Preparation method of naphthyl siloles, naphthyl siloles having heterocyclic groups, and graphene nanoribbons having heterocyclic groups

Abstract

The present invention provides a method for preparing naphthyl siloles, wherein the method comprises reacting a compound represented by formula (1) with an acid radical complex containing a lanthanide element and lithium to generate a lanthanide element complex of the compound represented by formula (1), and then further reacting the lanthanide element complex with a silyl compound represented by formula (2), thereby being able to more safely prepare naphthyl siloles used as a raw material for GNR. In formula (1), R 1a and R 1b are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a halogen atom, an aromatic hydrocarbon group or a heterocyclic group; R 1a With R 1b Optionally bond to each other to form a ring; R 2 represents an aromatic hydrocarbon group or a heterocyclic group; X represents a bromine atom or an iodine atom. 3a R 3b SiCl2(2) In formula (2), R 3a and R 3b The same or different groups represent an alkyl group having 1 to 4 carbon atoms which may have a branch or a phenyl group.

Description

Technical Field

[0001] The present invention relates to a method for producing naphthylsiloles which are raw materials of graphene nanoribbons (hereinafter, sometimes referred to as "GNR"). Background Art

[0002] GNR is a material that can be expected to be applied to semiconductors, solar cells, transparent electrodes, high-speed transistors, organic EL elements, etc. As the preparation method of the GNR, it is known that it can be roughly divided into two methods: top-down method and bottom-up method. The latter is particularly attractive in that it can precisely control the edge structure and width and synthesize a large amount of GNR.

[0003] The inventors of the present application focused on the preparation of GNRs based on the bottom-up method and conducted intensive research on the preparation method thereof. As a result, they discovered a preparation method using naphthyl siloles as raw materials as a preparation method of GNRs with a small number of steps and suppressed side reactions (Patent Document 1).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: International Publication No. 2020 / 184625 Summary of the invention

[0007] Technical Problems to be Solved by the Invention

[0008] Patent Document 1 discloses that, for example, a compound represented by the following general formula (9) is reacted with n-butyl lithium (n-BuLi) and then reacted with dimethylsilyl chloride to obtain a silyl compound represented by the following general formula (10), and the silyl compound is cyclized using di-tert-butyl peroxide ((t-BuO)2) to prepare naphthyl siloles as a raw material for GNR (Synthesis Example 2 of Patent Document 1).

[0009] [Chemical formula 1]

[0010]

[0011] In formula (9), R represents a substituent.

[0012] [Chemical formula 2]

[0013]

[0014] In formula (10), R is the same as the above R.

[0015] However, the production method requires the use of dimethylchlorosilane having very low flash points and boiling points, and requires the use of di-tert-butyl peroxide, which is a self-reactive organic peroxide. This raises concerns about disaster prevention in terms of industrial implementation.

[0016] An object of the present invention is to provide a method for more safely preparing naphthylsiloles used as raw materials for GNRs.

[0017] Technical means to solve technical problems

[0018] In order to solve the above technical problems, the inventors of the present application have conducted intensive studies and found that naphthylsiloles can be prepared more safely from less dangerous compounds by the following method. Specifically, the invention includes the following.

[0019] Item 1. A method for preparing a compound represented by the general formula (3), which comprises, in sequence, a step of reacting a compound represented by the general formula (1) with an acid complex containing a lanthanide element and lithium to generate a lanthanide complex of the compound represented by the general formula (1), and a step of reacting the lanthanide complex with a silyl compound represented by the general formula (2).

[0020] [Chemical formula 3]

[0021]

[0022] In formula (3), R 1a and R 1b are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a halogen atom, an aromatic hydrocarbon group or a heterocyclic group; R 1a With R 1b Optionally bond to each other to form a ring; R 2’ represents an aromatic hydrocarbon ring or a heterocyclic ring; R 3a and R 3b The same or different groups represent an alkyl group having 1 to 4 carbon atoms which may have a branch or a phenyl group.

[0023] [Chemical formula 4]

[0024]

[0025] In formula (1), R 1a and R 1b With the R 1a and R 1b Same; R 2 represents an aromatic hydrocarbon group or a heterocyclic group; and X represents a bromine atom or an iodine atom.

[0026] R 3a R 3b SiCl2(2)

[0027] In formula (2), R 3a and R 3b With the R 3a and R 3b same.

[0028] Item 2. A compound represented by the general formula (1).

[0029] [Chemical formula 5]

[0030]

[0031] In formula (1), R 1a and R 1b are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a halogen atom, an aromatic hydrocarbon group or a heterocyclic group; R 1a With R 1b Optionally bond to each other to form a ring; R 2 represents an aromatic hydrocarbon group or a heterocyclic group; and X represents a bromine atom or an iodine atom.

[0032] Item 3. A method for producing the compound according to Item 2, comprising reacting a compound represented by the general formula (4) with a compound represented by the general formula (5).

[0033] [Chemical formula 6]

[0034]

[0035] In formula (4), R 1a , R 1b and X and R 1a , R 1b Same as X; R 4 It represents an optionally branched alkyl group having 1 to 4 carbon atoms, an optionally branched halogenated alkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon group.

[0036] R 2 MgBr(5)

[0037] In formula (5), R 2 With the R 2 same.

[0038] Item 4. A compound represented by the general formula (4).

[0039] [Chemical formula 7]

[0040]

[0041] In formula (4), R 1a and R 1bare the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a halogen atom, an aromatic hydrocarbon group or a heterocyclic group; R 1a With R 1b Optionally bond to each other to form a ring; R 4 represents an optionally branched alkyl group having 1 to 4 carbon atoms, an optionally branched halogenated alkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon group; and X represents a bromine atom or an iodine atom.

[0042] Item 5. A compound represented by the general formula (3a).

[0043] [Chemical formula 8]

[0044]

[0045] In formula (3a), R 1a and R 1b are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a halogen atom, an aromatic hydrocarbon group or a heterocyclic group; R 1a With R 1b Optionally bond to each other to form a ring; R 2a’ Represents an aromatic heterocycle; R 3a and R 3b The same or different groups represent an alkyl group having 1 to 4 carbon atoms which may have a branch or a phenyl group.

[0046] Item 6. A graphene nanoribbon having at least one structural unit represented by the general formula (6).

[0047] [Chemical formula 9]

[0048]

[0049] In formula (6), * represents a bonding site; n represents an integer greater than 0; R 1a and R 1b are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a halogen atom, an aromatic hydrocarbon group or a heterocyclic group; R bonded to the same benzene ring 1a With R 1b Optionally bond to each other to form a ring; R 2a’ It represents an aromatic heterocycle.

[0050] Item 7. The graphene nanoribbon according to Item 6, further comprising at least one structural unit represented by the general formula (7).

[0051] [Chemical formula 10]

[0052]

[0053] In formula (7), the dashed line indicates the absence of a bond or a single bond; * indicates a bonding site; R 6a , R 6b , R 6c , R 6d , R 6e and R 6f are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a boric acid or an ester group thereof, an aromatic hydrocarbon group, or a heterocyclic group; R 6c With R 6d They are optionally bonded to each other to form a ring.

[0054] Item 8. The graphene nanoribbon according to Item 6 or 7, which has at least one structural unit represented by the general formula (8).

[0055] [Chemical formula 11]

[0056]

[0057] In formula (8), the dashed lines are the same or different and represent the absence of a bond or represent a single bond; *1 represents a bonding site; when the dashed line connected to *2 is a single bond, *2 represents a bonding site; n represents an integer greater than 0; R 1a and R 1b are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a halogen atom, an aromatic hydrocarbon group or a heterocyclic group; R bonded to the same benzene ring 1a With R 1b Optionally bond to each other to form a ring; R 2a’ Represents an aromatic heterocycle; R 6a , R 6b , R 6c , R 6d , R 6e and R 6f are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a boric acid or an ester group thereof, an aromatic hydrocarbon group, or a heterocyclic group; R 6c With R 6d They are optionally bonded to each other to form a ring.

[0058] Effects of the Invention

[0059] According to the present invention, naphthyl siloles can be prepared without using compounds having very low flash points and boiling points or self-reactive organic peroxides. In addition, naphthyl siloles can be prepared from the compound represented by the general formula (1) by a one-pot method, so naphthyl siloles can be prepared more simply than the above-mentioned known production methods.

