 7.21 (d, J = 8.9 Hz, 8H), 6.99 (t, J = 7.9 Hz, 2H), 4.23 (t, J = 4.5 Hz, 8H), 3.88 (t, J = 4.5 Hz, 8H), 3.73-3.72 (m, 8H), 3.68-3.66 (m, 8H), 3.65-3.63 (m, 8H), 3.54-3.53 (m, 8H), 3.36 (s, 12H). 13 C NMR (151 MHz, CDCl3) δ 164.0, 135.0, 133.4, 131.5, 130.3, 129.3 (2C), 128.0, 124.3, 124.2, 122.3, 120.8, 117.9, 113.4, 71.9, 70.9, 70.7, 70.60, 69.3, 68.4, 59.1. 19 F NMR (373 MHz, CDCl3) -150.90. ESI-HRMS calcd for C 72 H 86 O 16 S2[M-(BF4)2] 2+ : 635.2673; found: 635.2676.

[0252] (Example 9: Bis(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)(pyrene-1-yl)sulfonium tetrafluoroborate (14f))

[0253] [ka]

[0254] Compound 14f was prepared according to GP-3 using pyrene (40.5 mg, 0.2 mmol, 1.0 equivalent). The target compound, bis(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)(pyrene-1-yl)sulfonium tetrafluoroborate (14f), was obtained as a yellow oil (119.2 mg, 0.149 mmol, 75%) by silica gel flash column chromatography (hexane / CH2Cl2 = 100 : 0 - 0 : 100; then CH2Cl2 / methanol = 100 : 0 - 97 : 3). R f (CH2Cl2 / methanol = 95 : 5) : 0.2. 1 H NMR (600 MHz, CDCl3) δ 8.43 (d, J = 9.1 Hz, 1H), 8.25-8.16 (m, 3H), 8.16-8.08 (m, 2H), 8.00 (t, J = 7.7 Hz, 1H), 7.94 (d, J = 8.9 Hz, 1H), 7.77 (d, J = 8.3 Hz, 1H), 7.63 (d, J = 9.1 Hz, 4H), 7.14 (d, J = 8.9 Hz, 4H), 4.17-4.10 (m, 4H), 3.79 (t, J = 4.5 Hz, 4H), 3.65 (t, J = 4.7 Hz, 4H), 3.62-3.59 (m, 4H), 3.59-3.55 (m, 4H), 3.50-3.45 (m, 4H), 3.29 (s, 6H). 13 C NMR (151 MHz, CDCl3) δ 163.9, 135.4, 133.3, 132.5, 131.8, 131.2, 131.1, 130.4, 128.2, 128.2, 127.8, 127.1, 126.3, 125.4, 123.6, 120.7, 118.0, 116.3, 113.9 (2C), 72.0, 70.9, 70.9, 70.7, 70.7, 70.5, 69.4, 68.4, 59.2. 19F NMR (471 MHz, CDCl3) δ -152.31. ESI-HRMS calcd for C 42 H 47 O8S [M-BF4] + : 711.2992, observed 711.2987.

[0255] (Example 10: Dibenzo[g,p]chrysen-3-ylbis(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)sulfonium tetrafluoroborate (14g))

[0256] [ka]

[0257] 14 g of the compound was prepared according to GP-2 using dibenzo[g,p]chrysene (32.8 mg, 0.1 mmol, 1.0 equivalent). The target compound, dibenzo[g,p]chrysene-3-ylbis(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)sulfonium tetrafluoroborate (14 g), was obtained as a colorless oil (62.5 mg, 0.067 mmol, 67%) by silica gel flash column chromatography (hexane / CH2Cl2 = 100 : 0 - 0 : 100; then CH2Cl2 / methanol = 100 : 0 - 97 : 3). R f (CH2Cl2 / methanol = 95 : 5) : 0.1. 1H NMR (600 MHz, CDCl3) δ 8.96 (d, J = 2.3 Hz, 1H), 8.69 (d, J = 8.9 Hz, 1H), 8.59 (t, J = 7.6 Hz, 2H), 8.53 (d, J = 8.2 Hz, 1H), 8.47 (dd, J = 8.3, 5.2 Hz, 2H), 8.35 (d, J = 8.0 Hz, 1H), 7.67-7.50 (m, 11H), 7.15 (d, J = 8.9 Hz, 4H), 4.16 (dd, J = 6.0, 3.7 Hz, 4H), 3.82 (t, J = 4.7 Hz, 4H), 3.68 (q, J = 3.6, 2.8 Hz, 4H), 3.64 (t, J = 4.6 Hz, 4H), 3.62-3.60 (m, 3H), 3.53-3.49 (m, 4H), 3.33 (s, 6H). 13 C NMR (151 MHz, CDCl3) δ 163.8, 135.5, 133.1, 132.3, 132.0, 131.9, 131.6, 130.9, 130.5, 129.6, 129.2, 129.2, 129.0, 128.5, 128.4, 128.4, 128.0, 127.9, 127.4, 127.0, 126.7, 125.9, 125.3, 124.1, 123.8, 122.8, 117.8, 114.8, 72.0, 70.9, 70.6, 70.6, 69.3, 68.4, 59.1. 19 F NMR (376 MHz, CDCl3) δ -151.38. ESI-HRMS calcd for C 52 H 53 O8S [M-BF4] + : 837.3461; found: 837.3454.

