Adamantane-fused oligothiophene compound and method for producing same

Abstract

General formula (1): [In the formula, A1 are the same or different and represent an adamantane ring. R1 and R2 are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group. n represents an integer from 2 to 8.] This adamantane-fused oligothiophene compound represented by the formula is an oligothiophene compound in which the thiophene ring takes an s-cis conformation, and can be easily synthesized.

Description

Adamantane-fused oligothiophene compound and method for producing the same

[0001] The present invention relates to an adamantane-fused oligothiophene compound and a method for producing the same.

[0002] Oligothiophene compounds, including terthiophene, have long been widely used as organic electronic materials. Among oligothiophene compounds, those in which the thiophene ring has an s-cis conformation are known to have superior conductivity compared to those in which the thiophene ring has an s-trans conformation (see, for example, Non-Patent Document 1).

[0003] J. Phys. Chem. Lett. 2019, 10, 5292.

[0004] However, there have been very few examples of oligothiophene compounds in which the thiophene ring takes an s-cis conformation.

[0005] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to simply synthesize an oligothiophene compound in which the thiophene ring has an s-cis conformation.

[0006] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that it is possible to synthesize highly soluble oligothiophene compounds in which the thiophene rings have an s-cis conformation by reacting an adamantane-fused dithiophene compound with a nucleophile, followed by reaction with an adamantanone compound, and then reaction with a Bronsted acid or a Lewis acid. By repeating this process, it is also possible to synthesize long-chain adamantane-fused oligothiophene compounds. Based on this finding, the present inventors have further intensively researched and completed the present invention. The present invention encompasses the following configurations.

[0007] Item 1. General formula (1):

[0008]

[0009] [In the formula, A １ are the same or different and represent an adamantane ring. １ and R ２are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group, and n represents an integer of 2 to 8.

[0010] Item 2. Said A １ are the same or different and represent general formula (1A) or (1B):

[0011]

[0012] [wherein the dashed line indicates the bond site where the ring is fused to the adjacent ring. ３ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group, and k represents an integer of 0 to 3.

[0013] Item 3. Said A １ are the same or different and are represented by the general formula (1A1), (1A2), (1B1) or (1B2):

[0014]

[0015] [wherein the dashed line indicates the bond site fused to the adjacent ring. R ３ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group, and k represents an integer of 0 to 3.

[0016] Item 4. General formula (1'):

[0017]

[0018] [In the formula, R １ and R ２ is the same as above. ３ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group. k represents an integer of 0 to 3. m represents an integer of 1 to 4.

[0019] Item 5. A method for producing the adamantane-fused oligothiophene compound according to any one of Items 1 to 4, comprising: (1) reacting a compound represented by the general formula (2):

[0020]

[0021] [In the formula, R １ , R ２ , n and A １ is the same as above. １ represents a halogen atom.] is reacted with a nucleophile, and then a compound represented by general formula (3A) or (3B):

[0022]

[0023] [In the formula, R ３ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group, and k represents an integer of 0 to 3.] to react with an adamantanone compound represented by the general formula (4):

[0024]

[0025] [In the formula, R １ , R ２ , R ３ , n, k and A １ (II) a step of reacting the adamantane-containing oligothiophene compound obtained in the step (I) with a Bronsted acid and / or a Lewis acid.

[0026] Item 6. The production method according to Item 5, wherein the nucleophilic agent is an organolithium compound and / or an organomagnesium compound.

[0027] Section 7. General formula (4):

[0028]

[0029] [In the formula, R １ and R ２are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group. ３ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group. n represents an integer of 2 to 8. k represents an integer of 0 to 3. A １ and are the same or different and represent an adamantane ring.] An adamantane-containing oligothiophene compound represented by the following formula:

[0030] Section 8. General formula (2):

[0031]

[0032] [In the formula, R １ and R ２ are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group. n represents an integer of 2 to 8. １ are the same or different and represent an adamantane ring. １ represents a halogen atom.] A compound represented by the following formula:

[0033] Item 9. General formula (2):

[0034]

[0035] [In the formula, R １ and R ２ are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group. n represents an integer of 2 to 8. １ are the same or different and represent an adamantane ring. １ represents a halogen atom.], the method for producing a compound represented by the general formula (5):

[0036]

[0037] [In the formula, R １ , n and A １are the same as above.] with an organolithium compound and a trialkyltin halide compound, and (IV) reacting the compound obtained in the step (III) with a compound represented by the general formula (6):

[0038]

[0039] [In the formula, X １ is the same as above. ２ represents a halogen atom] with a compound represented by the formula (I) in the presence of a palladium catalyst.

[0040] According to the present invention, an oligothiophene compound in which the thiophene ring has an s-cis conformation can be easily synthesized.

[0041] This shows the adamantane-bromoterthiophene compound 4 obtained in Example 1. This shows the ultraviolet-visible (UV / vis) absorption spectrum of the bis-adamantane-terthiophene compound 5 and terthiophene obtained in Example 2. This shows the fluorescence spectrum of the bis-adamantane-terthiophene compound 5 and terthiophene obtained in Example 2.

