Method for producing naphthylsiloles, naphthylsiloles having heterocyclic groups, and graphene nanoribbons having heterocyclic groups

Abstract

Provided is a method which makes it possible to more safely produce a naphthyl silole to be used as a GNR raw material, by: producing a lanthanoid complex of a compound represented by formula (1) by reacting the compound represented by formula (1) with a lanthanoid and a lithium-containing ate complex; and thereafter, reacting the lanthanoid complex with a silyl compound represented by formula (2). (1) (In the formula, R1a and R1b are identical or different, and each represent a hydrogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a halogen atom, an aromatic hydrocarbon group, a heterocyclic group; R1a and R1b are bonded to each other and may form a ring; R2 represents an aromatic hydrocarbon group or a heterocyclic group; and X represents a bromine atom or an iodine atom.) (2): R3aR3bSiCl2 (In the formula, R3a and R3b are identical or different and each represent a phenyl group or an alkyl group that has 1-4 carbon atoms and may have a branch.)

Description

[Technical field]

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

[0002] GNRs are expected to be applied to semiconductors, solar cells, transparent electrodes, high-speed transistors, organic electroluminescence devices, etc. There are two known methods for producing GNRs, roughly classified as top-down and bottom-up methods, and the latter is particularly attractive in that it allows the synthesis of large quantities of GNRs with precise control of edge structure and width.

[0003] The present inventors focused on the production of GNRs by the bottom-up method, and as a result of extensive investigation into the production method, they discovered a production method for GNRs that uses naphthylsiloles as a raw material, with a small number of steps and suppressed side reactions (Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2020 / 184625 Summary of the Invention [Problem to be solved by the invention]

[0005] In the above Patent Document 1, naphthylsiloles, which are raw materials for GNR, are represented by the following general formula (9):

[0006] [ka]

[0007] (In the formula, R represents a substituent.) The compound represented by the following general formula (10) is reacted with n-butyl lithium (n-BuLi) and then with dimethylsilyl chloride.

[0008] [ka]

[0009] (In the formula, R is the same as above.) and cyclizing the silyl compound with di-tert-butyl peroxide ((t-BuO)2) (Patent Document 1, Synthesis Example 2). However, this production method requires the use of dimethylsilyl chloride, which has a very low flash point and boiling point, and the use of di-tert-butyl peroxide, which is a self-reactive organic peroxide, and thus raises concerns about disaster prevention when implemented industrially.

[0010] The object of the present invention is to provide a method for safely producing naphthylsiloles, which are used as raw materials for GNR. [Means for solving the problem]

[0011] As a result of intensive research aimed at solving the above problems, the present inventors have found that the following method makes it possible to more safely produce naphthylsiloles from relatively less dangerous compounds.

[0012] Term 1. General formula (3)

[0013] [ka]

[0014] (In the formula, R 1a and R 1b R may be the same or different and represents 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.1a and R 1b may be bonded to each other to form a ring. 2' R represents an aromatic hydrocarbon ring or a heterocycle. 3a and R 3b are the same or different and each represents an alkyl group having 1 to 4 carbon atoms or a phenyl group which may be branched.) A method for producing a compound represented by the following formula: General formula (1)

[0015] [ka]

[0016] (In the formula, R 1a and R 1b is the same as above. 2 represents an aromatic hydrocarbon group or a heterocyclic group. X represents a bromine atom or an iodine atom. with a lanthanide and a lithium-containing ate complex to produce a lanthanide complex of the compound represented by formula (1); And the lanthanide complex and general formula (2) R 3a R 3b SiCl2(2) (In the formula, R 3a and R 3b is the same as above.) With a silyl compound represented by the formula: The manufacturing method comprises, in this order:

[0017] Section 2. General formula (1)

[0018] [ka]

[0019] (In the formula, R 1a and R 1b R may be the same or different and represents 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.1a and R 1b may be bonded to each other to form a ring. 2 represents an aromatic hydrocarbon group or a heterocyclic group. X represents a bromine atom or an iodine atom. A compound represented by the formula:

[0020] Item 3. A method for producing the compound according to item 2, comprising the steps of: General formula (4)

[0021] [ka]

[0022] (In the formula, R 1a , R 1b and X are the same as above. 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 a compound represented by general formula (5) R 2 MgBr (5) (In the formula, R 2 is the same as above.) and a compound represented by the formula:

[0023] Section 4. General formula (4)

[0024] [ka]

[0025] (In the formula, R 1a and R 1b R may be the same or different and represents 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. 1a and R 1b may be bonded to each other to form a ring. 4represents 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. X represents a bromine atom or an iodine atom. A compound represented by the formula:

[0026] Section 5. General formula (3a)

[0027] [ka]

[0028] (In the formula, R 1a and R 1b R may be the same or different and represents 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. 1a and R 1b may be bonded to each other to form a ring. 2a' R represents a heteroaromatic ring. 3a and R 3b are the same or different and each represents an alkyl group having 1 to 4 carbon atoms or a phenyl group which may be branched.) A compound represented by the formula:

[0029] Section 6. General formula (6)

[0030] [ka]

[0031] (In the formula, * indicates a bonding point. n indicates an integer of 0 or more. 1a and R 1b are the same or different and each represents 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 and R 1b may be bonded to each other to form a ring. 2a' indicates a heteroaromatic ring.) Graphene nanoribbons having at least one constitutional unit represented by the formula:

[0032] Item 7. Furthermore, the general formula (7)

[0033] [ka]

[0034] (In the formula, a dotted line indicates no bond or a single bond. * indicates a bond point. R 6a , R 6b , R 6c , R 6d , R 6e and R 6f R may be 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 boronic acid or an ester group thereof, an aromatic hydrocarbon group, or a heterocyclic group. 6c and R 6d may be bonded to each other to form a ring.) Item 7. The graphene nanoribbon according to item 6, having at least one constitutional unit represented by:

[0035] Section 8. General formula (8)

[0036] [ka]

[0037] (In the formula, dotted lines are the same or different and indicate no bond or a single bond. *1 indicates a bonding point. When the dotted line connecting to *2 is a single bond, *2 indicates a bonding point. n indicates an integer of 0 or more. R 1a and R 1b are the same or different and each represents 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 and R 1b may be bonded to each other to form a ring. 2a' R represents a heteroaromatic ring. 6a , R6b , R 6c , R 6d , R 6e and R 6f R may be 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 boronic acid or an ester group thereof, an aromatic hydrocarbon group, or a heterocyclic group. 6c and R 6d may be bonded to each other to form a ring.) Item 6. The graphene nanoribbon according to item 6 or 7, having at least one constitutional unit represented by: Effect of the Invention

[0038] According to the present invention, naphthylsiloles can be produced without using compounds with very low flash points and boiling points or self-reactive organic peroxides. In addition, since naphthylsiloles can be produced in one pot from the compound represented by general formula (1), naphthylsiloles can be produced more simply than by the above-mentioned known production methods.

[0039] In addition, according to the present invention, an innovative method for producing a compound represented by general formula (1) can be provided. Specifically, according to the production method discovered by the present inventors, that is, the production method in which a compound represented by a new general formula (4) is reacted with an arylmagnesium bromide represented by general formula (5), the arylmagnesium bromide represented by general formula (5) selectively reacts with the sulfonyl site of the compound represented by general formula (4), so that when producing a compound represented by general formula (1), it is not necessary to introduce a bromine or iodine atom after the coupling reaction, and therefore compounds represented by general formula (1) having various structures can be produced, and high-purity compounds represented by general formula (1) can be provided at a lower cost. As a result, according to the production method of naphthylsiloles of the present invention, naphthylsiloles having structures that could not be produced by conventionally known methods can be produced, which are useful not only as raw materials for GNR but also as raw material monomers other than GNR (for example, raw material monomers for organic EL elements, organic semiconductors, organic thin-film solar cells, etc.).