[0258] (Example 11: Dibenzo[ghi,mno]fluorantene-2-ylbis(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)sulfonium tetrafluoroborate (14h))

[0259] [ka]

[0260] Compound 14h was prepared according to GP-2 using dibenzo[ghi,mno]fluorantene (50.6 mg, 0.2 mmol, 1.0 equivalent). The target compound, dibenzo[ghi,mno]fluorantene-2-ilbis(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)sulfonium tetrafluoroborate (14h), was obtained as a yellow oil (113.6 mg, 0.134 mmol, 67%) by silica gel flash column chromatography (hexane / CH2Cl2 = 100 : 0 - 0 : 100; then CH2Cl2 / methanol = 100 : 0 - 97 : 3). R f (CH2Cl2 / methanol = 95 : 5) : 0.1. 1 H NMR (600 MHz, CDCl3) δ 7.84-7.75 (m, 5H), 7.72-7.65 (m, 6H), 7.65-7.55 (m, 2H), 7.26-7.17 (m, 4H), 4.19 (dd, J = 5.6, 3.5 Hz, 4H), 3.87-3.79 (m, 4H), 3.68 (dd, J = 6.0, 3.4 Hz, 4H), 3.63 (dd, J = 5.9, 3.4 Hz, 4H), 3.64-3.56 (m, 4H), 3.54-3.46 (m, 4H), 3.32 (s, 6H). 13C NMR (151 MHz, CDCl3) δ 164.0, 137.2, 135.7, 135.6, 134.8, 134.4, 133.5, 132.6, 132.1, 131.3, 131.1, 129.8, 129.4, 129.2, 129.0, 128.8, 128.7, 127.7, 127.3, 127.1, 126.9, 122.9, 122.7, 118.0, 113.7, 71.8, 70.7, 70.5, 70.5, 69.2, 68.3, 59.0. 19 F NMR (376 MHz, CDCl3) δ -151.41. ESI-HRMS calcd for C 46 H 47 O8S [M-BF4] + : 758.2992, found 759.2985.

[0261] (Example 12: Coronen-1-Ilbis(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)sulfonium tetrafluoroborate (14i))

[0262] [ka]

[0263] Compound 14i was prepared according to GP-2 using coronene (scale as follows, 1.0 equivalent). By silica gel flash column chromatography (hexane / CH2Cl2 = 100 : 0 - 0 : 100; then CH2Cl2 / methanol = 100 : 0 - 97 : 3), the target compound, coronene-1-ilbis(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)sulfonium tetrafluoroborate (14i), was obtained as a dark yellow viscous oil. Isolation yield using GP-2 (0.2 mmol scale): 101.8 mg, 0.114 mmol, 57%. GP-2(0.5 mmol glucose) yield: 357.7 mg, 0.399 mmol, 80 %. Rf (CH2Cl2 / lead = 95:5): 0.1. 1 H NMR (600 MHz, CDCl3) δ 8.31 (d, J = 8.2 Hz, 1H), 8.14 (s, 1H), 8.09 (d, J = 8.3 Hz, 1H), 7.93 (d, J = 8.8 Hz, 4H), 7.85 (d, J = 8.2 Hz, 1H), 7.80 (d, J = 8.4 Hz, 1H), 7.58 (d, J = 8.1 Hz, 1H), 7.47 (d, J = 8.1 Hz, 1H), 7.40 (d, J = 8.1 Hz, 1H), 7.33 (d, J = 8.2 Hz, 1H), 7.28 (d, J = 9.2 Hz, 5H), 7.22 (d, J = 8.1 Hz, 1H), 4.23 (qd, J = 11.2, 10.7, 6.4 Hz, 4H), 3.85 (t, J = 4.6 Hz, 4H), 3.69 (dd, J = 5.9, 3.5 Hz, 4H), (dd, J = 5.8, 3.7 Hz, 4H), 3.63–3.52 (m, 4H), 3.54–3.43 (m, 4H), 3.31 (s, 6H). 13 C NMR (151 MHz, CDCl3) δ 163.9; 124.9, 124.6, 124.6, 124.5, 122.8, 121.7, 121.0, 118.6, 118.3, 118.3, 118.3, 118.0 (2C), 117.8, 114.0, 71.9, 70.8. 70.6, 70.5, 69.3, 68.4, 19 F NMR (373 MHz, CDCl3) δ-150.32. ESI-HRMS calcd for C 50 H 49 O8S [M-BF4] + : 809.3148; found 809.3132.

[0264] Example 13: Suzuki-Miyaura coupling of perylene monosulfonium salt (3-phenylperylene(20a)) Since there are no precedents in the literature for selectively introducing acyclic triarylsulfonium salts into cross-coupling reactions, the possibility of converting the bis(4-alkoxyphenyl)sulfonium group on compound 14 was investigated. As described below, 3-phenylperylene (20a) was preferentially obtained in 78% yield by Suzuki-Miyaura cross-coupling of bis(4-alkoxyphenyl)(perylene-3-yl)sulfonium salt (14d) with phenylboronic acid.