[0042] In this specification, the term "containing" is a concept that encompasses all of "comprise," "consist essentially of," and "consist only of."

[0043] In addition, in this specification, when a numerical range is expressed as "A to B," it means A or more and B or less.

[0044] 1. Adamantane-fused oligothiophene compound The adamantane-fused oligothiophene compound of the present invention is represented by the general formula (1):

[0045]

[0046] [In the formula, A １ are the same or different and represent an adamantane ring. １ and R ２are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group, and n represents an integer of 2 to 8.

[0047] This adamantane-fused oligothiophene compound is a compound in which the thiophene ring is fixed in an s-cis conformation, and it is understood that the structure thereof has high electrical conductivity and also high solubility. In particular, since the adamantane-fused oligothiophene compound of the present invention is soluble in hexane, which does not dissolve many other materials, it is understood that the compound has high solubility in other solvents as well, and improves operability.

[0048] Furthermore, this adamantane-fused oligothiophene compound has a high HOMO (highest occupied molecular orbital) and a small HOMO (highest occupied molecular orbital)-LUMO (lowest unoccupied molecular orbital) gap, and electrons can easily transition to the conduction band, which increases the current flow ability and provides good semiconductor properties.

[0049] In general formula (1), A １ represents an adamantane ring. １ is fused to the adjacent ring at the bonding site between the two carbon atoms, and depending on the positions of the sp2 carbon atom and the sp3 carbon atom in the two carbon atoms, it can be represented by the general formulas (1A) and (1B):

[0050]

[0051] [wherein the dashed line indicates the bond site fused to the adjacent ring. R ３ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group, and k represents an integer of 0 to 3.

[0052] In addition, the above-mentioned A １ The configuration (R-configuration and S-configuration) of the adamantane ring represented by the general formulae (1A1), (1A2), (1B1) and (1B2):

[0053]

[0054] [wherein the dashed line indicates the bond site fused to the adjacent ring. R ３ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group. k represents an integer of 0 to 3. ] can be used. According to the production method of the present invention described below, the configuration of the most adjacent adamantane ring is likely to be such that the R- and S-configurations are arranged alternately. For example, the adamantane rings most adjacent to the adamantane rings of general formulae (1A1) and (1B1) are likely to be the adamantane rings of general formulae (1A2) and (1B2), and the adamantane rings most adjacent to the adamantane rings of general formulae (1A2) and (1B2) are likely to be the adamantane rings of general formulae (1A1) and (1B1).

[0055] From the above, for example, the ring closest to the adamantane ring of general formula (1A1) is likely to be the adamantane ring of general formula (1B2), the ring closest to the adamantane ring of general formula (1A2) is likely to be the adamantane ring of general formula (1B1), the ring closest to the adamantane ring of general formula (1B1) is likely to be the adamantane ring of general formula (1A2), and the ring closest to the adamantane ring of general formula (1B2) is likely to be the adamantane ring of general formula (1A1).

[0056] From the above, the adamantane-fused oligothiophene compound of the present invention is represented by the general formula (1'):

[0057]

[0058] [In the formula, R １ and R ２ is the same as above. ３ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group; k represents an integer of 0 to 3; and m represents an integer of 1 to 4.] are preferred, and compounds represented by general formula (1'A) or (1'B):

[0059]

[0060] [In the formula, R １ and R ２is the same as above. ３ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group. k represents an integer of 0 to 3. m represents an integer of 1 to 4 (preferably an integer of 1 to 3, more preferably 1 or 2).] is more preferred.

[0061] In the general formulae (1A), (1A1), (1A2), (1B), (1B1) and (1B2), R ３ The alkyl group represented by the formula (I) is not particularly limited, and either a linear alkyl group or a branched alkyl group can be employed. Examples of the alkyl group include alkyl groups having 1 to 6 carbon atoms (particularly 1 to 4 carbon atoms), such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

[0062] These alkyl groups may have a substituent. Examples of the substituent that the alkyl group may have include a halogen atom, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, an adamantyl group, etc., which will be described later. When the alkyl group has a substituent, the number of the substituents may be, for example, 1 to 6, and particularly 1 to 3.

[0063] In the general formulae (1A), (1A1), (1A2), (1B), (1B1) and (1B2), R ３ The cycloalkyl group represented by the formula (I) is not particularly limited, and examples thereof include cycloalkyl groups having 3 to 10 carbon atoms (particularly 4 to 8 carbon atoms), such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group.

[0064] These cycloalkyl groups may have a substituent. Examples of the substituent that the cycloalkyl group may have include a halogen atom described below, the alkyl group described above, the cycloalkyl group described above, an aryl group described below, a cyano group, a carbamoyl group, an amino group, a silyl group, an adamantyl group, etc. When the cycloalkyl group has a substituent, the number of the substituents can be, for example, 1 to 6, and particularly 1 to 3.

[0065] In the general formulae (1A), (1A1), (1A2), (1B), (1B1) and (1B2), R ３ The aryl group represented by the formula (I) is a monovalent group having an aromatic ring, and is a group obtained by eliminating one hydrogen atom bonded to one carbon atom constituting this aromatic ring.