[0060] Furthermore, according to the present invention, a revolutionary method for preparing a compound represented by the general formula (1) can be provided. Specifically, according to the preparation method discovered by the inventors of the present application, i.e., a novel preparation method of reacting a compound represented by the general formula (4) with an arylmagnesium bromide represented by the general formula (5), the arylmagnesium bromide represented by the general formula (5) reacts selectively at the sulfonyl site of the compound represented by the general formula (4), so that when preparing the compound represented by the general formula (1), it is not necessary to introduce a bromine or iodine atom after the coupling reaction, thereby being able to prepare compounds represented by the general formula (1) having various structures while providing a high-purity compound represented by the general formula (1) at a lower price. As a result, according to the preparation method of naphthyl siloles of the present invention, naphthyl siloles having structures that cannot be prepared by conventional known methods can be prepared, and the naphthyl siloles can be used as raw materials for GNRs as well as raw material monomers other than GNRs (e.g., raw material monomers for organic EL devices, organic semiconductors, organic thin-film solar cells, etc.).

[0061] As a typical example of the naphthyl siloles having a structure that cannot be prepared by the conventionally known methods, naphthyl siloles having a structure represented by the general formula (3a) and having an aromatic heterocycle can be cited. In addition, naphthyl siloles having an aromatic heterocycle can be polymerized (APEX polymerization) under the conditions described in the patent document 1 to prepare GNRs having an aromatic heterocycle (specifically, GNRs having a structural unit represented by the general formula (6), (7) or (8)), thereby providing GNRs having properties different from those of conventionally known GNRs (specifically, GNRs having improved properties such as electron-hole acceptance capacity, redox response and charge transport capacity based on precise control of the band gap). In addition, the GNRs having an aromatic heterocycle can be used in particular for light-emitting materials, organic semiconductors, conductive materials, etc. DETAILED DESCRIPTION

[0062] In this specification, "comprising" is a concept including any one of "including", "consisting essentially of" and "consisting only of". In addition, in this specification, when a numerical range is expressed as "A to B", it means A or more and B or less.

[0063] (1-1) Preparation method of naphthyl siloles of the present invention

[0064] As shown in the following reaction formula, the method for preparing naphthyl thiorroles represented by the general formula (3) of the present invention is characterized in that it comprises the following two steps in sequence: a step of reacting a compound represented by the general formula (4) with an aryl magnesium bromide represented by the general formula (5) to obtain a compound represented by the general formula (1) (step 1); and a step of reacting the compound represented by the general formula (1) with an acid radical complex containing a lanthanide element and lithium to generate a lanthanide complex of the compound represented by the general formula (1) in the system, and reacting the lanthanide complex with a silyl compound represented by the general formula (2) (step 2).

[0065] [Chemical formula 12]

[0066]

[0067] In the formula, R 1a and R 1b are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a halogen atom, an aromatic hydrocarbon group or a heterocyclic group; R 1a With R 1b Optionally bond to each other to form a ring; R 2 represents an aromatic hydrocarbon group or a heterocyclic group; R 2’ represents an aromatic hydrocarbon ring or a heterocyclic ring; R 3a and R 3b are the same or different and represent an alkyl group having 1 to 4 carbon atoms which may have a branch or a phenyl group; X represents a bromine atom or an iodine atom; R 4 It represents an optionally branched alkyl group having 1 to 4 carbon atoms, an optionally branched halogenated alkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon group.

[0068] Hereinafter, the above-mentioned compounds and steps will be described in detail.

[0069] (1-1-1) Compounds represented by the general formula (1) to compounds represented by the general formula (5)

[0070] In the general formula (4), as R 1a and R 1b The alkyl group shown is, for example, a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 15, more preferably 1 to 13), and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, n-heptyl, n-octyl, n-nonyl, and n-decyl.

[0071] The alkyl group may be partially substituted, and the substituent when substituted is not particularly limited, and examples thereof include halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms. The number of substituents when substituted is not particularly limited, and for example, 1 to 3 substituents may be present.

[0072] In the general formula (4), as R 1a and R 1b The cycloalkyl group shown is preferably a cycloalkyl group having 3 to 20 (preferably 4 to 15, more preferably 5 to 13) carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl.

[0073] A part of the cycloalkyl group may be substituted, and the substituent when substituted is not particularly limited, and examples thereof include halogens such as fluorine atoms, chlorine atoms, and bromine atoms; hydrocarbon groups having 1 to 20 carbon atoms (such as methyl, ethyl, and n-propyl groups). When substituted by a substituent, the number of substituents is not particularly limited, and may be 1 to 3, for example.

[0074] In the general formula (4), R 1a and R 1b The (poly)ether group represented by means of is an ether group or a polyether group. 11c (R 11c represents the above-mentioned alkyl group. ) represents a group, etc. An alkyl group having 1 to 4 carbon atoms can be preferably used as R 11c As the polyether group, for example, -(OR 11a ) k -OR 11b (R 11a and R 11b are the same or different and represent an alkyl group. k represents an integer of 1 to 20. ) represents a group, etc. These repeating units OR 11a The same repeating unit may be included in the above formula, or two or more different repeating units may be included. An alkyl group having 1 to 4 carbon atoms may be preferably used as R 11a and R 11b Polyether group.

[0075] R 11a and R 11b All are alkyl groups, and the above-mentioned alkyl groups can be cited. When having a substituent, the above-mentioned types and numbers can also be cited. In addition, k is preferably an integer of 1 to 20, more preferably an integer of 1 to 15, and even more preferably an integer of 1 to 5.

[0076] Examples of such polyether groups include -(OC2H5)2OCH3, -(OC2H5)3OCH3, -(OC2H5)4OCH3, -(OC2H5)11 OCH3, -(OC2H5) 12 OCH3, -(OC2H5) 13 OCH3, etc.

[0077] In the general formula (4), as R 1a and R 1b The ester group shown in FIG. 1 includes, for example, —COOR 11d (R 11d represents the above-mentioned alkyl group. ) represents a group, etc. An alkyl group having 1 to 4 carbon atoms can be preferably used as R 11d Ester group.

[0078] As R 1a and R 1b Specific examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.

[0079] In the general formula (4), R 1a and R 1b The aromatic hydrocarbon group shown in means a group having an aromatic hydrocarbon ring. In addition, at least one hydrogen atom bonded to a carbon atom constituting the aromatic hydrocarbon ring may be substituted with a substituent.

[0080] As the aromatic hydrocarbon ring constituting the aromatic hydrocarbon group, not only a benzene ring but also a ring formed by condensing a plurality of benzene rings (benzene condensed ring), a ring formed by condensing a benzene ring with other aromatic hydrocarbon rings, etc. can be listed (hereinafter, a ring formed by condensing a plurality of benzene rings and a ring formed by condensing a benzene ring with other rings are sometimes collectively referred to as a "condensed hydrocarbon ring"). As the above-mentioned condensed hydrocarbon ring, for example, a pentalene ring, an indene ring, a naphthalene ring, a dihydronaphthalene ring, 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, a phenanthrene ring, etc. can be listed.

[0081] The substituent when at least one hydrogen atom of the aromatic hydrocarbon ring constituting the aromatic hydrocarbon group is substituted is not particularly limited, and examples thereof include halogens such as fluorine atoms, chlorine atoms, and bromine atoms; hydrocarbon groups having 1 to 20 carbon atoms (e.g., methyl, ethyl, n-propyl, etc.), etc. The number of substituents when substituted by a substituent is not particularly limited, and for example, may be 1 to 3.

[0082] In the general formula (4), R 1a and R 1b The heterocyclic group shown in the figure means a group (substituent) having a heterocyclic ring. In addition, it may be a derivative group in which at least one hydrogen atom bonded to a carbon atom constituting the heterocyclic ring is substituted with a functional group.

[0083] As the heterocycle constituting the heterocyclic group, for example, a heterocycle having at least one atom selected from a nitrogen atom, an oxygen atom, a boron atom, a phosphorus atom, a silicon atom and a sulfur atom can be listed (specifically, an aromatic heterocycle or an alicyclic heterocycle, especially an aromatic heterocycle can be listed). As specific examples of the heterocycle, a furan ring, a thiophene ring, a pyrrole ring, a thiol ring, a borole ring, a phosphole ring, an oxazole ring, a dioxole ring, a thiazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, an aromatic heterocycle such as a pyrazine ring, etc. can be listed. In addition, it can also be a condensed heterocycle of these heterocycles themselves, or a condensed heterocycle of these heterocycles and a benzene ring, the above-mentioned condensed hydrocarbon ring, etc. (thienothiophene ring, quinoline ring, benzodioxole ring, etc.).