[0265] [ka]

[0266] Under air, bis(4-(2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)(perylene-3-yl)sulfonium tetrafluoroborate (14d) (83.5 mg, 0.098 mmol, 1.0 equivalent), phenylboronic acid (16.8 mg, 0.14 mmol, 1.4 equivalent), K3PO4 (39.6 mg, 0.19 mmol, 1.9 equivalent), 1,1'-bis(diphenylphosphino)ferrocene)dichloropalladium(II)(PdCl2(dppf))·CH2Cl2 (1.0 mg, 1.2 μmol, 1.2 mol%), 1,4-dioxane (0.4 mL), and ethanol (0.4 mL) were added to a 7 mL test tube equipped with a polytetrafluoroethylene-coated stirring rod. The mixture was degassed by bubbling with N2, and the test tubes were capped with plastic caps and polytetrafluoroethylene-coated septums. The mixture was stirred at 50°C for 14.5 hours, then passed through a silica gel short pad, and the solvent was removed under reduced pressure. The residue was purified by silica gel flash column chromatography (eluent: CH2Cl2) to obtain 3-phenylperylene (20a) as a yellow solid (25.3 mg, 0.077 mmol, 78%). R f (Hexane / ethyl acetate = 95 : 5) : 0.4. 1 H NMR (600 MHz, CDCl3) δ 8.25-8.21 (m, 4H), 7.77 (d, J = 8.2 Hz, 1H), 7.70 (d, J = 8.2 Hz, 2H), 7.54-7.48 (m, 6H), 7.46-7.42 (m, 3H). 13 C NMR (151 MHz, CDCl3) δ 140.9, 140.1, 134.9, 133.1, 131.6, 131.6, 131.4, 130.8, 130.1 (2C), 129.2, 128.8, 128.5 (2C), 128.0, 127.9, 127.9, 127.5, 126.8 (2C), 126.7, 126.3, 120.5 (2C), 120.3, 120.1. DART-HRMS calcd for C 26 H 17 [M+H] + : 329.1330; found: 329.1335.

[0267] Examples 14-15: Suzuki-Miyaura coupling and Scholl reaction of perylenebissulfonium salts Inspired by the results of Example 13, we also investigated the double cross-coupling of perylenebissulfonium salt (14d') with phenylboronic acid and (3,6-di-tert-butylnaphthalene-1-yl)boronic acid pinacol ester, yielding diarylated perylene (20b and 20c) in high yields (77% and 83%). Dinaphthylperylene (20c) was extended to tetra-tert-butyl quaternary arylene compound (21) in high yield of 86% via a Scholl reaction using FeCl3 as an accelerator.

[0268] Compared to the synthesis of compound 21 from naphthalene oligomers by Mullen et al. (A. Bohnen, K.-H. Koch, W. Luttke, K. Mullen, Angew. Chem. Int. Ed. 1990, 29, 525-527., K.-H. Koch, K. Mullen, Chem. Ber. 1991, 124, 2091-2100., U. Scherf, K. Mullen, Synthesis 1992, 23-38.), the synthetic route for compound 21 according to the present invention offers several advantages, including cost-effectiveness of steps, the ability to use readily available perylene as a starting material, the absence of aromatic ring rearrangement in the Scholl reaction, and the possibility of a two-step APEX reaction in high yield.

[0269] (Example 14: 3,10-diphenylperylene(20b))

[0270] [ka]

[0271] Under air, perylene-3,10-diylbis(bis(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)sulfonium)ditetrafluoroborate (14d') (141.2 mg, 0.098 mmol, 1.0 equivalent), phenylboronic acid (32.1 mg, 0.26 mmol, 2.7 equivalents), K3PO4 (84.8 mg, 0.40 mmol, 4.1 equivalents), 1,1'-bis(diphenylphosphino)ferrocene)dichloropalladium(II)(PdCl2(dppf))·CH2Cl2 (3.1 mg, 3.8 μmol, 3.9 mol%), 1,4-dioxane (0.4 mL), and ethanol (0.4 mL) were added to a 7 mL test tube equipped with a polytetrafluoroethylene-coated stirring rod. The mixture was degassed by bubbling with N2, and the test tubes were capped with plastic caps and polytetrafluoroethylene-coated septums. The mixture was stirred at 50°C for 14.5 hours, and then passed through a short pad of silica gel. The solvent was removed under reduced pressure, and the residue was purified by silica gel flash column chromatography (eluent: CH2Cl2). The product was vacuum-dried to obtain 3,10-diphenylperylene (20b) as a yellow solid (30.5 mg, 0.75 mmol, 77%). R f (hexane / EtOAc = 95 : 5) : 0.4. 1 H NMR (600 MHz, CDCl3) δ 8.27 (d, J = 7.6 Hz, 2H), 8.26 (d, J = 6.2 Hz, 2H), 7.78 (d, J = 8.2 Hz, 2H), 7.55-7.51 (m, 8H), 7.47-7.44 (m, 6H). 13 C NMR (600 MHz, CDCl3) δ 140.9, 140.1, 133.0, 131.6, 131.0, 130.1, 129.1, 128.5, 128.0, 127.5, 126.7, 126.2, 120.4, 120.2. DART-HRMS calcd for C 32 H21 [M+H] + : 405.1643; found: 405.1647.