[0066] Examples of the aromatic ring include not only a benzene ring but also a ring formed by condensing a plurality of benzene rings (a benzene-fused ring) and a ring formed by condensing a benzene ring with another ring (hereinafter, a ring formed by condensing a plurality of benzene rings and a ring formed by condensing a benzene ring with another ring may be collectively referred to simply as a "condensed ring"). Examples of the condensed ring include a pentalene ring, an indene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, a perylene ring, a triphenylene ring, an azulene ring, a heptalene ring, a biphenylene ring, an indacene ring, an acenaphthylene ring, a fluorene ring, a phenalene ring, and a phenanthrene ring.

[0067] That is, examples of the aryl group include a phenyl group, a pentalenyl group, an indenyl group, a naphthyl group, an anthracenyl group, a tetracenyl group, a pentacenyl group, a pyrenyl group, a perylenyl group, a triphenylenyl group, an azulenyl group, a heptalenyl group, a biphenylenyl group, an indacenyl group, an acenaphthyl group, a fluorenyl group, a phenalenyl group, and a phenanthrenyl group.

[0068] These aryl groups may also have a substituent. Examples of the substituent that the aryl group may have include a halogen atom described below, the alkyl group described above, the cycloalkyl group described above, the aryl group described above, a cyano group, a carbamoyl group, an amino group, a silyl group, an adamantyl group, etc. When the aryl group has a substituent, the number of the substituents can be, for example, 1 to 6, and particularly 1 to 3.

[0069] In the general formulae (1A), (1A1), (1A2), (1B), (1B1) and (1B2), R ３The carbamoyl group represented by the following formula may have a substituent. Examples of the substituent that the carbamoyl group may have include a halogen atom described below, the alkyl group described above, the cycloalkyl group described above, the aryl group described above, a cyano group, a carbamoyl group, an amino group, a silyl group, an adamantyl group, etc. When the carbamoyl group has a substituent, the number of the substituents may be, for example, 1 to 2, and particularly 1.

[0070] In the general formulae (1A), (1A1), (1A2), (1B), (1B1) and (1B2), R ３ The amino group represented by the formula (I) may have a substituent. Examples of the substituent that the amino group may have include a halogen atom described below, the alkyl group described above, the cycloalkyl group described above, the aryl group described above, a cyano group, a carbamoyl group, an amino group, a silyl group, an adamantyl group, and the like. When the amino group has a substituent, the number of the substituents can be, for example, 1 to 3, and particularly 1 to 2.

[0071] In the general formulae (1A), (1A1), (1A2), (1B), (1B1) and (1B2), R ３ The silyl group represented by the formula (I) may have a substituent. Examples of the substituent that the silyl group may have include a halogen atom described below, the alkyl group described above, the cycloalkyl group described above, the aryl group described above, a cyano group, a carbamoyl group, an amino group, a silyl group, an adamantyl group, etc. When the silyl group has a substituent, the number of the substituents can be, for example, 1 to 3, and particularly 1 to 2.

[0072] In the general formulae (1A), (1A1), (1A2), (1B), (1B1) and (1B2), R ３ The adamantyl group represented by the following formula is not particularly limited, and examples thereof include a 1-adamantyl group and a 2-adamantyl group.

[0073] These adamantyl groups may have a substituent. Examples of the substituent that the adamantyl group may have include a halogen atom described below, the alkyl group described above, the cycloalkyl group described above, the aryl group described above, a cyano group, a carbamoyl group, an amino group, a silyl group, and an adamantyl group. When the silyl group has a substituent, the number of the substituents may be, for example, 1 to 3, and particularly 1 to 2.

[0074] In addition, R ３ The number (k) of R is not particularly limited and can be, for example, an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 0 or 1. ３ When R ３ When there are three of these, the adamantane ring moiety is represented by general formula (1A-1) or (1B-1):

[0075]

[0076] [wherein the dashed line indicates the bond site fused to the adjacent ring. R ３ａ , R ３ｂ and R ３ｃ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group.

[0077] In general formulas (1A-1) and (1B-1), R ３ａ , R ３ｂ and R ３ｃ The alkyl group, cycloalkyl group, aryl group, cyano group, carbamoyl group, amino group, silyl group and adamantyl group represented by the formula (I) can be any of those mentioned above. The same applies to the type and number of the substituents.

[0078] In general formula (1), R １ and R ２ The alkyl group, cycloalkyl group, aryl group, cyano group, carbamoyl group, amino group, silyl group and adamantyl group represented by the formula (I) can be any of those mentioned above. The same applies to the type and number of the substituents.

[0079] In general formula (1), R １ and R ２ The halogen atom represented by the formula (I) is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0080] In general formula (1), n ​​corresponds to the number of thiophene rings contained in the adamantane-fused oligothiophene compound of the present invention, and from the viewpoints of ease of synthesis, solubility, electrical conductivity, and the like, n is preferably an integer of 2 to 8, more preferably an integer of 2 to 7, and even more preferably an integer of 2 to 6.

[0081] Specifically, the adamantane-fused oligothiophene compound of the present invention that satisfies the above-mentioned conditions is

[0082]

[0083]

[0084] etc.