[0040] Typical examples of naphthylsiloles having a structure that could not be produced by such conventional methods include naphthylsiloles having a heteroaromatic ring and a structure represented by general formula (3a). In addition, naphthylsiloles having a heteroaromatic ring can be polymerized (APEX polymerization) under the conditions described in Patent Document 1 to produce GNRs having a heteroaromatic ring (specifically, GNRs having a structural unit represented by general formula (6), (7) or (8)). This makes it possible to provide GNRs having properties different from those of conventional GNRs (specifically, GNRs having improved properties such as electron / hole acceptance, redox response and charge transport ability due to precise control of the band gap). In addition, such GNRs having a heteroaromatic ring are particularly useful for light-emitting materials, organic semiconductors, conductive materials, etc. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0041] In this specification, "containing" is a concept that encompasses all of "comprise," "consist essentially of," and "consist only of." In addition, in this specification, when a numerical range is shown as "A to B," it means A or more and B or less.

[0042] (1-1) Method for producing naphthylsiloles according to the present invention The method for producing naphthylsiloles represented by general formula (3) of the present invention is characterized by comprising, in this order, two steps, as shown in the following reaction scheme: a step (step 1) of reacting a compound represented by general formula (4) with an arylmagnesium bromide represented by general formula (5) to obtain a compound represented by general formula (1); and a step (step 2) of reacting the compound represented by general formula (1) with a lanthanoid and a lithium-containing ate complex to generate a lanthanoid complex of the compound represented by general formula (1) in the system, and reacting the lanthanoid complex with a silyl compound represented by general formula (2).

[0043] [ka]

[0044] (In the formula, R 1a and R 1b R may be the same or different and represents 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. 1a and R 1b may be bonded to each other to form a ring. 2 R represents an aromatic hydrocarbon group or a heterocyclic group. 2' R represents an aromatic hydrocarbon ring or a heterocycle. 3a and R 3b R are the same or different and may be branched alkyl groups or phenyl groups having 1 to 4 carbon atoms. X represents a bromine atom or an iodine atom. 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.

[0045] Each of the above compounds and each step will be described in detail below.

[0046] (1-1-1) Compounds represented by general formulas (1) to (5) In general formula (4), R 1a and R 1b The alkyl group represented by the formula (I) is, for example, preferably a straight-chain or branched-chain alkyl group having 1 to 20 carbon atoms (preferably 1 to 15, more preferably 1 to 13), and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, an isohexyl group, a 1,1-dimethylbutyl group, a 2,2-dimethylbutyl group, a 3,3-dimethylbutyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group.

[0047] The alkyl group may be partially substituted, and when substituted, the substituent is not particularly limited, and examples thereof include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, etc. When substituted with a substituent, the number of the substituents is not particularly limited, and may be, for example, 1 to 3.

[0048] In general formula (4), R 1a and R 1b The cycloalkyl group represented by the formula (I) is, for example, preferably a cycloalkyl group having 3 to 20 carbon atoms (preferably 4 to 15, more preferably 5 to 13), and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group.

[0049] The cycloalkyl group may be partially substituted, and when substituted, the substituent is not particularly limited, and examples thereof include halogens such as a fluorine atom, a chlorine atom, and a bromine atom; a hydrocarbon group having 1 to 20 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, etc.). When substituted, the number of the substituents is not particularly limited, and can be, for example, 1 to 3.

[0050] In general formula (4), R 1a and R 1b The (poly)ether group represented by the formula: means an ether group or a polyether group. Examples of the ether group include, for example, -OR 11c (R 11c represents the above-mentioned alkyl group. Preferably, R 11c As the polyether group, for example, -(OR 11a ) k -OR 11b (R 11a and R 11b are the same or different and each represents an alkyl group; and k represents an integer of 1 to 20. 11amay contain not only the same repeating unit but also two or more different repeating units. 11a and R 11b As the alkyl group, a polyether group having an alkyl group having 1 to 4 carbon atoms can be used.