[0272] (Example 15: 3,10-bis(3,6-di(tert-butyl)naphthyl)perylene(20c))

[0273] [ka]

[0274] Under air, perylene-3,10-diylbis(bis(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)sulfonium)ditetrafluoroborate (14d') (70.3 mg, 0.049 mmol, 1.0 equivalent), phenylboronic acid (51.1 mg, 0.14 mmol, 2.9 equivalents), K3PO4 (41.6 mg, 0.20 mmol, 4.0 equivalents), 1,1'-bis(diphenylphosphino)ferrocene)dichloropalladium(II)(PdCl2(dppf))·CH2Cl2 (1.5 mg, 1.8 μmol, 3.8 mol%), 1,4-dioxane (0.2 mL), and ethanol (0.2 mL) were added to a 7 mL test tube equipped with a polytetrafluoroethylene-coated stirring rod. The mixture was degassed by bubbling with N2, and the test tubes were capped with plastic caps and polytetrafluoroethylene coated septums. The mixture was stirred at 50°C for 24 hours, and the reaction mixture was passed through a silica short pad, with the solvent removed under reduced pressure. The residue was purified by pTLC (eluent: hexane). The product was vacuum-dried to obtain 3,10-bis(3,6-di(tert-butyl)naphthyl)perylene (20c) as a yellow solid (29.4 mg, 0.040 mmol, 83%). R f (Hexane / ethyl acetate = 95 : 5) : 0.5. 1H NMR (600 MHz, CDCl3) δ 8.34 (dd, J = 7.9, 1.7 Hz, 2H), 8.29-8.28 (m, 2H), 7.88 (d, J = 7.6 Hz, 4H), 7.59 (d, J = 2.1 Hz, 2H), 7.53 (d, J = 7.6 Hz, 2H), 7.43 (dd, J = 8.9, 5.5 Hz, 2H), 7.39 (dd, J = 8.9, 2.1 Hz, 2H), 7.37-7.35 (m, 4H), 1.48 (s, 9H), 1.47 (s, 9H), 1.42 (s, 9H), 1.41 (s, 9H). 13 C NMR (151 MHz, CDCl3) δ 148.7, 148.3, 139.0, 137.7, 134.3, 133.7, 131.6, 131.1, 129.3, 128.9, 126.9, 126.7, 126.4, 125.9, 125.9, 124.6, 123.4, 123.2, 120.3, 120.1, 35.1, 34.9, 31.5, 31.4. MALDI-TOF MS calcd for C 56 H 56 ·+ [M] ·+ : 728.4377; found: 728.4381.

[0275] (Example 16: 2,5,12,15-tert-ブチルクアテリレン(21))

[0276]

change

[0277] In a 100 mL two-necked round-bottom flask equipped with a polytetrafluoroethylene-coated stirring bar, 3,10-bis(3,6-di(tert-butyl)naphthyl)perylene (20c) (27.0 mg, 0.037 mmol, 1.0 equivalent) obtained in Example 15 and CH2Cl2 (24 mL) were added under a nitrogen atmosphere. The mixture was degassed by bubbling with nitrogen, and the flask was sealed with a rubber cepter. Next, a solution of FeCl3 (181.3 mg, 1.4 mmol, 37 equivalents) in CH3NO2 (0.6 mL) was added dropwise by syringe. The mixture was stirred at room temperature (24°C) for 15 hours, and the reaction was quenched by adding excess methanol. The deep blue precipitate was collected using a membrane filter and washed with methanol. The deep blue solid was transferred to a vial and washed with hexane to remove the soluble red fluorescent component. This hexane washing was repeated until the red solvent color became clear. Finally, this solid was dried in a vacuum to obtain 2,5,12,15-tetrakis(tert-butyl)quaterylene (21) as a deep blue solid (23.2 mg, 0.32 mmol, 86%). R f (Hexane / ethyl acetate = 95 : 5) : 0.4. 1 H NMR (600 MHz, CDCl3) δ 8.46-8.22 (m, 12H), 7.67 (br s, 4H), 1.51 (s, 36H). MALDI-TOF MS calcd C 56 H 52 ·+ [M] ·+ : 724.4064; found: 724.4072. Furthermore, the absorption spectrum of the obtained 2,5,12,15-tetrakis(tert-butyl)quaterylene (21) is shown in Figure 2 and was equivalent to that previously reported (K.-H. Koch, K. Mullen, Chem. Ber. 1991, 124, 2091-2100).

[0278] [General Procedure for Rubicen 4 (GP-4)] 4,4'-Sulfinylbis((2-(2-methoxyethoxy)ethoxy)ethoxy)benzene (1.0 equivalent) and rubicene (1.0 equivalent) were added to a two-necked round-bottom flask (100 mL or 200 mL) equipped with a polytetrafluoroethylene-coated stirring bar under air. Dry 1,2-dichloroethane (0.0125 M relative to the polycyclic aromatic hydrocarbon compound) was added, and the mixture was stirred at 26°C until all solids were dissolved. Next, trifluoromethanesulfonic anhydride (Tf2O; 3.0 equivalents) and concentrated H2SO4 (1.5 equivalents) were added dropwise, respectively, under air. The reaction mixture was stirred at 26°C for 24 hours. After completion, the reaction mixture was diluted with CH2Cl2, saturated aqueous NaHCO3 was added, and the mixture was stirred for 1 minute, after which the layers were separated. The organic layer was washed twice with saturated aqueous NaBF4, dried over anhydrous Na2SO4, filtered, and concentrated under vacuum. Silica gel flash column chromatography (CH2Cl2 / methanol = 100:0 - 80:20) yielded monoaddition and diaddition sulfonium salts as viscous oils.