[0085] These adamantane-fused oligothiophene compounds of the present invention have a robust adamantane skeleton and are stable aromatic compounds, while the thiophene rings are fixed in an s-cis conformation, and as such have high electrical conductivity as a structure, and can also improve solubility, and can be used, for example, as electronic materials, pharmacologically active substances, organic EL devices, ligands in metal complexes, etc.

[0086] 2. Method for Producing Adamantane-Fused Aromatic Compound The adamantane-fused oligothiophene compound of the present invention can be produced, for example, by a method comprising producing an adamantane-fused oligothiophene compound represented by the following general formula (1):

[0087]

[0088] [In the formula, R １ , R ２ , n and A １ is the same as above. １ represents a halogen atom.] is reacted with a nucleophile, and then a compound represented by general formula (3A) or (3B):

[0089]

[0090] [In the formula, R ３ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group, and k represents an integer of 0 to 3.] to react with an adamantanone compound represented by the general formula (4):

[0091]

[0092] [In the formula, R １ , R ２ , R ３ , n, k and A １ are the same as above.], and (II) a step of reacting the adamantane-containing oligothiophene compound obtained in the step (I) with a Bronsted acid and / or a Lewis acid.

[0093] (2-1) Step (I) Starting Compound (General Formula (2)) In the general formula (2), X １ Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0094] From the above, the compound represented by the general formula (2) as a raw material is specifically

[0095]

[0096] etc.

[0097] The aromatic compounds used as raw materials may be known or commercially available products. The compound represented by the general formula (2) is a novel compound that has not been described in the literature.

[0098] Nucleophilic Agent The nucleophilic agent is not particularly limited, and any nucleophilic agent that can induce the Friedel-Crafts reaction can be used. Among them, organolithium compounds, organomagnesium compounds, etc. are preferred from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction.

[0099] The organolithium compound is not particularly limited, and known compounds can be used, including alkyllithiums such as methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, and n-hexyllithium; cycloalkyllithiums such as cyclohexyllithium; and aryllithiums such as phenyllithium. These organolithium compounds can be used alone or in combination of two or more. Of these, in this step, alkyllithiums are preferred, and n-butyllithium is more preferred, from the viewpoints of reaction conversion, yield, selectivity, and the like.

[0100] Examples of the organic magnesium compound include alkyl magnesium halides such as methyl magnesium chloride, methyl magnesium bromide, n-butyl magnesium chloride, n-butyl magnesium bromide, n-hexyl magnesium chloride, and n-hexyl magnesium bromide; phenyl magnesium chloride, phenyl magnesium bromide, 4-n-butylphenyl magnesium chloride, and 4-n-butylphenyl magnesium bromide.

[0101] These nucleophiles can be used alone or in combination of two or more.

[0102] The amount of the nucleophilic agent used is not particularly limited, but is preferably 0.2 to 5.0 mol, more preferably 0.3 to 3.0 mol, and even more preferably 0.5 to 2.0 mol per mol of the aromatic compound as the raw material, from the viewpoints of the reaction conversion rate, yield, selectivity, etc. When multiple nucleophilic agents are used, it is preferable to adjust the total amount thereof to be within the above range.

[0103] Adamantanone Compound (General Formula (3A) or (3B)) Specific examples of the usable adamantanone compound include:

[0104]

[0105] etc.

[0106] The amount of the adamantanone compound used is not particularly limited, but from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction, it is preferably 0.2 to 5.0 mol, more preferably 0.3 to 3.0 mol, and even more preferably 0.5 to 2.0 mol relative to 1 mol of the aromatic compound as a raw material.

[0107] Solvent In the present invention, step (I) can usually be carried out in an organic solvent.

[0108] The organic solvent that can be used is not particularly limited, but from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction, hydrocarbons, ethers, etc. are preferred. Examples of hydrocarbons include aliphatic saturated hydrocarbons such as pentane, hexane, and heptane; and aromatic hydrocarbons such as benzene. Examples of ethers include diethyl ether, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether. Of these, from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction, ethers are preferred, and diethyl ether is more preferred. These organic solvents can be used alone or in combination of two or more.

[0109] The amount of these organic solvents used is not particularly limited, and can be the amount of the solvent.

[0110] Other Conditions In this step, the reaction between the aromatic compound as a raw material and the nucleophile can be carried out usually at −120 to −30° C., preferably −100 to −50° C., and the subsequent reaction with the adamantanone compound can be carried out usually at 0 to 70° C., preferably 10 to 50° C. Furthermore, in this step, the reaction between the aromatic compound as a raw material and the nucleophile can be carried out usually for 1 minute to 10 hours, preferably 5 minutes to 5 hours, and more preferably 10 minutes to 3 hours, and the subsequent reaction with the adamantanone compound can be carried out usually for 1 to 100 hours, preferably 2 to 50 hours, and more preferably 5 to 30 hours.

[0111] After completion of this step, the adamantane-containing oligothiophene compound can be obtained by purifying it by a conventional method as needed. Specifically, for example, an organic solvent (e.g., ethyl acetate) can be added to the reaction mixture to dissolve the organic substance in the organic layer, followed by drying with sodium sulfate or the like and concentrating it under vacuum.