[0084] When at least one hydrogen atom of the heterocyclic ring constituting the heterocyclic group is replaced, the substituent is not particularly limited, and examples thereof include halogens such as fluorine atoms, chlorine atoms, and bromine atoms; hydrocarbon groups having 1 to 20 carbon atoms (such as methyl, ethyl, and n-propyl), etc., but the present invention is not limited thereto, and any substituent may be used. When the substituent is replaced by a substituent, the number of the substituents is not particularly limited, and for example, it may be 1 to 3.

[0085] In addition, R in the general formula (4) 1a and R 1b They may be bonded to each other to form a ring. Examples of the ring formed in this case include the above-mentioned alicyclic ring (cycloalkyl group), aromatic hydrocarbon ring, and heterocyclic ring.

[0086] When the naphthyl silole represented by the general formula (3) obtained by the production method of the present invention is used as a raw material for GNR, it is preferred that R in the general formula (4) 1a and R 1b All are hydrogen atoms, or one is a hydrogen atom and the other is an alkyl group or a (poly)ether group, or R 1a and R 1b They are bonded to each other to form a ring.

[0087] X in the general formula (4) is a bromine atom or an iodine atom, and is preferably a bromine atom from the viewpoint of ease of preparation of the compound represented by the general formula (4).

[0088] In the general formula (4), as R 4 The alkyl group having 1 to 4 carbon atoms and optionally having a branch as shown in the embodiment of the present invention may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. In addition, as the halogenated alkyl group having 1 to 4 carbon atoms and optionally having a branch, a group in which at least one hydrogen atom of the alkyl group is substituted by a halogen atom may be exemplified, specifically, -CH2F, -CHF2, -CF3, -CH2Cl, -CHCl2, -CCl3, etc. may be exemplified.

[0089] In the general formula (4), as R4 The aromatic hydrocarbon group shown in the formula (a) may be the above-mentioned aromatic hydrocarbon group. Specifically, for example, a compound in which at least one hydrogen atom of the aromatic hydrocarbon ring constituting the aromatic hydrocarbon group is substituted, and as the substituent, for example, an alkyl group having 1 to 4 carbon atoms and optionally having a branch, a nitro group, etc. may be mentioned.

[0090] As described later, the compound represented by the general formula (4) is prepared by reacting the hydroxyl group of the corresponding brominated (or iodinated) naphthol with a sulfonic acid anhydride or the acyl halide which is generally used as a sulfonyl protecting group. Therefore, R in the general formula (4) 4 Preferred are substituents derived from sulfonic acid, which are commonly used as sulfonyl protecting groups. Specific examples thereof include -CF3, -CH3, -C6H4CH3 (tolyl) and -C6H4NO2 (nitrophenyl).

[0091] The general formula (4) can be prepared by the following method: for example, by conventional methods, the corresponding substituent R 1a and R 1b The naphthols are brominated (or iodinated) to obtain brominated (or iodinated) naphthols, and the brominated (or iodinated) naphthols are reacted with a sulfonylating agent such as a corresponding sulfonic anhydride or sulfonyl chloride. Specifically, the preparation can be performed by the method described in the Examples section described later.

[0092] As R in the general formula (5) 2 The aromatic hydrocarbon group or heterocyclic group shown in the formula (5) may be any of the above aromatic hydrocarbon groups or heterocyclic groups. The types and numbers of substituents are also the same. In addition, from the perspective of ease of preparation of the general formula (5), R 2 An aromatic hydrocarbon group or a heterocyclic group having no substituent or having a hydrocarbon group having 1 to 12 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, etc.) as a substituent is preferred.

[0093] In the general formula (2), R 3a and R 3b Examples of the optionally branched alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl.

[0094] In the general formula (2), from the viewpoint of the ease of preparation of the compound, R 3a and R 3b Preferably, methyl, ethyl or phenyl is present. Furthermore, preferably, R 3a and R 3b are the same substituents.

[0095] X and R in the general formula (1) 1a , R 1b and R 2The above-mentioned groups can be used. For the groups having substituents, the types and numbers of the substituents are also the same. In addition, the preferred embodiments are also the same. Therefore, as the compound having a structure represented by the general formula (1), specifically, for example, the following general formulas (1a1) to (1e1) can be listed. From the perspective of the ease of obtaining the raw materials, the formulas (1b1), (1c1) and (1e1) without heterocyclic groups are preferred. In addition, as a straight-chain or branched alkyl group, the above-mentioned alkyl group can be used. The types and numbers of the substituents are also the same.

[0096] [Chemical formula 13]

[0097]

[0098] Wherein, X is the same as the above X; R 1b1 represents a linear or branched alkyl group having 1 to 20 (preferably 1 to 15, more preferably 1 to 13) carbon atoms; R 1c1 represents a linear or branched alkyl group having 1 to 20 (preferably 2 to 15, more preferably 2 to 12) carbon atoms; R 2a represents a heterocyclic group.

[0099] R in the general formula (3) 1a , R 1b , R 3a and R 3b The above-mentioned groups can be used. For the groups having substituents, the types and numbers of the substituents are also the same. In addition, the preferred embodiments are also the same. In the general formula (3), R 2’ The aromatic hydrocarbon ring and heterocyclic ring shown in the formula (1) and (5) are the same as those constituting R 2 The ring corresponding to the ring of the aromatic hydrocarbon group and the heterocyclic group shown in the figure can be used for R 2 The aromatic hydrocarbon ring and heterocyclic ring described above. For the group having a substituent, the type and number of the substituent are also the same. In addition, the preferred embodiment is also the same. In addition, it is presumed that step 2 is carried out as follows, so the substituent R in the general formula (3) 2’ In the general formula (1), the substituent R 2 The bond to the naphthyl group and the bond connecting the carbon atom to which the bond is connected and the carbon atom adjacent to the carbon atom form a structure of a part of the silole ring.

[0100] The estimated reaction formula and examples of the generated compounds are described below.

[0101] <R 2 An example of an acylate complex containing a lanthanide element and lithium in which nBu2LaCl·4LiCl is used as a monovalent aromatic hydrocarbon group (benzene ring)>

[0102] [Chemical formula 14]

[0103]

[0104] In the formula, X, R 1a , R 1b , R 3a and R 3b With the X, R 1a , R 1b , R 3a and R 3b Similarly, nBu represents an n-butyl group. In addition, Formula (1-a') represents a model structure of a lanthanide complex of the compound represented by General Formula (1).

[0105] <R 2 An example of a monovalent heterocyclic group (thiophene ring) and using nBu2LaCl·4LiCl as an acid radical complex containing a lanthanide element and lithium>

[0106] [Chemical formula 15]

[0107]

[0108] In the formula, X, R 1a , R 1b , R 3a and R 3b With the X, R 1a , R 1b , R 3a and R 3b Similarly, nBu represents an n-butyl group. In addition, Formula (1-b') represents a model structure of a lanthanoid complex of the compound represented by General Formula (1).

[0109] (1-1-2) About process 1

[0110] The compound represented by the general formula (5) used in the step (1) is usually used in an amount of 0.8 to 2.0 mol, preferably 1.0 to 1.7 mol, based on 1 mol of the compound represented by the general formula (4).

[0111] In step (1), a Pd compound, a ligand, and a lithium halide salt may be used simultaneously. As the Pd compound that can be used simultaneously, for example, a Pd compound that can be commonly used in a cross-coupling reaction may be used, specifically, for example, tris(dibenzylideneacetone)dipalladium (Pd2(dba)3), palladium acetate (Pd(OAc)2), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4), etc. may be cited. One of these Pd compounds may be used, or two or more thereof may be used simultaneously. The amount of the Pd compound used is generally 0.1 to 10 mol%, preferably 1 to 5 mol%, relative to 1 mol of the compound represented by the general formula (4).

[0112] As the ligand that can be used in step (1), for example, a phosphine ligand that can be generally used in a cross-coupling reaction can be used, and specific examples thereof include 1,1-bis(diphenylphosphino)methane (DPPM), 1,2-bis(diphenylphosphino)ethane (DPPE), 1,3-bis(diphenylphosphino)propane (DPPP), 1,2-bis(diphenylphosphino)butane (DPPB), 1,1'-bis(diphenylphosphino)ferrocene (DPPF), 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP), 4,5'-bis(diphenylphosphino)-9,9'-dimethylxanthene (Xantophos), triphenylphosphine (PPh3), tricyclohexylphosphine (PCy3), tri-tert-butylphosphine (P t Bu3) etc. These ligands can be used alone or in combination of two or more. The amount of the ligand used is usually 0.1 to 10 mol%, preferably 1 to 5 mol%, relative to 1 mol of the compound represented by the general formula (4).

[0113] Specific examples of the lithium halide salt in step (1) include LiBr, LiI, and the like. One or more of these lithium halide salts may be used. The amount of the lithium halide salt used is usually 0.7 to 3 mol, preferably 0.9 to 2 mol, relative to 1 mol of the compound represented by the general formula (4).