[0279] (Example 17: Rubicen-5-yl(bis(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)sulfonium)tetrafluoroborate (22a) and rubicen-5,12-diylbis(bis(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)sulfonium)ditetrafluoroborate (22b))

[0280] [ka]

[0281] In the formula, Tf2O represents trifluoromethanesulfonic anhydride. 1,2-DCE represents 1,2-dichloroethane. TEG represents a triethylene glycol group.

[0282] Compounds 22a and 22b were prepared according to GP-4 using rubicene (1.0 equivalent). The target compounds were obtained as a red, viscous oil that appeared fluorescent red when diluted by silica gel flash column chromatography (CH2Cl2 / methanol = 100:0 → 80:20) in the isolation yields shown below. Isolation yield using GP-4 (0.3 mmol scale): 1 adduct 140.7 mg, 0.152 mmol, 51%. Diadduct 37.2 mg, 0.024 mmol, 8%. Rf (CH2Cl2 / methanol = 90 : 10): 1 adduct 0.5 (broad). 2 adducts 0.3-0.4 (broad).

[0283] 1 adduct 1 H NMR (400 MHz, CDCl3) δ 8.07-8.01 (m, 3H), 7.89-7.87 (m, 1H), 7.85 (d, J = 8.7 Hz, 1H), 7.80 (d, J = 8.7 Hz, 4H), 7.77 (s, 1H), 7.72-7.70 (m, 1H), 7.58 (d, J = 6.9 Hz, 1H), 7.50 (d, J = 8.5 Hz, 1H), 7.37 (d, J = 8.0 Hz, 1H), 7.33 (dd, J = 7.9, 3.5 Hz, 3H), 7.27-7.25 (m, 10H; Note: including CDCl3peak.), 4.25 (t, J = 4.5 Hz, 4H), 3.90-3.88 (m, 4H), 3.73 (dd, J = 5.5, 3.9 Hz, 4H), 3.68-3.62 (m, 8H), 3.54-3.52 (m, 4H), 3.35 (t, J = 0.6 Hz, 6H). 1313C NMR (101 MHz, CDCl3) δ 163.7, 143.4, 140.5, 139.3, 138.7, 137.2, 135.2, 133.6, 133.1, 132.3, 131.5, 129.5, 128.9, 128.2, 128.0, 127.8, 127.5, 125.1, 124.8, 124.6, 123.9, 123.3, 122.9, 122.6, 122.3, 121.5, 121.3, 119.9, 117.8, 115.7, 77.5, 77.4, 77.2, 76.8, 72.0, 70.9, 70.7, 70.6, 69.4, 68.4, 59.1. 19 19F NMR (376 MHz, CDCl3) δ -150.9. HRMS (MALDI + ) calcd for C 52 H 51 O8S + ([M-BF4] + ): 835.3300; found: 835.3318.

[0284] 2 Adduct 1 1H NMR (400 MHz, CHLOROFORM-D) δ 8.46 (br, 2H), 8.24-8.33 (br, 2H), 7.96 (d, J = 8.7 Hz, 8H), 7.91 (br, 2H), 7.76-7.83 (br, 2H), 7.70 (m, 4H), 7.34 (d, J = 8.9 Hz, 8H), 4.28 (t, J = 4.7 Hz, 8H), 3.90 (t, J = 4.6 Hz, 8H), 3.74-3.72 (m, 8H), 3.67-3.61 (m, 16H), 3.53-3.51 (m, 8H), 3.34 (s, 12H). 19 19F NMR (376 MHz, CDCl3) δ -150.4.

[0285] Example 18: Suzuki-Miyaura coupling reaction of rubicene monosulfonium salt (5-(3,5-di-tert-butylphenyl)rubicene(23a)) Since there are no precedents in the literature for selectively introducing acyclic triarylsulfonium salts into cross-coupling reactions, the possibility of converting the bis(4-alkoxyphenyl)sulfonium group on compound 22a was investigated. As described below, 5-(3,5-di-tert-butylphenyl)rubicene (23a) was preferentially obtained in 61% yield by Suzuki-Miyaura cross-coupling of rubicen-5-yl(bis(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)sulfonium) tetrafluoroborate (22a) and 3,5-di-tert-butylphenylboronic acid.

[0286] [ka]

[0287] During the ceremony, t Bu indicates a tert-butyl group. Ph indicates a phenyl group. dppf indicates 1,1'-bis(diphenylphosphin)ferrocene. EtOH indicates ethanol.