[0112] (2-2) Step (II) Adamantane-Containing Oligothiophene Compound (General Formula (4)) The adamantane-containing oligothiophene compound is a compound obtained by the above-mentioned step (I), and specifically,

[0113]

[0114] The adamantane-containing oligothiophene compound represented by the general formula (4) is a novel compound that has not been described in any literature.

[0115] Brønsted Acid and / or Lewis Acid The Brønsted acid and / or Lewis acid is not particularly limited, and various acids can be used, for example, inorganic acids such as sulfuric acid, nitric acid, phosphoric acid, polyphosphoric acid, hydrogen fluoride (HF), hydrofluoric acid, hydrochloric acid, hydrogen bromide, hydrogen iodide, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, perbromic acid, and periodic acid; sulfonic acids such as fluorosulfonic acid, chlorosulfonic acid, methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, difluoromethanesulfonic acid, trichloromethanesulfonic acid, perfluorobutanesulfonic acid, perfluorooctane sulfonic acid, benzenesulfonic acid, toluenesulfonic acid, and nitrobenzenesulfonic acid; mono- or polycarboxylic acids such as formic acid, acetic acid, propionic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, glycolic acid, lactic acid, benzoic acid, oxalic acid, and succinic acid; ３ , B.F. ３ , BCl ３ , B(OCH ３ ) ３ , AlCl ３ , AlBr ３ , SbF ３ , SbCl ３ , SbF ５ , P.F. ３ , P.F.５ , AsF ３ , AsCl ３ , AsF ５ , TiCl ４ , NbF ５ , TaF ５ Lewis acids such as HBF ４ , HPF ６ , HAsF ６ , HSbF ６ , HSbCl ６ and acids composed of a Lewis acid such as Brønsted acid and hydrogen halide. These acids can be used alone or in combination of two or more. Among them, from the viewpoints of reaction conversion, yield, selectivity, etc., Brønsted acids are preferred, inorganic acids are more preferred, and phosphoric acid is even more preferred. In this specification, Lewis acids refer to compounds that are not acids according to the Brønsted definition but are acids according to the Lewis definition.

[0116] The amount of Bronsted acid and / or Lewis acid used is not particularly limited, but from the viewpoints of reaction conversion rate, yield, selectivity, etc., it is preferably 2 to 50 moles, more preferably 3 to 30 moles, and even more preferably 5 to 20 moles per mole of the starting adamantane-containing oligothiophene compound. When the Bronsted acid and / or Lewis acid is liquid, the amount used can be the amount of solvent. When multiple Bronsted acids and / or Lewis acids are used, it is preferable to adjust the total amount to be within the above range.

[0117] Solvent In the present invention, step (II) can usually be carried out in an organic solvent.

[0118] The organic solvent that can be used is not particularly limited, but from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction, hydrocarbons, halogenated hydrocarbons, ethers, etc. are preferred. Examples of hydrocarbons include aliphatic hydrocarbons such as pentane, hexane, and heptane, and aromatic hydrocarbons such as benzene, toluene, and xylene. Examples of halogenated hydrocarbons include chloroform, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, and dichlorobenzene. Examples of ethers include 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether. Among these, from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction, halogenated hydrocarbons are preferred, and tetrachloroethane is more preferred. These organic solvents can be used alone or in combination of two or more.

[0119] The amount of these organic solvents used is not particularly limited, and can be the amount of the solvent.

[0120] Other Conditions This step can be carried out usually at 80 to 180° C., preferably 100 to 150° C. Furthermore, this step can be carried out usually for 1 to 72 hours, preferably 2 to 48 hours, more preferably 3 to 36 hours.

[0121] After completion of this step, the adamantane-fused oligothiophene compound of the present invention can be obtained by purification by a conventional method, if necessary. Specifically, for example, an organic solvent (e.g., ethyl acetate) is added to the reaction mixture to dissolve the organic substance in the organic layer, followed by drying with sodium sulfate or the like, concentration under vacuum, and purification by flash column chromatography and gel permeation chromatography.

[0122] 3. Method for Producing Starting Compound In the present invention, the compound represented by general formula (2) which is the starting compound can be, for example, a compound represented by general formula (5): (III)

[0123]

[0124] [In the formula, R １ , n and A １are the same as above.] with a lithium compound and a trialkyltin halide compound, and (IV) reacting the compound obtained in the step (III) with a compound represented by the general formula (6):

[0125]

[0126] [In the formula, X １ is the same as above. ２ represents a halogen atom] in the presence of a palladium catalyst.

[0127] (3-1) Step (III) Starting Compound (General Formula (5)) Specific examples of the compound represented by general formula (5) as a raw material include:

[0128]

[0129] etc.

[0130] As the aromatic compounds used as raw materials, known or commercially available products can be used.

[0131] Organolithium Compound The organolithium compound is not particularly limited, and known compounds can be used. Examples include alkyllithium compounds such as methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, and n-hexyllithium; cycloalkyllithium compounds such as cyclohexyllithium; and aryllithium compounds such as phenyllithium. These organolithium compounds can be used alone or in combination of two or more. Of these, in this step, alkyllithium compounds are preferred, and n-butyllithium is more preferred, from the viewpoints of reaction conversion, yield, selectivity, and the like.