[0114] Step (1) can be carried out in the presence of a solvent as required. Examples of usable solvents include ethers. Specifically, examples of ethers include diethyl ether, cyclopentyl methyl ether, and tetrahydrofuran. Usually, the amount of the solvent used is usually 0.2 to 10 parts by mass, preferably 0.5 to 5 parts by mass, relative to 1 part by mass of the compound represented by the general formula (4).

[0115] Step (1) is implemented in the following manner: for example, a compound represented by the general formula (4), and optionally a Pd compound, a ligand, a lithium halide and a solvent are added to a reaction vessel, the reaction vessel is temporarily cooled to -20 to 0°C, and a compound represented by the general formula (5) is added at the same temperature. The temperature is then raised to 10 to 40°C, and the reaction is continued at the same temperature until the reaction is completed.

[0116] After the reaction is completed, for example, an acid is added to the reaction solution to quench the reaction, and then an organic solvent and water are added to the reaction solution to separate the liquid and remove the aqueous layer, thereby removing inorganic salts and the like into the aqueous layer, and then concentrating the organic layer containing the compound to obtain a compound represented by the general formula (1). The obtained compound represented by the general formula (1) can be purified by distillation, crystallization, column chromatography using silica gel, etc. as needed.

[0117] (1-1-3) About process 2

[0118] The lanthanoid-containing ate complex used in step (2) is a complex containing lanthanoids and lithium. Lanthanoids are atoms having atomic numbers of 57 to 71, and specific examples thereof include lanthanum, cerium, and neodymium.

[0119] Specific examples of the acid anion-type complex containing a lanthanoid element and lithium include a complex represented by the following general formula (11).

[0120] R 20a p MX 20a q ·4LiX 20b (11)

[0121] In formula (11), R 20a represents an alkyl group having 1 to 4 carbon atoms which may have a branch, M represents a lanthanide atom, and X 20a and X 20b are the same or different and represent a halogen atom, p and q are the same or different and represent an integer of 0 to 3, and p+q=3.

[0122] As R in the general formula (11) 20a The alkyl group having 1 to 4 carbon atoms and optionally having branches as represented by X may include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl. The lanthanide atom represented by M may include atoms having atomic numbers of 57 to 71, for example, lanthanum atoms, cerium atoms, and neodymium atoms. 20a and X 20b Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0123] Specific examples of the acid anion-type complex containing a lanthanoid element and lithium having the above-mentioned characteristics include nBu2LaCl·4LiCl, nBu2CeCl·4LiCl, and nBu2NdMe·4LiCl.

[0124] The acid anion-type complex containing a lanthanoid element and lithium used in step (2) can be prepared, for example, by the method described in the Examples section below.

[0125] The acid salt complex containing lanthanoid elements and lithium may be used alone or in combination of two or more. Usually, the amount of the complex salt used is 0.8 to 3 mol, preferably 0.9 to 2 mol, per mol of the compound represented by the general formula (1).

[0126] Step (2) can be carried out in the presence of a solvent as required. Examples of usable solvents include ethers. Specifically, examples of ethers include diethyl ether, cyclopentyl methyl ether, and tetrahydrofuran. One solvent may be used, or two or more solvents may be used simultaneously. Usually, the amount of solvent used is usually 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, relative to 1 part by weight of the compound represented by the general formula (1).

[0127] Step (2) can be carried out in the following manner: for example, a compound represented by the general formula (1) and a solvent are added to a reaction vessel and the temperature is set to -20°C or below, preferably -75 to -30°C, then an acid complex containing a lanthanide element and lithium is added at the same temperature and stirred for a certain period of time, thereby generating a lanthanide element complex of the general formula (1), then the temperature is raised to -10°C to 10°C, and a silyl compound represented by the general formula (2) is added to the reaction vessel at the same temperature, thereby reacting the lanthanide element complex of the general formula (1) with the silyl compound represented by the general formula (2). In addition, from the viewpoint of increasing the reaction rate, after adding the silyl compound represented by the general formula (2), the reaction solution may be heated to 10 to 40°C as needed.

[0128] After the reaction is completed, for example, an organic solvent and water are added to the reaction solution, the liquid is separated and the water layer is removed, thereby removing the inorganic salt and the like into the water layer, and then the organic layer containing the compound is concentrated to obtain the compound represented by the general formula (1). The obtained compound represented by the general formula (1) can be purified by distillation, crystallization, column chromatography using silica gel, etc. as needed.

[0129] (1-2) Naphthylsiloles with aromatic heterocycles

[0130] According to the method for producing naphthyl siloles of the present invention, naphthyl siloles having an aromatic heterocyclic ring and a structure represented by the general formula (3a) can be produced. 1a , R 1b , R 3a and R 3b The above groups can be used. 2a’ The aromatic heterocyclic ring and its structure are also as described above. For the group having a substituent, the type and number of the substituent are also the same. 2a’ Preferred examples of the aromatic heterocyclic ring include a furan ring, a thiophene ring, a pyrrole ring, and a pyridine ring.

[0131] [Chemical formula 16]

[0132]

[0133] In formula (3a), R 1a , R1b , R 2a’ , R 3a and R 3b With the R 1a , R 1b , R 2a’ , R 3a and R 3b same.

[0134] As the naphthyl siloles having an aromatic heterocyclic ring and having a structure represented by the general formula (3a), specifically, for example, naphthyl siloles represented by the following general formulas (3a1), (3a2) and (3a3), or naphthyl siloles represented by the following general formulas (3a4), (3a5), (3a6) and (3a7) can be cited.

[0135] [Chemical formula 17]

[0136]

[0137] In formula (3a1), (3a2) and (3a3), R 30a represents a hydrogen atom or an alkyl group; R 30c and R 30d are the same or different and represent a hydrogen atom, an alkyl group or an aromatic hydrocarbon group; R 30c With R 30d When adjacent, R 30c With R 30d Optionally bond to each other to form a ring; X 30b represents an oxygen atom, a sulfur atom or NR 30e , where R 30e represents an alkyl group, an aromatic hydrocarbon group, an acetyl group, a tert-butoxycarbonyl group, a methylsulfonyl group or a toluenesulfonyl group.

[0138] [Chemical formula 18]

[0139]

[0140] In formulas (3a4), (3a5), (3a6) and (3a7), R 30a represents a hydrogen atom or an alkyl group; R 30f , R 30g and R 30h are the same or different and represent a hydrogen atom, an alkyl group or an aromatic hydrocarbon group; R 30f , R 30g and R 30h When adjacent, R 30e , R 30f and R 30g They are optionally bonded to each other to form a ring.

[0141] More specifically, naphthyl siloles represented by the following formula are mentioned.

[0142] [Chemical formula 19]

[0143]

[0144] In the formula, n-octyl represents n-octyl, and Et represents ethyl.

[0145] In the above, as R 30a , R 30c , R 30d , R 30e , R 30f , R 30g and R 30h The alkyl group shown, R 30c , R 30d , R 30e , R 30f , R 30g and R 30h The aromatic hydrocarbon group, R 30c With R 30d When the rings are bonded to each other, R 30e , R 30f and R 30g The rings when bonded to each other include the above-mentioned alkyl, aromatic hydrocarbon groups, and rings. For the groups having substituents, the types and numbers of the substituents are also the same. In addition, the preferred embodiments are also the same.

[0146] (1-3) GNRs with heterocyclic aromatic rings

[0147] The GNR of the present invention has at least one structural unit represented by the general formula (6). 1a , R 1b and R 2a’ The above-mentioned groups can be used. For the groups having substituents, the types and numbers of the substituents are also the same. In addition, the preferred embodiments are also the same. 1a With R 1b When they are bonded to form a ring, R 1a With R 1b They are optionally bonded to each other to form a ring.

[0148] [Chemical formula 20]

[0149]

[0150] In formula (6), * represents a bonding site; n represents an integer greater than 0; R 1a , R 1b and R 2a’ With the R 1a , R 1b and R 2a’Same; R bonded to the same benzene ring 1a With R 1b They are optionally bonded to each other to form a ring.

[0151] The GNR of the present invention can be produced, for example, by the method of Patent Document 1. Therefore, at least one terminal may be a structural unit represented by the general formula (7).

[0152] [Chemical formula 21]

[0153]

[0154] In formula (7), the dashed line indicates the absence of a bond or a single bond; * indicates a bonding site; R 6a , R 6b , R 6c , R 6d , R 6e and R 6f R is the same or different and represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a boric acid or an ester group thereof, a monovalent aromatic hydrocarbon group, or a monovalent heterocyclic group. 6c With R 6d They are optionally bonded to each other to form a ring.