[0051] R 11a and R 11b Each of the alkyl groups is an alkyl group, and examples thereof include those mentioned above, and when the alkyl group has a substituent, the type and number of the substituents are also those mentioned above. Furthermore, k is preferably an integer of 1 to 20, more preferably an integer of 1 to 15, and further preferably an integer of 1 to 5.

[0052] Examples of such polyether groups include -(OC2H5)2OCH3, -(OC2H5)3OCH3, -(OC2H5)4OCH3, and -(OC2H5) 11 OCH3, -(OC2H5) 12 OCH3, -(OC2H5) 13 OCH3, etc.

[0053] In general formula (4), R 1a and R 1b Examples of the ester group represented by the formula: 11d (R 11d represents the above-mentioned alkyl group. Preferably, R 11d As the alkyl group, an ester group having an alkyl group having 1 to 4 carbon atoms can be used.

[0054] R 1a and R 1b Specific examples of the halogen atom represented by the formula (I) include a fluorine, chlorine, bromine and iodine atom.

[0055] In general formula (4), R 1a and R 1b The aromatic hydrocarbon group represented by the formula (I) is a group having an aromatic hydrocarbon ring. At least one hydrogen atom bonded to a carbon atom constituting this aromatic hydrocarbon ring may be substituted with a substituent.

[0056] Examples of the aromatic hydrocarbon ring constituting the aromatic hydrocarbon group include not only a benzene ring, but also a ring in which a plurality of benzene rings are condensed (a benzene condensed ring), a ring in which a benzene ring is condensed with another aromatic hydrocarbon ring, etc. (hereinafter, a ring in which a plurality of benzene rings are condensed and a ring in which a benzene ring is condensed with another ring may be collectively referred to simply as a "condensed hydrocarbon ring"). Examples of the condensed hydrocarbon ring include a pentalene ring, an indene ring, a naphthalene ring, a dihydronaphthalene 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.

[0057] When at least one hydrogen atom of the aromatic hydrocarbon ring constituting the aromatic hydrocarbon group is substituted, the substituent is not particularly limited, and examples thereof include halogens such as a fluorine atom, a chlorine atom, and a bromine atom; a hydrocarbon group having 1 to 20 carbon atoms (e.g., a methyl group, an ethyl group, an n-propyl group, etc.); etc. When substituted with a substituent, the number of the substituents is not particularly limited, and can be, for example, 1 to 3.

[0058] In general formula (4), R 1a and R 1b The heterocyclic group represented by the formula (I) is a group (substituent) having a heterocycle. Note that the heterocycle may be a derivative group in which at least one hydrogen atom bonded to a carbon atom constituting the heterocycle is substituted with a functional group.

[0059] Examples of the heterocyclic ring constituting the heterocyclic group include heterocyclic rings having at least one atom selected from nitrogen atom, oxygen atom, boron atom, phosphorus atom, silicon atom and sulfur atom (specifically, heteroaromatic ring or heteroaliphatic ring, particularly heteroaromatic ring).Specific examples of the heterocyclic ring include heteroaromatic rings such as furan ring, thiophene ring, pyrrole ring, silole ring, borole ring, phosphole ring, oxazole ring, dioxole ring, thiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, etc.Furthermore, these may be heterocondensed rings (thienothiophene ring, quinoline ring, benzodioxole ring, etc.) between these or between these and benzene ring or the above-mentioned condensed hydrocarbon ring.

[0060] In the case where at least one hydrogen atom of the heterocyclic ring constituting the heterocyclic group is substituted, the substituent is not particularly limited, and examples thereof include halogens such as fluorine atom, chlorine atom, and bromine atom; hydrocarbon groups having 1 to 20 carbon atoms (e.g., methyl group, ethyl group, n-propyl group, etc.); but are not limited thereto, and any substituent can be adopted. In the case where the heterocyclic group is substituted with a substituent, the number of the substituents is not particularly limited, and can be, for example, 1 to 3.