[0132] These organolithium compounds can be used alone or in combination of two or more.

[0133] The amount of the organolithium compound used is not particularly limited, but is preferably 0.2 to 5.0 mol, more preferably 0.3 to 3.0 mol, and even more preferably 0.5 to 2.0 mol per mol of the aromatic compound as a raw material, from the viewpoints of reaction conversion, yield, selectivity, etc. When multiple organolithium compounds are used, it is preferable to adjust the total amount thereof to be within the above range.

[0134] Trialkyltin Halide Compound The trialkyltin halide compound is not particularly limited, and known compounds can be used. Examples include trialkyltin chlorides such as trimethyltin(IV) chloride, triethyltin(IV) chloride, tri(n-propyl)tin(IV) chloride, triisopropyltin(IV) chloride, tri(n-butyl)tin(IV) chloride, triisobutyltin(IV) chloride, tri(sec-butyl)tin(IV) chloride, and tri(tert-butyl)tin(IV) chloride. These trialkyltin halide compounds can be used alone or in combination of two or more. Of these, tri(n-butyl)tin(IV) chloride is preferred in this step from the viewpoints of reaction conversion, yield, selectivity, and the like.

[0135] These trialkyltin halide compounds can be used alone or in combination of two or more.

[0136] The amount of the trialkyltin halide compound used is not particularly limited, but is preferably 0.2 to 5.0 moles, more preferably 0.3 to 3.0 moles, and even more preferably 0.5 to 2.0 moles per mole of the aromatic compound as the raw material, from the viewpoints of reaction conversion, yield, selectivity, etc. When multiple trialkyltin halide compounds are used, it is preferable to adjust the total amount thereof to be within the above range.

[0137] Solvent In the present invention, step (III) can usually be carried out in an organic solvent.

[0138] The organic solvent that can be used is not particularly limited, but from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction, hydrocarbons, ethers, etc. are preferred. Examples of hydrocarbons include aliphatic saturated hydrocarbons such as pentane, hexane, and heptane; and aromatic hydrocarbons such as benzene. Examples of ethers include diethyl ether, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether. Of these, from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction, ethers are preferred, and tetrahydrofuran is more preferred. These organic solvents can be used alone or in combination of two or more.

[0139] The amount of these organic solvents used is not particularly limited, and can be the amount of the solvent.

[0140] Other Conditions In this step, the reaction between the aromatic compound as a raw material and the organolithium compound can be carried out usually at −80 to 10° C., preferably −50 to 0° C., and the subsequent reaction with the trialkyltin halide compound can be carried out usually at 0 to 70° C., preferably 10 to 50° C. Furthermore, in this step, the reaction between the aromatic compound as a raw material and the organolithium compound can be carried out usually for 1 minute to 10 hours, preferably 5 minutes to 5 hours, and more preferably 10 minutes to 3 hours, and the subsequent reaction with the trialkyltin halide compound can be carried out usually for 1 minute to 10 hours, preferably 5 minutes to 5 hours, and more preferably 10 minutes to 3 hours.

[0141] After completion of this step, the product can be purified by a conventional method as necessary, and then the next step can be carried out. Specifically, for example, an organic solvent (dichloromethane or the like) can be added to the reaction mixture to dissolve the organic substance in the organic layer, followed by drying with sodium sulfate or the like and concentration under vacuum.

[0142] (3-2) Step (IV) Thiophene Compound (General Formula (6)) In the general formula (6), X ２ The halogen atom represented by X １ Examples of the atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0143] From the above, specific examples of the compound represented by general formula (6) include:

[0144]

[0145] These compounds represented by the general formula (6) can be used alone or in combination of two or more.

[0146] The amount of the compound represented by general formula (6) used is not particularly limited, but is preferably 0.2 to 5.0 moles, more preferably 0.3 to 3.0 moles, and even more preferably 0.5 to 2.0 moles, per mole of the compound represented by general formula (5), which is the raw material in step (III), from the viewpoints of reaction conversion, yield, selectivity, etc. When multiple compounds represented by general formula (6) are used, it is preferable to adjust the total amount thereof to be within the above range.

[0147] Palladium Catalyst In the present invention, known palladium compounds and the like can be used as catalysts for synthesizing polymer compounds, etc., but divalent palladium compounds are preferred. Examples of usable palladium catalysts include tris(dibenzylideneacetone)dipalladium, tetrakis(triphenylphosphine)palladium, palladium hydroxide, palladium acetate, palladium trifluoroacetate, palladium chloride, palladium bromide, palladium iodide, and palladium nitrate. From the viewpoints of reaction conversion, yield, selectivity, and the like, tris(dibenzylideneacetone)dipalladium, tetrakis(triphenylphosphine)palladium, and the like are preferred, and tetrakis(triphenylphosphine)palladium is more preferred. These palladium catalysts can be used alone or in combination of two or more.