[0155] R in the general formula (7) 6a , R 6b , R 6c , R 6d , R 6e and R 6f Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0156] As R in the general formula (7) 6a , R 6b , R 6c , R 6d , R 6e and R 6f The alkyl group shown in the figure may be the above-mentioned alkyl group. For the group having a substituent, the type and number of the substituent are also the same. In addition, the preferred embodiment is also the same.

[0157] As R in the general formula (7) 6a , R 6b , R 6c , R 6d , R 6e and R 6f The cycloalkyl group shown in the figure may be the above-mentioned cycloalkyl group. For the group having a substituent, the type and number of the substituent are also the same. In addition, the preferred embodiment is also the same.

[0158] R in the general formula (7) 6a , R 6b, R 6c , R 6d , R 6e and R 6f The (poly)ether group shown refers to an ether group or a polyether group. As the (poly)ether group, the above-mentioned (poly)ether group can be used. For the group having a substituent, the type and number of the substituent are also the same. In addition, the preferred embodiment is also the same.

[0159] As R in the general formula (7) 6a , R 6b , R 6c , R 6d , R 6e and R 6f The ester groups shown in the formula (a) may be the ester groups described above. For the groups having substituents, the types and numbers of the substituents are also the same. In addition, the preferred embodiments are also the same.

[0160] As R in the general formula (7) 6a , R 6b , R 6c , R 6d , R 6e and R 6f Examples of the boronic acid or ester group thereof include a boryl group and a pinacol boryl group.

[0161] As R in the general formula (7) 6a , R 6b , R 6c , R 6d , R 6e and R 6f The aromatic hydrocarbon group or heterocyclic group shown in the formula (a) may be the aromatic hydrocarbon group or heterocyclic group described above, and the type and number of the substituents are also the same.

[0162] As R in the general formula (7) 6a , R 6b , R 6c , R 6d , R 6e and R 6f , from the perspective of raw material availability, water solubility, etc., preferably a hydrogen atom, an alkyl group, a (poly)ether group, etc. When it is an alkyl group, a branched alkyl group is more preferred, and isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, etc. are further preferred, and tert-butyl is particularly preferred.

[0163] R in the general formula (7) 6c With R 6d They may optionally bond to each other to form a ring. Examples of the ring formed in this case include the aromatic hydrocarbon ring and heterocyclic ring described above.

[0164] As described above, the GNR of the present invention has at least one structural unit represented by the general formula (6) and at least one structural unit represented by the general formula (7). Therefore, the GNR has a structural unit represented by the general formula (8).

[0165] [Chemical formula 22]

[0166]

[0167] In formula (8), the dashed lines are the same or different and represent the absence of a bond or a single bond; *1 represents a bonding site; when the dashed line connected to *2 is a single bond, *2 represents a bonding site; n represents an integer greater than 0; R 1a , R 1b , R 2a’ , R 6a , R 6b , R 6c , R 6d , R 6e and R 6f With the R 1a , R 1b , R 2a’ , R 6a , R 6b , R 6c , R 6d , R 6e and R 6f Same; R bonded to the same benzene ring 1a With R 1b Optionally bond to each other to form a ring; R 6c With R 6d They are optionally bonded to each other to form a ring.

[0168] R in the general formula (8) 1a , R 1b , R 2a’ , R 6a , R 6b , R 6c , R 6d , R 6e and R 6f The above-mentioned groups can be used. For the groups having substituents, the types and numbers of the substituents are also the same. In addition, the preferred embodiments are also the same.

[0169] Specific examples of the structural unit represented by the general formula (8) include structural units represented by the following general formulae (8a1), (8a2), ​​(8a3), (8a4), (8a5), (8a6), (8a7), (8a8), (8a9), (8a10), (8a11), (8a12), (8a13), and (8a14).

[0170] [Chemical formula 23]

[0171]

[0172] [Chemical formula 24]

[0173]

[0174] [Chemical formula 25]

[0175]

[0176] In the formula, * represents a bonding site; n represents an integer greater than 0; R 30a , R 30c , R 30d , X 30b , R 30f , R 30g and R 30h With the R 30a , R 30c , R 30d , X 30b , R 30f , R 30g and R 30h same.

[0177] More specifically, structural units represented by the following formulae can be mentioned.

[0178] [Chemical formula 26]

[0179]

[0180] In the formula, * represents a bonding site; n represents an integer greater than 0; n-octyl represents n-octyl; and Et represents ethyl.

[0181] In addition, the GNR having the above structural unit can be subjected to a ring contraction reaction to prepare a GNR having the following structural unit. The ring contraction reaction can be applied to the method described in Patent Document 1 (specifically, for example, the Scholl reaction (dehydrogenation cyclization reaction)).

[0182] Specific examples of the GNR subjected to the ring contraction reaction include structural units represented by the following general formulae (9a1), (9a2), (9a3), (9a4), (9a5), (9a6) and (9a7).

[0183] [Chemical formula 27]

[0184]

[0185] [Chemical formula 28]

[0186]

[0187] In the formula, * represents a bonding site; n represents an integer greater than 0; R 30a , R 30c , R 30d , X 30b , R 30f , R 30g and R 30h With the R 30a , R 30c , R 30d , X 30b , R 30f , R 30g and R 30h In addition, in the general formulas (9a5) and (9a6), R 30h and R 30f When it is a hydrogen atom, a single bond is formed.

[0188] More specifically, the structural unit represented by the following formula can be mentioned.

[0189] [Chemical formula 29]

[0190]

[0191] In the formula, * represents a bonding site; n represents an integer greater than 0; n-octyl represents n-octyl; and Et represents ethyl.

[0192] In the GNR of the present invention, n in the general formula (6) and (8) is not particularly limited, and is an integer greater than 0, and can be appropriately selected according to the desired properties, for example, preferably 10 to 1000, more preferably 10 to 500. In addition, for example, oligomers in which n in the general formula (6) and (8) is 1 to 99, preferably 2 to 49, more preferably 2 to 19, and further preferably 3 to 9 can be prepared. n of the GNR of the present invention can be calculated from the number average molecular weight measured in terms of polystyrene by gel permeation chromatography.

[0193] For the GNR of the present invention, the number average molecular weight is not particularly limited and can be appropriately selected according to the desired properties. From the perspective of solubility, for example, it is preferably 10,000 or more, more preferably 15,000 to 300,000, further preferably 20,000 to 200,000, and particularly preferably 30,000 to 150,000. In addition, for example, when an oligomer is prepared, the number average molecular weight of the GNR of the present invention can be prepared, for example, to be 500 to 5,000. The number average molecular weight of the GNR of the present invention can be measured by gel permeation chromatography in terms of polystyrene.

[0194] In addition, the length of the GNR of the present invention is preferably 10 nm or more, more preferably 20 to 500 nm, further preferably 50 to 400 nm, and particularly preferably 100 to 300 nm. In addition, for example, when the GNR of the present invention is made into an oligomer, the length of the GNR of the present invention can be appropriately selected according to the desired characteristics. GNRs with longer lengths can be expected to be applied to semiconductors, solar cells, etc., and GNRs with shorter lengths can be expected to be applied to organic EL elements, etc.

[0195] Example

[0196] Hereinafter, the present invention will be specifically described with reference to Examples and the like, but the present invention is not limited thereto.

[0197] (1) NMR measurement

[0198] for 1 H-NMR and 13 C-NMR was performed using a JEOL-ESC600 ( 1 H 600MHz, 13 C 150MHz) or JEOL-ESC400( 1 H 400MHz, 13 C 100MHz, 19 F376MHz) spectrometer for recording.

[0199] In addition, each data is described as follows.

[0200] Chemical shift, multiplicity (s=singlet, d=doublet, dd=doublet ofdoublets, ddd=doublet of doublet of doublets, t=triplet, td=triplet of doublets, q=quartet, m=multiplet), bond constant (Hz), and integration.

[0201] (2) Fast Atom Bombardment Mass Spectrometry (FAB-MS)

[0202] For FAB-MS, 3-nitrobenzyl alcohol was used as a matrix and high resolution mass spectra (HRMS) were obtained using a double focusing magnetic mass spectrometer (JEOL JMS-700).

[0203] (3) Determination of molecular weight (Mn) and Mw / Mn (PDI) of GNRs using size exclusion chromatography (SEC)

[0204] The analysis was performed using the following apparatus and under the following conditions.