[0061] In addition, R in the general formula (4) 1a and R 1b 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 heterocycle.

[0062] R in general formula (4) 1a and R 1b When naphthylsiloles represented by the general formula (3) obtained by the production method of the present invention are used as raw materials for GNR, all of them are hydrogen atoms, one is a hydrogen atom and the other is an alkyl group or a (poly)ether group, or R 1a and R 1b are preferably bonded to each other to form a ring.

[0063] 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 production of the compound represented by the general formula (4).

[0064] In general formula (4), R 4 Examples of the alkyl group having 1 to 4 carbon atoms and which may have a branch include 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. Examples of the halogenated alkyl group having 1 to 4 carbon atoms and which may have a branch include the above-mentioned alkyl groups in which at least one hydrogen atom is substituted with a halogen atom, and specific examples thereof include -CH2F, -CHF2, -CF3, -CH2Cl, -CHCl2, and -CCl3.

[0065] In general formula (4), R 4 The aromatic hydrocarbon group represented by the formula (I) may be any of the above. Specific examples include compounds in which at least one hydrogen atom of an aromatic hydrocarbon ring constituting the aromatic hydrocarbon group is substituted, and examples of the substituent include an alkyl group having 1 to 4 carbon atoms which may have a branch, a nitro group, and the like.

[0066] As described later, the compound represented by the general formula (4) is produced by reacting the hydroxyl group of the corresponding brominated (or iodized) naphthol with a sulfonic acid anhydride or an acid halide thereof, which are widely used as a sulfonyl protecting group. 4 is preferably a substituent derived from sulfonic acid, which is commonly used as a sulfonyl protecting group, specifically, for example, -CF3, -CH3, -C6H4CH3 (tolyl group) and -C6H4NO2 (nitrophenyl group).

[0067] The general formula (4) can be, for example, a corresponding substituent R 1a and R 1bThe naphthols having the formula (I) are brominated (or iodized) by a conventional method to obtain brominated (or iodized) naphthols, and the brominated (or iodized) naphthols are reacted with a sulfonylating agent such as a corresponding sulfonic anhydride or sulfonic acid chloride. Specifically, the compound can be produced by the method described in the Examples section below.

[0068] R in general formula (5) 2 The aromatic hydrocarbon group or heterocyclic group represented by the formula (5) may be the same as above. The types and numbers of the substituents are also the same. From the viewpoint of ease of production of the formula (5), R 2 is preferably an aromatic hydrocarbon group or a heterocyclic group which has no substituent or has a hydrocarbon group having 1 to 12 carbon atoms as a substituent (for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, etc.).

[0069] In general formula (2), R 3a and R 3b Examples of the alkyl group which may have a branch include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.

[0070] In the general formula (2), R 3a and R 3b is preferably a methyl group, an ethyl group, or a phenyl group, and R 3a and R 3b are preferably the same substituents.

[0071] X and R in general formula (1) 1a , R 1b and R 2 The above-mentioned can be used for the compound having a substituent. The same applies to the type and number of the substituent. The same also applies to the preferred embodiment. Therefore, specific examples of the compound having a structure represented by such general formula (1) include the following general formulas (1a1) to (1e1):

[0072] [ka]

[0073] (In the formula, X is the same as above. R 1b1 R represents a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 15, more preferably 1 to 13). 1c1 R represents a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 2 to 15, more preferably 2 to 12). 2a represents a heterocyclic group. From the viewpoint of availability of raw materials, the formulas (1b1), (1c1) and (1e1) which do not have a heterocyclic group are preferred. As the linear or branched alkyl group, the above-mentioned ones can be used. The same applies to the type and number of the substituents.