[0148] The amount of the palladium catalyst used is preferably 0.01 to 0.3 mol, more preferably 0.02 to 0.2 mol, per 1 mol of the compound represented by general formula (5), which is the raw material in step (III), from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction.

[0149] Solvent In the present invention, step (IV) can usually be carried out in an organic solvent.

[0150] The organic solvent that can be used is not particularly limited, but from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction, hydrocarbons, ethers, etc. are preferred. Examples of hydrocarbons include aliphatic saturated hydrocarbons such as pentane, hexane, heptane, etc.; and aromatic hydrocarbons such as benzene and toluene. Examples of ethers include diethyl ether, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, etc. Among these, from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction, hydrocarbons are preferred, aromatic hydrocarbons are more preferred, and toluene is even more preferred. These organic solvents can be used alone or in combination of two or more.

[0151] The amount of these organic solvents used is not particularly limited, and can be the amount of the solvent.

[0152] Other Conditions This step can be carried out usually at 80 to 180° C., preferably 100 to 150° C. Furthermore, this step can be carried out usually for 1 to 120 hours, preferably 3 to 96 hours, more preferably 5 to 72 hours.

[0153] After completion of this step, purification may be carried out by a conventional method, if necessary, to obtain the compound represented by general formula (5) as the starting material. Specifically, for example, an organic solvent (e.g., ethyl acetate) may be added to the reaction mixture to dissolve the organic substance in the organic layer, followed by drying with sodium sulfate or the like, concentration under vacuum, and purification by thin layer chromatography.

[0154] The present invention will be specifically explained below by way of examples, but the present invention is not limited thereto.

[0155] The adamantane-bithiophene compound 3 was synthesized according to a previous report (J. Am. Chem. Soc. 2023, 145, 21, 11754-11763).

[0156] Example 1: Synthesis of adamantane-bromoterthiophene compound 4

[0157]

[0158] Adamantane-bithiophene compound 3 (89.5 mg, 30.0 μmol, 1.00 equivalents) was added to a dry Schlenk tube equipped with a stir bar. The flask was degassed, and tetrahydrofuran (THF) (0.300 mL) was added. After cooling to 25°C, n-butyllithium ( n BuLi) (1.51 M solution in hexane, 0.21 mL, 33.0 μmol, 1.10 equiv.) was slowly added at −25° C., and the mixture was stirred at this temperature for 30 min. Then, tri(n-butyl)tin chloride ( n BuSnCl) (103 mg, 31.5 μmol, 1.05 equiv.) was added and the reaction mixture was stirred at room temperature for 1 h. The reaction mixture was quenched by adding aqueous NH4Cl to the reaction mixture. The organic layer was extracted three times with dichloromethane, dried over Na2SO4, and concentrated in vacuo. The crude product was used without further purification.

[0159] A 50 mL two-neck flask was dried and filled with N2, and the crude product obtained above, tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) (17.3 mg, 15.0 μmol, 5 mol%), 2,3-dibromothiophene (79.8 mg, 33.0 μmol, 1.10 equiv.), and dry toluene (9.00 mL) were added. The mixture was stirred at 110 °C for 48 h. After the mixture was cooled to room temperature, the organic layer was extracted three times with ethyl acetate, dried over Na2SO4, and concentrated in vacuo. The crude product was purified by preparative thin-layer chromatography (eluent: hexane) to obtain a mixture of two isomers of adamantane-bromoterthiophene compound 4 as a brown solid (70.0 mg, 51%). The NMR spectrum of the resulting adamantane-bromoterthiophene compound 4 is shown in Figure 1. Chemical Formula: C 22 H 19BrS3 Exact Mass: 457.98 Molecular Weight: 459.48 m / z: 459.98 (100.0%), 457.98 (90.2%), 460.98 (26.1%), 458.99 (21.7%), 461.98 (12.5%), 462.98 (3.2%), 459.99 (3.9%), 461.99 (2.8%), 458.98 (2.2%) Elemental Analysis: C, 57.51; H, 4.17; Br, 17.39; S, 20.93.

[0160] Example 2: Synthesis of bis-adamantane-terthiophene compound 5

[0161]

[0162] Adamantane-bromoterthiophene compound 4 (264.8 mg, 550 μmol, 1.10 equivalents) obtained in Example 1 was added to a dry Schlenk tube equipped with a stir bar. After degassing the Schlenk tube, diethyl ether (5.00 mL) was added. After cooling the Schlenk tube to −78°C, n-butyllithium ( n BuLi) (1.51 M solution in hexane, 0.40 mL, 0.60 mmol, 1.20 equiv.) was slowly added and stirred at the same temperature for 1 h. 4-Protoadamantanone 2 (76.1 mg, 0.50 mmol, 1.00 equiv.) was added as a solid to the reaction mixture under a nitrogen stream at the same temperature and stirred at the same temperature for 1 h. The reaction mixture was then stirred at room temperature for 12 h. Methanol was added to the reaction mixture to quench the reaction. The organic layer was extracted three times with ethyl acetate, dried over Na2SO4, and concentrated in vacuo. The crude product was used without further purification.