[0205] Installation: Shimadzu Prominence 2000

[0206] Chromatographic column: TOSOH TSKgel Multipore H manufactured by TOSOH CORPORATION XL -M SEC Column 7.8mm×300mm×2 (connected in series)

[0207] Measurement temperature: 40℃

[0208] Eluent: Tetrahydrofuran containing 0.1% by mass of tetrabutylammonium bromide

[0209] Standard molecular weight: based on standard polystyrene (TOSOH TSKgel polystyrene standard).

[0210] (4) Regarding the substances used for analysis / purification etc. in the following examples etc.

[0211] Thin layer chromatography (TLC) for analysis: E. Merck silica gel 60 F254 pre-coated plates (0.25 mm)

[0212] Silica gel for column chromatography: KANTO silica gel 60N (spherical, neutral, 40-100 μm)

[0213] Metal scavenger (metal scavenger): Biotage Metal Scavenger Si-TMT.

[0214] (5) Preparative size exclusion chromatography (SEC) and preparation conditions:

[0215] Device: JAI LC-9210II NEXT manufactured by Japan Analytical Industry.

[0216] Chromatographic column: JAIGEL-3H / JAIGEL-5H manufactured by Japan Analytical Industry.

[0217] Solvent: Chloroform

[0218] Flow rate: 3.5 mL / min.

[0219] <Production Example 1>

[0220] Preparation Example of 3-chloro-3-ethylundecane

[0221] [Chemical formula 30]

[0222]

[0223] In the formula, Et represents ethyl, n-octyl represents n-octyl, and THF represents tetrahydrofuran.

[0224] Magnesium shavings (5.8 g, 240 mmol) was added to a 200 mL two-necked round-bottom flask with a magnetic stirrer, and stirring was started. The flask was heated for 10 minutes using a heat gun under reduced pressure, and then replaced with nitrogen. After nitrogen replacement, the flask was cooled to room temperature, and n-octyl bromide (37.1 mL, 225 mmol) and THF (100 mL) were added to the flask at the same temperature. 1,2-dibromoethane (2 drops, for activation of magnesium shavings) was further added, and the temperature was raised to 40°C, and stirred at the same temperature for 1 hour to prepare the corresponding Grignard reagent. 3-Pentanone (Compound S1; 16.0 mL, 150 mmol) and THF (100 mL) were added to another 300 mL two-necked round-bottom flask with a magnetic stirrer. The Grignard reagent solution prepared in the above manner was added dropwise to the mixed solution of 3-pentanone and THF at 0°C with vigorous stirring, and then the temperature was raised to 40°C and stirred at the same temperature for 14 hours.

[0225] After confirming the progress of the reaction by TLC, the obtained reaction mixture was quenched with water. The organic layer was washed with saturated NH4Cl aqueous solution and water, and dried over Na2SO4, and then the Na2SO4 was filtered and the solvent was removed under reduced pressure to obtain a crude product of 3-ethyl-3-hydroxyundecane (compound S2).

[0226] Next, concentrated hydrochloric acid (35 mL) was added to a 200 mL double-mouthed round-bottomed flask containing the crude product of compound S2 obtained by the above operation and a magnetic stirrer, and then stirred at room temperature for 1 hour, and organic matter was extracted 3 times from the obtained mixture using diethyl ether (100 mL). The extracted organic layers were combined, washed with brine, and then dried with Na2SO4. Then, Na2SO4 was filtered, and the solvent was removed under reduced pressure to obtain a crude product, which was purified by flash column chromatography on silica gel (eluent: hexane) to obtain 3-chloro-3-

[0227] Ethyl undecane (Compound S3; 17.0 g, yield 76%).

[0228] <Production Example 2>

[0229] Preparation Example of Naphthol with Substitutents

[0230] [Chemical formula 31]

[0231]

[0232] In the formula, Et represents ethyl, and n-octyl represents n-octyl.

[0233] Under nitrogen atmosphere, 2-naphthol (compound S4; 12.0 g, 83.2 mmol), 3-chloro-3-ethylundecane (compound S3; 27.3 g, 124.9 mol) and CH2Cl2 (120 mL) were added to a 200 mL two-necked round-bottom flask with a magnetic stirrer, and stirring was started. Then, AlCl3 (11.0 g, 83.2 mmol) was added at room temperature. Then, the temperature was raised to 40°C, and after stirring at the same temperature overnight, methanol (30 mL) was added to quench the reaction.

[0234] Then, the organic layer was washed with water and dried over Na2SO4, then filtered, and the solvent was removed under reduced pressure to obtain a crude product. The crude product was purified by open column chromatography on silica gel (eluent: CH2Cl2 / hexane=4:1) to obtain 6-(3-ethyl-undecyl)-2-naphthol (compound S5) (13.0 g, yield 48%) as a colorless oil.

[0235] <Example 1>

[0236] Preparation Example of Compound Represented by General Formula (4)

[0237] [Chemical formula 32]

[0238]

[0239] In the formula, NBS represents N-bromosuccinimide, DMF represents N,N-dimethylformamide, Et represents ethyl, and n-octyl represents n-octyl.

[0240] Under nitrogen atmosphere, S5 (17.00 g, 52.1 mmol) and DMF (112 ml) were added to a 1 L double-necked round-bottom flask with a magnetic stirrer, and stirring was started. Then, NBS (10.19 g, 57.3 mmol) dissolved in DMF (200 ml) was slowly added dropwise at room temperature over 30 minutes. After stirring at room temperature for 14 hours, the mixture was quenched with water and extracted three times with ethyl acetate (40 ml). The combined organic layer was washed with brine, then dried over Na2SO4, and then Na2SO4 was filtered and the solvent was removed under reduced pressure to obtain a crude product. The crude product was purified by open column chromatography on silica gel (eluent: hexane / ethyl acetate = 20:1) to obtain 1-bromo-6-(3-ethyl-undecyl)-2-naphthol (compound S6) (17.16 g, yield 81%) as a colorless oil.

[0241] Under nitrogen atmosphere, compound S6 (17.16 g, 42.3 mmol) and CH2Cl2 (84 ml) were added to a 100 ml double-necked round-bottom flask with a magnetic stirrer, and stirring was started. Then, after cooling to 0°C, pyridine (4.11 ml, 50.8 mmol) was added at the same temperature, and further stirred at the same temperature for 10 minutes. Then, trifluoromethanesulfonic anhydride (7.83 ml, 46.6 mmol) was added, and after stirring at 0°C for 2 hours, water was added to quench the reaction. After extracting the organic matter from the obtained reaction mixture three times with ethyl acetate (30 ml), the combined organic layer was washed with brine, then dried with Na2SO4, and then filtered Na2SO4, and the solvent was removed under reduced pressure to obtain a crude product. The obtained crude product was purified by open column chromatography on silica gel (eluent: hexane) to obtain yellow oily 1-bromo-6-(3-ethyl-3-undecyl)-2-naphthyl trifluoromethanesulfonate (Compound 4-1) (16.9 g, yield 74%). The analytical values ​​of the obtained compound (4-1) are as follows.

[0242] 1 H NMR (400MHz, CDCl3): δ8.23(d,J=8.7Hz,1H),7.85(d,J=8.7Hz,1H),7.68-7.73(m(dd,d),2H),7.40(d,J=8.7Hz, 1H),1.78(q,J=7.3Hz,4H),1.68-1.75(m,2H),1.17-1.31(m,10H),0.85(t,J=6.9Hz,3H),0.67(t,J=7.3Hz,6H);

[0243] 19 F NMR (382MHz, CDCl3): δ-73.2.

[0244] <Example 2>

[0245] Preparation Example (1) of the compound represented by the general formula (1)

[0246] [Chemical formula 33]

[0247]

[0248] In the formula, Ph represents phenyl, dba represents dibenzylideneacetone, dppp represents 1,3-bis(diphenylphosphino)propane, Et represents ethyl, and n-octyl represents n-octyl.

[0249] Under nitrogen atmosphere, (4-1) (7.54 g, 14.0 mmol), Pd2(dba)3 (231 mg, 0.28 mmol), dppp (231 mg, 0.56 mmol), LiBr (1.22 g, 14.0 mmol) and Et2O (12 ml) were added to a 100 ml two-necked round-bottom flask with a magnetic stirrer, and stirring was started. Then, after cooling to 0°C, phenylmagnesium bromide (3.0 M in Et2O, 7.01 ml) was added dropwise while stirring at the same temperature. After warming to room temperature and stirring for 20 hours at the same temperature, the mixture was quenched with 1 M hydrochloric acid and extracted three times with ethyl acetate (20 ml). The combined organic layer was washed with brine, then dried over Na2SO4, and then the Na2SO4 was filtered, and the solvent was removed under reduced pressure to obtain a crude product. The crude product was purified by open column chromatography on silica gel (eluent: hexane / ethyl acetate = 20:1) to obtain 1-bromo-6-(3-ethyl-undecyl)-2-phenylnaphthalene (Compound 1-1) (5.14 g, yield 79%) as a pale yellow oil. The analytical values ​​of the obtained compound (1-1) are as follows.