[0074] R in general formula (3) 1a , R 1b , R 3a and R 3b The above-mentioned can be used for R. For those having a substituent, the type and number of the substituent are the same. The same also applies to preferred embodiments. In the general formula (3), R 2' As the aromatic hydrocarbon ring and the heterocyclic ring represented by the formula (1) and (5), R 2 R 2 The aromatic hydrocarbon ring and the heterocyclic ring described above can be used. The types and numbers of the substituents are the same for those having a substituent. The same also applies to the preferred embodiments. In addition, the substituent R in the general formula (3) can be used. 2' Since it is assumed that step 2 proceeds as follows, the substituent R 2 and the naphthyl group, and the carbon atom to which said bond is connected and the bond connecting the carbon atom adjacent to said carbon atom form a part of a silole ring.

[0075] The estimated reaction scheme and examples of the compounds produced are shown below.

[0076] <R2 Example of nBu2LaCl·4LiCl as ate complex containing monovalent aromatic hydrocarbon group (benzene ring), lanthanide and lithium>

[0077] [ka]

[0078] In the formula, X, R 1a , R 1b , R 3a and R 3b is the same as above. nBu represents an n-butyl group. Formula (1-a') represents a model structure of a lanthanoid complex of the compound represented by general formula (1).

[0079] <R 2 Example of nBu2LaCl·4LiCl as ate complex containing monovalent heterocyclic group (thiophene ring), lanthanide and lithium>

[0080] [ka]

[0081] In the formula, X, R 1a , R 1b , R 3a and R 3b is the same as above. nBu represents an n-butyl group. Formula (1-b') represents a model structure of a lanthanoid complex of the compound represented by general formula (1).

[0082] (1-1-2) Step 1 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, per 1 mol of the compound represented by the general formula (4).

[0083] In step (1), a Pd compound, a ligand, and a halogen salt of lithium may be used in combination. Examples of the Pd compound that can be used in combination include Pd compounds that can be generally used in cross-coupling reactions, and specific examples include tris(dibenzylideneacetone)dipalladium (Pd2(dba)3), palladium acetate (Pd(OAc)2), and tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). These Pd compounds may be used alone or in combination of two or more. The amount of the Pd compound 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).

[0084] As the ligand usable in step (1), for example, a phosphine ligand that can be generally used in a cross-coupling reaction can be used. Specifically, for example, 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). These ligands may 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 %, based on 1 mol of the compound represented by formula (4).

[0085] Specific examples of lithium halogen salts in step (1) include LiBr, LiI, etc. These lithium halogen salts may be used alone or in combination of two or more. The amount of lithium halogen salt used is usually 0.7 to 3 mol, preferably 0.9 to 2 mol, per mol of the compound represented by general formula (4).

[0086] Step (1) may be carried out in the presence of a solvent, if necessary. Examples of the solvent that can be used include ethers. Specific examples of the ethers include diethyl ether, cyclopentyl methyl ether, and tetrahydrofuran. The amount of the solvent used is usually 0.2 to 10 parts by mass, preferably 0.5 to 5 parts by mass, per part by mass of the compound represented by formula (4).

[0087] Step (1) is carried out, for example, by placing the compound represented by general formula (4), and if necessary, a Pd compound, a ligand, a lithium halogen salt, and a solvent in a reaction vessel, cooling the vessel once to −20 to 0° C., adding the compound represented by general formula (5) at the same temperature, and then heating the vessel to 10 to 40° C. and continuing the reaction at the same temperature until the reaction is completed.

[0088] 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, and the liquids are separated and the aqueous layer is removed to remove inorganic salts and the like, and the organic layer containing the compound is then concentrated to obtain the compound represented by general formula (1). The obtained compound represented by general formula (1) may be purified, if necessary, by distillation, crystallization, column chromatography using silica gel, or the like.

[0089] (1-1-3) Step 2 The lanthanoid- and lithium-containing ate complex used in step (2) is a complex containing lanthanoid and lithium. Lanthanoids are atoms with atomic numbers of 57 to 71, and specific examples thereof include lanthanum, cerium, and neodymium.