[0163] The resulting crude product was added to a Schlenk tube equipped with a stir bar. 1,1,2,2-Tetrachloroethane (2.50 mL) and H3PO4 (10 equiv., 0.258 mL) were added to the Schlenk tube, and the reaction mixture was stirred at 130 °C for 24 h. Saturated aqueous NaHCO3 was carefully added to the reaction mixture at 0 °C to quench the reaction, and the organic layer was extracted three times with ethyl acetate. The combined organic layers were dried over Na2SO4 and concentrated under vacuum to obtain the crude product. The crude product was then purified by flash column chromatography using an Isorela (Biotage, hexane only) and gel permeation chromatography (GPC, CHCl3 only, 10 mL / min) to obtain bis-adamantane-terthiophene compound 5 as a red solid (5.9 mg, 2%). 1 H-NMR (600 MHz, CDCl3) δ 7.05 (d, J = 5.2 Hz, 2H), 6.92 (d, J = 5.2 Hz, 2H), 3.00 (s, 2H), 2.57 (bs, 2H), 2.34-2.32 (m, 2H), 2.16 (bs, 2H), 2.10 (d, J = 12.0 Hz, 2H), 1.89-1.85 (m, 6H), 1.72-1.70 (m, 6H), 1.59 (d, J = 13.4 Hz, 4H), 1.32 (d, J = 12.7 Hz, 2H). 13 C-NMR (151 MHz, CDCl3) δ 144.0, 138.8, 131.1, 128.1, 123.4, 121.4, 48.6, 41.7, 41.6, 38.3, 37.8, 36.8, 32.2, 30.4, 28.5, 26.6.

[0164] Test Example 1: Electronic Properties For bis-adamantane-terthiophene compound 5 obtained in Example 2, the ultraviolet-visible (UV / vis) absorption spectrum was recorded with a Shimadzu UV-3600 spectrometer at a resolution of 0.5 nm. The fluorescence spectrum was measured with a Shimadzu RF-6000 Hitachi spectrometer and recorded with a resolution of 0.2 nm. The results are shown in Figures 2 and 3.

[0165] For reference, Figures 2 and 3 also show the ultraviolet-visible (UV / vis) absorption spectrum and fluorescence spectrum of terthiophene that does not have an adamantane ring. In the ultraviolet-visible (UV / vis) absorption spectrum and fluorescence spectrum, the longer the observed maximum wavelength, the smaller the HOMO-LUMO gap. Therefore, it can be understood that the adamantane-fused oligothiophene compound of the present invention can easily transfer electrons to the conduction band, thereby enhancing the current flow ability and providing excellent semiconductor properties.

Claims

1. General formula (1): [In the formula, A １ are the same or different and represent an adamantane ring. １ and R ２ are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group, and n represents an integer of 2 to 8.

2. The above A １ are the same or different and represent general formula (1A) or (1B): [wherein the dashed line indicates the bond site fused to the adjacent ring. R ３ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group, and k represents an integer of 0 to 3.

3. The above A １ are the same or different and are represented by the general formula (1A1), (1A2), (1B1) or (1B2): [wherein the dashed line indicates the bond site fused to the adjacent ring. R ３ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group, and k represents an integer of 0 to 3.

4. General formula (1'): [In the formula, R １ and R ２ is the same as above. ３ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group. k represents an integer of 0 to 3. m represents an integer of 1 to 4.

5. A method for producing the adamantane-fused oligothiophene compound according to any one of claims 1 to 4, comprising: (1) reacting a compound represented by general formula (2): [In the formula, R １ , R ２ , n and A １ is the same as above. １ represents a halogen atom.] is reacted with a nucleophile, and then a compound represented by the general formula (3A) or (3B): [In the formula, R ３ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group, and k represents an integer of 0 to 3.] to react with an adamantanone compound represented by the general formula (4): [In the formula, R １ , R ２ , R ３ , n, k and A １ (II) a step of reacting the adamantane-containing oligothiophene compound obtained in the step (I) with a Bronsted acid and / or a Lewis acid.

6. The method of claim 5, wherein the nucleophilic agent is an organolithium compound and / or an organomagnesium compound.

7. General formula (4): [In the formula, R １ and R ２ are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group. ３ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group. n represents an integer of 2 to 8. k represents an integer of 0 to 3. A １ and are the same or different and represent an adamantane ring.] An adamantane-containing oligothiophene compound represented by the following formula:

8. General formula (2): [In the formula, R １ and R ２ are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group. n represents an integer of 2 to 8. １ are the same or different and represent an adamantane ring. １ represents a halogen atom.] A compound represented by the following formula:

9. General formula (2): [In the formula, R １ and R ２ are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, a carbamoyl group, an amino group, a silyl group, or an adamantyl group. n represents an integer of 2 to 8. １ are the same or different and represent an adamantane ring. １ represents a halogen atom.], the method for producing a compound represented by the general formula (5): [In the formula, R １ , n and A １ are the same as above.] with an organolithium compound and a trialkyltin halide compound, and (IV) reacting the compound obtained in the step (III) with a compound represented by the general formula (6): [In the formula, X １ is the same as above. ２ represents a halogen atom] in the presence of a palladium catalyst.

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