[0288] Under air, rubicen-5-yl(bis(4-(2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)sulfonium)tetrafluoroborate (22a) (113.2 mg, 0.123 mmol, 1.0 equivalent), 3,5-di-tert-butylphenylboronic acid (41.3 mg, 0.172 mmol, 1.4 equivalents), K3PO4 (51.0 mg, 0.234 mmol, 1.9 equivalents), (1,1'-bis(diphenylphosphino)ferrocene)dichloropalladium(II)(PdCl2(dppf))·CH2Cl2 (4.0 mg, 4.9 μmol, 4.0 mol%), 1,4-dioxane (0.5 mL), and ethanol (0.5 mL) were added to a 7 mL test tube equipped with a polytetrafluoroethylene-coated stirring rod. The mixture was degassed by bubbling with N2, and the test tubes were capped with plastic caps and polytetrafluoroethylene-coated septums. The mixture was stirred at 50°C for 3 days, then passed through a short pad of silica gel, and the solvent was removed under reduced pressure. The residue was purified by silica gel flash column chromatography (hexane / CH2Cl2 = 100:0 → 80:20) to obtain 5-(3,5-di-tert-butylphenyl)rubicene (23a) as a red solid (38.4 mg, 0.075 mmol, 61%). Rf (hexane / CH2Cl2 = 80 : 20): 0.4. 1 H NMR (400 MHz, CDCl3) δ 8.52-8.49 (m, 2H), 8.31-8.25 (m, 2H), 8.15-8.13 (m, 1H), 8.03 (d, J = 6.6 Hz, 1H), 7.97-7.93 (m, 2H), 7.75-7.71 (m, 2H), 7.68 (dd, J = 8.0, 1.6 Hz, 1H), 7.62-7.60 (m, 2H), 7.52 (t, J = 1.7 Hz, 1H), 7.47-7.42 (m, 1H), 7.40-7.36 (m, 1H), 1.47 (s, 18H). 13C NMR (101 MHz, CDCl3) δ 151.4, 141.4, 141.0, 140.1, 140.0, 139.5, 138.7, 138.2, 133.5, 133.5, 133.4, 133.1, 129.0, 128.2, 127.4, 127.0, 125.6, 125.4, 124.7, 124.6, 123.9, 123.8, 121.8, 121.8, 121.7, 120.8, 120.4, 120.4, 35.2, 31.8. HRMS (MALDI + ) calcd for C 40 H 34 ([M] + ): 514.2661; found: 514.2665.

[0289] Example 19: Suzuki-Miyaura coupling reaction of rubicenebissulfonium salt (5,12-bis(3,5-di-tert-butylphenyl)rubicene(23b)) Inspired by the results of Example 18, we also investigated a double Suzuki-Miyaura cross-coupling of rubicenebissulfonium salt (22b) with 3,5-di-tert-butylphenylboronic acid, which yielded diarylylated rubicene (23b) in high yield (54%).

[0290] [ka]

[0291] During the ceremony, t Bu indicates a tert-butyl group. Ph indicates a phenyl group. dppf indicates 1,1'-bis(diphenylphosphin)ferrocene. EtOH indicates ethanol.

[0292] Under air, in a 7 mL test tube equipped with a polytetrafluoroethylene-coated stirring rod, the following were added: rubicen-5,12-diylbis(bis(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)sulfonium)ditetrafluoroborate (22b) (41.8 mg, 0.028 mmol, 1.0 equivalent) obtained in Example 17, 3,5-di-tert-butylphenylboronic acid (11.4 mg, 0.049 mmol, 1.8 equivalents), K3PO4 (15.4 mg, 0.073 mmol, 2.6 equivalents), (1,1'-bis(diphenylphosphino)ferrocene)dichloropalladium(II)(PdCl2(dppf))·CH2Cl2 (1.7 mg, 2.1 μmol, 7.4 mol%), and 1,4-dioxane (0.13 (mL) and ethanol (0.13 mL) were added. The mixture was degassed by bubbling with N2, and the test tubes were capped with plastic caps and polytetrafluoroethylene-coated septums. The mixture was stirred at 50°C for 3 days, then passed through a silica gel short pad, and the solvent was removed under reduced pressure. The residue was purified by silica gel flash column chromatography (hexane / CH2Cl2 = 100 : 0 → 80 : 20) to obtain 5,12-bis(3,5-di-tert-butylphenyl)rubicene (23b) as a red solid (11.4 mg, 0.016 mmol, 54%). Rf (hexane / CH2Cl2 = 80 : 20): 0.4. 1 H NMR (400 MHz, CDCl3) δ 8.58 (d, J = 8.5 Hz, 2H), 8.35 (d, J = 8.0 Hz, 2H), 8.17 (s, 2H), 8.09 (d, J = 6.6 Hz, 2H), 7.78 (dd, J = 8.6, 6.7 Hz, 2H), 7.71-7.69 (m, 2H), 7.61 (d, J = 1.6 Hz, 4H), 7.52 (s, 2H), 1.46 (d, J = 1.6 Hz, 36H). 13C NMR (101 MHz, CDCl3) δ 151.4, 141.5, 141.0, 140.1, 138.8, 138.3, 133.6, 133.4, 129.0, 127.5, 125.6, 124.8, 123.9, 121.8, 120.9, 120.5, 35.2, 31.8. HRMS (MALDI + ) calcd for C 54 H 54 ([M] + ): 702.4226; found: 702.4253.

[0293] Test Example 1: Crystallographic Data The 2,5,12,15-tetrakis(tert-butyl)quinterylene (21) obtained in Example 16 was recrystallized from CHCl3 / hexane by vapor phase growth.