[0250] 1 HNMR (400MHz, CDCl3): δ8.32(d,J=9.1Hz,1H),7.81(d,J=9.1Hz,1H),7.71(d,J=2.0Hz,1H),7.64(dd,J=2.0,9.1Hz,1H),7.45-7.49(m,4H), 7.41(m,2H),1.81(q,J=7.5Hz,4H),1.69-1.76(m,2H),1.16-1.32(m,10H),0.98-1.08(m,2H),0.86(t,J=7.5Hz,3H),0.68(t,J=7.5Hz,6H).

[0251] 13 CNMR (100MHz, CDCl3): δ146.2,142.4,139.9,133.4,130.6,129.7(2C),128.3,127.9(2C),127.5,127. 4(2C),127.2,125.8,122.1,43.7,36.4,31.9,30.5,29.5,29.3,28.9(2C),23.5,22.6,14.1,8.1(2C).

[0252] HRMS(FAB+)m / z calcd for C 29 H 37 Br[M+H] +;464.2079,found464.2073.

[0253] <Example 3>

[0254] Preparation Example (2) of the compound represented by the general formula (1)

[0255] [Chemical formula 34]

[0256]

[0257] In the formula, dba represents dibenzylideneacetone, dppp represents 1,3-bis(diphenylphosphino)propane, Et represents ethyl, and n-octyl represents n-octyl.

[0258] Magnesium shavings (90.4 mg, 3.72 mmol) were added to a Schrenck tube with a magnetic stirrer, stirring was started, and the Schrenck tube was heated with a heat gun under reduced pressure and then replaced with nitrogen. After nitrogen replacement, the tube was cooled to room temperature, diethyl ether (1 ml) was added to the Schrenck tube at the same temperature, and 2-bromo-5-methylthiophene (0.139 ml, 2.79 mmol) was further added dropwise at room temperature, and then stirred at the same temperature for 1 hour to prepare a Grignard reagent of 2-bromo-5-methylthiophene.

[0259] In another test tube with a cap, (4-1) (1.00 g, 1.86 mmol), LiBr (0.162 mg, 1.86 mmol), dppp (30.7 mg, 74.4 μmmol), Pd2(dba)3 (34.0 mg, 37.2 μmmol) and Et2O (1 ml) were added, and stirring was started. The mixture was cooled to 0°C, and the Grignard reagent of 2-bromo-5-methylthiophene prepared separately was added dropwise at 0°C using a syringe. After the addition, the mixture was heated to room temperature and stirred at the same temperature for 15 hours.

[0260] After the reaction is completed, the obtained reaction mixture is quenched with 1M hydrochloric acid, and after separating the oil layer and the water layer by liquid separation, ethyl acetate is added to the separated water layer to extract organic matter from the water layer. Then, the separated oil layer is combined with the organic layer obtained by extracting organic matter from the water layer, dried with Na2SO4, and then, Na2SO4 is filtered, and the solvent is removed under reduced pressure to obtain a crude product. The crude product is purified by open column chromatography on silica gel (eluent: hexane), thereby quantitatively obtaining 2-(1-bromo-6-(3-ethylundecane-3-yl)naphthalene-2-yl)-5-methylthiophene (compound 1-2) (0.982g).

[0261] <Example 4>

[0262] Preparation Example (1) of the compound represented by the general formula (3)

[0263] [Chemical formula 35]

[0264]

[0265] In the formula, nBu represents n-butyl, THF represents tetrahydrofuran, Me represents methyl, Et represents ethyl, and n-octyl represents n-octyl.

[0266] Under nitrogen atmosphere, a 0.6 M hexane solution of LaCl3·2LiCl (11.92 mL, 7.15 mmol) and THF (6 mL) were added to a Schlenk tube with a magnetic stirrer, and stirring was started, and the mixture was cooled to -50°C. After cooling, a 1.6 M hexane solution of n-BuLi (9.0 mL, 7.15 mmol) was added dropwise at -50°C.

[0267] 14.3 mmol), and then stirred at the same temperature for 30 minutes to prepare an acid anion complex containing lanthanide elements and lithium. Next, (1-1) (3.03 g, 6.5 mmol) was added at -50°C, and after addition, stirring was continued at the same temperature for 5 minutes.

[0268] Then, the temperature was raised to 0°C over 30 minutes while stirring, and dichlorodimethylsilane (1.17 mL, 9.75 mmol) was added at the same temperature. Then, the temperature was further raised to room temperature and stirred at the same temperature for 1 hour.

[0269] After the reaction is completed, water is added, and the oil layer and the water layer are separated by liquid separation. Ethyl acetate is added to the separated water layer to extract organic matter from the water layer. This extraction operation is performed a total of 3 times. Then, the separated oil layer is combined with the organic layer obtained by extracting organic matter from the water layer, dried with Na2SO4, and then, Na2SO4 is filtered, and the solvent is removed under reduced pressure to obtain a crude product. The crude product is purified by recrystallization to obtain 3-(3-ethyl-3-undecyl)-11,11-dimethyl-11H-benzo[b]naphtho[2,1-d]silole (Compound 3-1) (1.52 g, yield 53%).

[0270] <Example 5>

[0271] Preparation Example (2) of the compound represented by the general formula (3)

[0272] [Chemical formula 36]

[0273]

[0274] In the formula, nBu represents n-butyl, THF represents tetrahydrofuran, Me represents methyl, Et represents ethyl, and n-octyl represents n-octyl.

[0275] Under nitrogen atmosphere, a 0.6M hexane solution of LaCl3·2LiCl (1.51 mL, 0.906 mmol) and THF (0.8 mL) were added to a Schlenk tube with a magnetic stirrer, and stirring was started, and the mixture was cooled to -50°C. After cooling, a 1.6M hexane solution of n-BuLi (1.13 mL, 1.81 mmol) was added dropwise at -50°C, and then stirred at the same temperature for 30 minutes to prepare an acid radical complex containing lanthanide elements and lithium. Next, (1-2) (0.40 g, 0.824 mmol) was added at -50°C, and stirring was continued at the same temperature for 5 minutes after addition.

[0276] Then, the temperature was raised to 0°C over 30 minutes while stirring. After the temperature was raised, dichlorodimethylsilane (0.120 mL, 1.24 mmol) was added at the same temperature. Then, the temperature was further raised to room temperature and stirred at the same temperature for 1 hour.

[0277] After the reaction is completed, water is added, and the oil layer and the water layer are separated by liquid separation. Ethyl acetate is added to the separated water layer to extract organic matter from the water layer. This extraction operation is performed 3 times in total. Then, the separated oil layer is combined with the organic layer obtained by extracting organic matter from the water layer, dried with Na2SO4, and then the Na2SO4 is filtered, and the solvent is removed under reduced pressure to obtain a crude product. The crude product is purified by open column chromatography on silica gel (eluent: hexane) and preparative size exclusion chromatography (SEC) to obtain 3-(3-ethylundecane-3-yl)-8,10,10-trimethyl-10H-naphtho[2'1':4,5]thiole[3,2-b]thiophene (compound 3-2) (69.3 mg, yield 18%). The analytical values ​​of the obtained compound (3-2) are as follows.

[0278] 1 H NMR (600MHz, CDCl3): δ7.671 (d, J = 8.4Hz, 1H), δ7.646 (s, 1H), δ7.565 (d, J = 9.0Hz, 1H), δ7.4703 (dd, J = 4.5Hz, J = 1.8Hz 1H),δ6.829(s,1H),δ2.554(s,3H)δ0.545(s,6H)

[0279] HRMS (FAB+) m / z=462.

[0280] <Example 6>

[0281] Preparation Example (3) of the compound represented by the general formula (3)

[0282] [Chemical formula 37]

[0283]

[0284] In the formula, nBu represents n-butyl, THF represents tetrahydrofuran, and Me represents methyl.

[0285] Under nitrogen atmosphere, a 0.6M hexane solution of LaCl3·2LiCl (48 mL, 28.8 mmol) and THF (30 mL) were added to a Schlenk tube with a magnetic stirrer, and stirring was started, and the mixture was cooled to -50°C. After cooling, a 1.6M hexane solution of n-BuLi (36 mL, 57.6 mmol) was added dropwise at -50°C, and then stirred at the same temperature for 30 minutes to prepare an acid radical complex containing lanthanide elements and lithium. Next, (1-3) (7.5 g, 26.5 mmol) was added at -50°C, and stirring was continued at the same temperature for 5 minutes after the addition.