[0090] Specific examples of lanthanoid and lithium-containing ate complexes include those represented by the following general formula (11): R 20a p MX 20a q · 4LiX 20b (11) (In the formula, R 20arepresents an optionally branched alkyl group having 1 to 4 carbon atoms, M represents a lanthanoid atom, and X 20a and X 20b are the same or different and each represents a halogen atom, and p and q are the same or different and each represents an integer of 0 to 3, provided that p+q=3. Examples of the complex include those represented by the following formula:

[0091] In the general formula (11), R 20a Specific examples of the alkyl having 1 to 4 carbon atoms and which may have a branch, represented by the formula: methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, and tert-butyl group. Examples of the lanthanoid atom represented by M include atoms having atomic numbers of 57 to 71, specifically, lanthanum atom, cerium atom, neodymium atom, and the like. In addition, X 20a and X 20b Specific examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0092] Specific examples of lanthanide- and lithium-containing ate complexes having the above-mentioned characteristics include nBu2LaCl·4LiCl, nBu2CeCl·4LiCl, and nBu2NdMe·4LiCl.

[0093] The lanthanoid- and lithium-containing ate complex used in step (2) can be prepared, for example, by the method described in the Examples section below.

[0094] The lanthanoid- and lithium-containing ate complexes may be used alone or in combination of two or more. The amount of the double salt used is usually 0.8 to 3 mol, preferably 0.9 to 2 mol, per mol of the compound represented by formula (1).

[0095] Step (2) may be carried out in the presence of a solvent, if necessary. Examples of solvents that can be used include ethers. Specific examples of ethers include diethyl ether, cyclopentyl methyl ether, and tetrahydrofuran. One type of solvent may be used, or two or more types may be used in combination. The amount of the solvent used is usually 0.5 to 20 times by weight, preferably 1 to 10 times by weight, per 1 time by weight of the compound represented by formula (1).

[0096] Step (2) is carried out, for example, by placing the compound represented by general formula (1) and a solvent in a reaction vessel, lowering the temperature to -20°C or lower, preferably -75 to -30°C, then adding a lanthanoid and a lithium-containing ate complex at the same temperature and stirring for a certain period of time to generate a lanthanoid complex of general formula (1), and then raising the temperature to -10°C to 10°C, and then adding a silyl compound represented by general formula (2) to the reaction vessel at the same temperature to react the lanthanoid complex of general formula (1) with the silyl compound represented by general formula (2). From the viewpoint of improving the reaction rate, the reaction solution may be heated to 10 to 40°C as necessary after adding the silyl compound represented by general formula (2).

[0097] After the reaction is completed, for example, an organic solvent and water are added to the reaction solution, and the aqueous layer is removed to remove inorganic salts and the like, and then the organic layer containing the compound is concentrated to obtain the compound represented by general formula (1). The obtained compound represented by general formula (1) may be purified, if necessary, by distillation, crystallization, column chromatography using silica gel, or the like.

[0098] (1-2) Naphthylsiloles with heteroaromatic rings According to the above-mentioned method for producing naphthylsiloles of the present invention, a naphthylsilole represented by the general formula (3a) can be obtained.

[0099] [ka]

[0100] (In the formula, R 1a , R 1b , R2a' , R 3a and R 3b is the same as above.) It is possible to produce naphthylsiloles having a heteroaromatic ring, which have a structure represented by the following general formula (3a): 1a , R 1b , R 3a and R 3b The above-mentioned can be used for R. 2a' The heteroaromatic ring represented by the formula (I) and its structure are as described above. The type and number of the substituents in the heteroaromatic ring represented by the formula (I) and its structure are as described above. 2a' Preferred examples of the heteroaromatic ring represented by the formula (I) include a furan ring, a thiophene ring, a pyrrole ring, and a pyridine ring.