[0294] Table 1 shows detailed crystal data and an overview of intensity data acquisition parameters for compound 21 (CCDC Nr.: 2397243). Appropriate crystals were mounted on MiTeGen MicroMounts with mineral oil and transferred to a kappagoniometer in a RIGAKU XtaLAB Synergy-S system equipped with a 1.2 kW MicroMax-007HF microfocus rotating anode (graphite monochromatic Mo Kα line (λ = 0.71073 Å)) and a PILATUS200K hybrid photon counting detector. Cell parameters were determined and refined using CrysAlisPro (Agilent Technologies, 2010), and raw frame data were integrated. The structure was determined by a direct method using (SHELXT) (GM Sheldrick, Acta Cryst. A 2015, 71, 3-8.), and refined for F2 (SHELXL-2018 / 3) (GM Sheldrick, Acta Cryst. A 2015, 71, 3-8.) using the Olex2 software package (OV Dolomanov, LJ Bourhis, RJ Gildea, JAK Howard, H. Puschmann, J. Appl. Crystallogr. 2009, 42, 339-341.) by the total matrix least squares method. Non-hydrogen atoms were purified anisotropically. Hydrogen atoms were positioned using the AFIX instructions. Visualization was performed in ORTEP style using Mercury (CF Macrae, IJ Bruno, JA Chisholm, PR Edgington, P. McCabe, E. Pidcock, L. Rodriguez-Monge, R. Taylor, J. van de Streek, PA Wood, J. Appl. Crystallogr. 2008, 41, 466-470.) 3.8. The results are shown in Figure 3.

[0295] [Table 1]

[0296] Next, single-crystal X-ray structural analysis was performed on 5,12-bis(3,5-di-tert-butylphenyl)rubicene (23b), the product of Example 19 obtained by the Suzuki-Miyaura cross-coupling reaction using rubicenebissulfonium salt as the starting material. As a result, it was clearly confirmed that sulfonium groups were introduced at two specific locations on the rubicene skeleton, as shown in Figure 4.

[0297] Since this reaction involves selective cross-coupling at the carbon atom corresponding to the position where the sulfonium group is introduced, the cross-coupling position of the monosulfonium compound obtained under the same reaction conditions can be easily determined based on the X-ray crystal structure of the bissulfonium compound.

[0298] Therefore, in the present invention Suzuki-Miyaura coupling reaction The fact that the process is proceeding with the expected regioselectivity is also supported by the results of the crystal structure analysis of the bissulfonium compound.

[0299] Test Example 2: Photochemical Properties It was found that the sulfonation strategy not only increases the solubility of polycyclic aromatic hydrocarbon compound adducts in organic solvents, but also enables their handling in aqueous solutions.

[0300] Compound 14d(c = 1.46 × 10) obtained in Example 7 -5 M), Compound 14d'(c = 1.71 × 10) obtained in Example 8 -5 M), Perylene in CH2Cl2 (Reference; c = 1.31 × 10) -5The UV-Vis absorption spectra of compound 14d obtained in Example 7 in M) and H2O were recorded at a resolution of 0.5 nm in a 1.0 × 1.0 cm square quartz cell of a SHIMADZU UV-3600 spectrophotometer. The emission spectra of compound 14d, compound 14d', and perylene in CH2Cl2 or H2O were recorded at a resolution of 0.2 nm in a 1.0 × 1.0 cm square quartz cell using a SHIMADZU RF-6000 spectrofluorometer, with excitation wavelengths of 400 nm (compound 14d in CH2Cl2), 450 nm (compound 14d in H2O), 400 nm (compound 14d' in CH2Cl2), and 400 nm (perylene in CH2Cl2), respectively. The results are shown in Figure 5.

[0301] Both the mono-(compound 14d) and bis-adduct (14d') are composed of the original perylene (λ) in CH2Cl2. abs (perylene) = 437 nm) Compared to this, the absorption shifted to red (absorption maximum λ) abs (14d) = λ abs (14d') = 470 nm) was observed. Regarding fluorescence, the emission maximum (λ) of the mono adduct (14d) was observed. em (14d) = 518 nm) is perylene (λ) for charge separation. em (perylene) shows a red shift compared to (442 nm). On the other hand, the bis adduct (14d') shows a slight blue shift (λ) with a small Stokes shift compared to (14d). em (14d') = 480 nm) is shown. Furthermore, the water-soluble monoadduct 14d has λ abs = Broad absorption with a maximum at 449 nm, and λ em It exhibits emission with a maximum peak at 528 nm, and the fluorescence quantum yield in H2O is Φ F The result was 0.58.

[0302] Example 3: Biological Experiment Since we were able to fully understand the photophysical properties and good solubility of the polycyclic aromatic sulfonium compound of the present invention, we performed imaging of HeLa cells using bis(4-(2-(2-(2-2-methoxyethoxy)ethoxy)ethoxy)phenyl)(perylene-3-yl)sulfonium tetrafluoroborate (14d) obtained in Example 7.

[0303] HeLa cells (ATCC, 0.5×10 5 Cells were seeded on the glass area of ​​a 35 mm glass-bottom dish (Matsunami) and cultured for 1 day at 37°C in a humidified atmosphere of 5% CO2 in air in high-glucose Dulbecco's modified Eagle medium (DMEM, Sigma-Aldrich) supplemented with 10% fetal bovine serum (FBS, Sigma F7524, Lot: BCBV4600) and 1% antibiotic-antifungal agent (Anti-Anti, Sigma-Aldrich). Cells were stained with a mitochondrial marker (MitoBright LT Red, Tongrentang) according to a general procedure. Subsequently, the medium was replaced with a DMEM solution (1.0 mL) of compound 14d (1 mM in dimethyl sulfoxide, 1 μL) without 10% FBS and 1% Anti-Anti, and cultured at 37°C in a humidified atmosphere of 5% CO2 in air. After a 30-minute incubation, the culture medium was replaced with fresh DMEM, and cell imaging was performed using a confocal laser scanning microscope equipped with a 63x oil immersion objective lens (Carl Zeiss LSM900). Compound 14d was excited at 488 nm and detected at 490-700 nm, while the mitochondrial marker was excited at 557 nm and detected at 560-700 nm.