[0286] Then, the temperature was raised to 0°C over 30 minutes while stirring, and dichlorodimethylsilane (5.1 mL, 34.5 mmol) was added at the same temperature. Then, the temperature was further raised to room temperature and stirred at the same temperature for 1 hour.

[0287] After the reaction is completed, water is added, and the oil layer and the water layer are separated by liquid separation. Toluene is added to the separated water layer to extract organic matter from the water layer. This extraction operation is performed a total of 3 times. Then, the separated oil layer is combined with the organic layer obtained by extracting organic matter from the water layer, dried with Na2SO4, and then Na2SO4 is filtered, and the solvent is removed under reduced pressure to obtain a crude product. The crude product is purified by recrystallization to obtain 11,11-dimethyl-11H-benzo[b]naphtho[2,1-d]silole (Compound 3-3) (4.65 g, yield 67.4%).

[0288] <Example 7>

[0289] Preparation example of GNR with aromatic heterocycle

[0290] [Chemical formula 38]

[0291]

[0292] In the formula, Et represents ethyl, and n-octyl represents n-octyl.

[0293] Under nitrogen atmosphere, monomer (compound (3-2)) (29.4 mg, 63.5 μmol), AgSbF6 (43.7 mg, 127 μmol), Pd(OCOCF3)2 (21.1 mg, 63.5 μmol) and o-tetrachlorobenzoquinone (31.2 mg, 127 μmol) were added to a 5 mL Schlenk tube with a magnetic stirrer, and stirring was started. Then, initiator I (diphenylacetylene) (0.11 mg, 0.635 μmol) dissolved in 1,2-dichloroethane (0.1 mL) was added, and then the wall of the Schlenk tube was washed with 1,2-dichloroethane (0.57 mL). Then, the temperature was raised to 80°C and stirred at the same temperature for 21.5 hours to obtain a reaction mixture.

[0294] The obtained reaction mixture was cooled to room temperature, and the obtained reaction mixture was washed with CH2Cl2 and passed through a silica gel short pad column and a metal purifier (metal scavenger). Then, the solvent was removed from the reaction mixture under reduced pressure to obtain GNR1.

[0295] The obtained GNR1 was analyzed by size exclusion chromatography (SEC), and the result showed that Mn=2.9

[0296] ×10 4 And Mw / Mn(PDI)=1.14.

[0297] <Example 8>

[0298] Preparation Example (3) of the compound represented by the general formula (1)

[0299] [Chemical formula 39]

[0300]

[0301] In the formula, dba represents dibenzylideneacetone, dppp represents 1,3-bis(diphenylphosphino)propane, Et represents ethyl, and n-Bu represents n-butyl.

[0302] Under nitrogen atmosphere, (4-2) (7.54 g, 14.0 mmol), Pd2(dba)3 (231 mg, 0.28 mmol), dppp (231 mg, 0.56 mmol), LiBr (1.22 g, 14.0 mmol) and Et2O (12 mL) were added to a 100 ml two-necked round-bottom flask with a magnetic stirrer, and stirring was started. Then, after cooling to 0°C, 4-butylphenylmagnesium bromide (3.0 M in Et2O, 7.01 mL) was added dropwise while stirring at the same temperature. After warming to room temperature and stirring for 20 hours at the same temperature, the mixture was quenched with 1 M hydrochloric acid and extracted three times with ethyl acetate (20 mL). The combined organic layer was washed with brine, then dried over Na2SO4, and then the Na2SO4 was filtered, and the solvent was removed under reduced pressure to obtain a crude product. The crude product was purified by open column chromatography on silica gel (eluent: hexane / ethyl acetate = 20:1) to obtain 1-bromo-2-(4-butylphenyl)naphthalene (Compound 1-4) (4.08 g, yield 86%) as a pale yellow oil. The analytical values ​​of the obtained Compound (1-4) are as follows.

[0303] 1 HNMR (400MHz, CDCl3): δ8.41 (d, J = 8.7Hz, 1H), 7.86 (d, J = 8.7Hz,

[0304] 1H),7.83(d,J=8.7Hz,1H),7.65-7.60(m,1H),7.56-7.51(m,1H),7.43(d,J=8.7Hz,1H),7.39(d,J=8.7Hz,2H),7.28 (d, J=8.7Hz, 2H), 2.71 (t, J=7.8Hz, 2H), 1.69 (quin, J=7.8Hz, 2H), 1.46 (sext, J=7.8Hz, 2H), 0.96 (t, J=7.8Hz, 3H).

[0305] 13 CNMR (100MHz, CDCl3): δ142.2,140.7,139.5,133.5,132.5,129.5(2C),128.7,1 28.04,127.98(2C),127.92,127.6,127.4,126.4,122.5,35.5,33.5,22.5,14.0.

[0306] <Example 9>

[0307] Preparation Example (4) of the compound represented by the general formula (3)

[0308] [Chemical formula 40]

[0309]

[0310] In the formula, nBu represents n-butyl, THF represents tetrahydrofuran, and Me represents methyl.

[0311] Under nitrogen atmosphere, a 0.6M hexane solution of LaCl3·2LiCl (27.0 mL, 16.2 mmol) and THF (30 mL) were added to a Schlenk tube with a magnetic stirrer, and stirring was started, and the mixture was cooled to -50°C. After cooling, a 1.6M hexane solution of n-BuLi (20.3 mL, 32.4 mmol) was added dropwise at -50°C, and then stirred at the same temperature for 30 minutes to prepare an acid radical complex containing lanthanide elements and lithium. Next, (1-4) (5.0 g, 14.7 mmol) was added at -50°C, and stirring was continued at the same temperature for 5 minutes after the addition.

[0312] Then, the temperature was raised to 0°C over 30 minutes while stirring, and dichlorodimethylsilane (2.69 mL, 22.11 mmol) was added at the same temperature. Then, the temperature was further raised to room temperature and stirred at the same temperature for 1 hour.

[0313] After the reaction is completed, water is added, and the oil layer and the water layer are separated by liquid separation. Toluene is added to the separated water layer to extract organic matter from the water layer. This extraction operation is performed a total of 3 times. Then, the separated oil layer is combined with the organic layer obtained by extracting organic matter from the water layer, dried with Na2SO4, and then the Na2SO4 is filtered, and the solvent is removed under reduced pressure to obtain a crude product. The crude product is purified by recrystallization to obtain 9-butyl-11,11-dimethyl-11H-benzo[b]naphtho[2,1-d]silole (Compound 3-4) (3.09 g, yield 66%). The analytical values ​​of the obtained compound (3-4) are as follows.

[0314] 1 H-NMR (400MHz, CDCl3) δ7.95(d,J=8.7Hz,1H),7.91(d,J=8.7Hz,1H),7.87-7.82(m,2H),7.80(d,J=7.8Hz,1H),7.53-7.47(m,2H),7.46-7.4 0m,1H),7.28(dd,J=1.8,7.8Hz,1H),2.68(t,J=7.3Hz,2H),1.71-1.62(m,2H),1.42(sext,J=7.3Hz,2H),0.97(t,J=7.3Hz,3H),0.58(s,6H).

[0315] 13C-NMR(100MHz,CDCl3)δ146.9,145.7,142.1,139.2,136.8,136.5,132.84,132.81,130.8,130.3,128.9,128.3,126.5,125.2,120.8,119.7,35.6,33.8,22.5,14.0,-2.7(2C).

Claims

1. A method for producing a compound represented by the general formula (3), comprising the steps of reacting a compound represented by the general formula (1) with an acid group-type complex containing a lanthanide element and lithium to produce a lanthanide complex of the compound represented by the general formula (1), and reacting the lanthanide complex with a silyl compound represented by the general formula (2). In formula (3), R 1a and R 1b are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a halogen atom, an aromatic hydrocarbon group or a heterocyclic group; R 1a With R 1b Optionally bond to each other to form a ring; R 2’ represents an aromatic hydrocarbon ring or a heterocyclic ring; R 3a and R 3b are the same or different and represent an alkyl group having 1 to 4 carbon atoms and optionally having a branch or a phenyl group, In formula (1), R 1a and R 1b With the R 1a and R 1b Same; R 2 represents an aromatic hydrocarbon group or a heterocyclic group; X represents a bromine atom or an iodine atom, R 3a R 3b SiCl2(2) In formula (2), R 3a and R 3b With the R 3a and R 3b same.

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