[0304] Cell imaging results are shown in Figure 6, and results regarding cell viability are shown in Figure 7. These results demonstrate that fluorescence was observed within cells without any signs of cytotoxicity, as seen in confocal microscopy images. The polycyclic aromatic sulfonium compounds of the present invention appear to localize to specific organelles, as confirmed by mitochondrial markers. This is consistent with the tendency of delocalized lipophilic cations (DLCs) to accumulate in mitochondria.

Claims

1. General formula (1): 【Chemistry 1】 [In the formula, Ar １ R represents a naphthalene ring, binaphthalene ring, or polycyclic aromatic hydrocarbon ring, which may have substituents. １ and R ２ This represents an aryl group which may have one or two substituents, and which may be identical or different. A polycyclic aromatic sulfonium compound having a cation represented by .

2. The aforementioned R １ and R ２ The polycyclic aromatic sulfonium compound according to claim 1, wherein the phenyl group may have substituents.

3. The aforementioned R １ and R ２ The polycyclic aromatic sulfonium compound according to claim 1, wherein the phenyl group has a substituent.

4. The aforementioned R １ and R ２ The polycyclic aromatic sulfonium compound according to claim 1, wherein the substituents in are a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted glycol group, or an optionally substituted dialkylamino group.

5. Furthermore, the polycyclic aromatic sulfonium compound according to claim 1, having a counter anion.

6. A fluorescent dye containing a polycyclic aromatic sulfonium compound according to any one of claims 1 to 5.

7. An intracellular organelle staining agent containing the fluorescent dye described in claim 6.

8. A method for producing a polycyclic aromatic sulfonium compound according to any one of claims 1 to 5, In the presence of strong acids and strong acid anhydrides, Naphthalene, binaphthalene, or polycyclic aromatic hydrocarbon compounds (Ar １ ;Ar １ (This is the same as above) General formula (2): 【Chemistry 2】 [In the formula, R １ and R ２ This is the same as above. A step of reacting with a sulfinyl compound represented by A manufacturing method that includes the following features.

9. General formula (3A): 【Transformation 3】 [In the formula, Ar １ The same applies as above. R ３ａ [where n1 represents a halogen atom or a cyano group, and n1 represents 1 or 2] A method for producing polycyclic aromatic compounds represented by, In the presence of a ruthenium catalyst and a copper compound, A step of reacting a polycyclic aromatic sulfonium compound according to any one of claims 1 to 5 with a compound having a halogen atom or a cyano group. A manufacturing method that includes the following features.

10. General formula (3B): 【Chemistry 4】 [In the formula, Ar １ The same applies as above. R ３ｂ n2 represents an optionally substituted alkenyl group or an optionally substituted alkynyl group. n2 represents 1 or 2. A method for producing polycyclic aromatic compounds represented by, In the presence of a palladium catalyst and a copper compound, A step of reacting a polycyclic aromatic sulfonium compound according to any one of claims 1 to 5 with a compound having an alkenyl group or an alkynyl group. A manufacturing method that includes the following features.

11. General formula (3C): 【Transformation 5】 [In the formula, Ar １ The same applies as above. R ３ｃ [where n3 represents an aryl group which may have substituents. n3 represents 1 or 2.] A method for producing polycyclic aromatic compounds represented by, In the presence of a palladium catalyst, A step of reacting a polycyclic aromatic sulfonium compound according to any one of claims 1 to 5 with a compound having an aryl group. A manufacturing method that includes the following features.

12. A method for producing extended polycyclic aromatic hydrocarbon compounds, A step of subjecting a polycyclic aromatic compound represented by general formula (3C) obtained by the manufacturing method described in claim 11 to a ring fusion reaction. A manufacturing method that includes the following features.

13. A method for increasing the fluorescence maximum wavelength of naphthalene, binaphthalene, or polycyclic aromatic hydrocarbon compounds, In the presence of strong acids and strong acid anhydrides, The naphthalene, binaphthalene, or polycyclic aromatic hydrocarbon compound, General formula (2): 【Transformation 6】 [In the formula, R １ and R ２ This represents a (hetero)aryl group which may have one or two substituents, either identical or different. A step of reacting with a sulfinyl compound represented by A method that includes [something].

14. A solubilizer for naphthalene, binaphthalene, or polycyclic aromatic hydrocarbon compounds, General formula (2): 【Transformation 7】 [In the formula, R １ and R ２ This represents a (hetero)aryl group which may have one or two substituents, either identical or different. A solubilizer for naphthalene, binaphthalene, or polycyclic aromatic hydrocarbon compounds, comprising a sulfinyl compound represented by , a strong acid, and a strong acid anhydride.

15. General formula (2A): 【Transformation 8】 [In the formula, R ４ and R ５ These are identical or different groups, representing alkoxy groups or glycol groups having 6 to 20 carbon atoms. A compound represented by the formula.

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