[0101] Specific examples of naphthylsiloles having a heteroaromatic ring having a structure represented by the general formula (3a) include those represented by the following general formulae (3a1), (3a2), and (3a3):

[0102] [ka]

[0103] (In the formula, R 30a R represents a hydrogen atom or an alkyl group. 30c and R 30d R may be the same or different and represent a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group. 30c and R 30d If are adjacent, R 30c and R 30d may be bonded to each other to form a ring. 30b is an oxygen atom, a sulfur atom or NR 30e (In the formula, R 30e represents an alkyl group, an aromatic hydrocarbon group, an acetyl group, a tert-butoxycarbonyl group, a methylsulfonyl group, or a tosyl group. Or the following general formulae (3a4), (3a5), (3a6) and (3a7):

[0104] [ka]

[0105] (In the formula, R 30a R represents a hydrogen atom or an alkyl group. 30f , R 30g and R 30h R may be the same or different and represent a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group. 30f , R 30g and R 30h If are adjacent, R 30e , R 30f and R 30g may be bonded to each other to form a ring.) More specifically, naphthylsiloles represented by the following formula are included.

[0106] [ka]

[0107] (In the formula, n-octyl represents an n-octyl group, and Et represents an ethyl group.) Examples include:

[0108] In the above, R 30a , R 30c , R 30d , R 30e , R 30f , R 30g and R 30h an alkyl group represented by the formula: 30c , R 30d , R 30e , R 30f , R 30g and R 30h an aromatic hydrocarbon group represented by R 30c and R 30d When these are bonded to each other, R 30e , R 30f and R 30g When the rings are bonded to each other, the rings may be those mentioned above. When the rings have a substituent, the type and number of the substituent are the same. The same also applies to preferred embodiments.

[0109] (1-3) GNRs with heteroaromatic rings The GNRs of the present invention are represented by the general formula (6)

[0110] [ka]

[0111] (In the formula, * indicates a bonding point. n indicates an integer of 0 or more. 1a , R 1b and R 2a' is the same as above. R bonded to the same benzene ring 1a and R 1b may be bonded to each other to form a ring.) In general formula (6), R 1a , R 1b and R 2a' The above-mentioned can be used for R. For those having a substituent, the type and number of the substituent are the same. The same also applies to the preferred embodiments. However, R 1a and R 1b When they are bonded to each other to form a ring, R bonded to the same benzene ring 1a and R 1b are bonded to each other to form a ring.

[0112] The GNR of the present invention is produced, for example, by the method of Patent Document 1 mentioned above. Therefore, at least one end of the GNR is represented by the general formula (7)

[0113] [ka]

[0114] (In the formula, a dotted line indicates no bond or a single bond. * indicates a bond point. R 6a , R 6b , R 6c , R 6d , R 6e and R 6fR may be 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 boronic acid or an ester group thereof, a monovalent aromatic hydrocarbon group, or a monovalent heterocyclic group. 6c and R 6d may be bonded to each other to form a ring.) It may also be a structural unit represented by the following formula:

[0115] R in general formula (7) 6a , R 6b , R 6c , R 6d , R 6e and R 6f The halogen atom represented by the formula (I) includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0116] R in general formula (7) 6a , R 6b , R 6c , R 6d , R 6e and R 6f The alkyl group represented by the formula (I) can be any of those mentioned above. For those having a substituent, the type and number of the substituent are the same. The same also applies to preferred embodiments.

[0117] R in general formula (7) 6a , R 6b , R 6c , R 6d , R 6e and R 6f The cycloalkyl group represented by the formula (I) can be any of those mentioned above. For those having a substituent, the type and number of the substituent are the same. The same also applies to preferred embodiments.

[0118] R in general formula (7) 6a , R 6b , R 6c , R 6d , R 6e and R 6fThe (poly)ether group represented by means an ether group or a polyether group. As the (poly)ether group, those mentioned above can be used. For those having a substituent, the type and number of the substituent are the same. The same also applies to preferred embodiments.

[0119] R in general formula (7) 6a , R 6b , R 6c , R 6d , R 6e and R 6f The above-mentioned ester groups can be used as the ester group represented by the formula: embedded image For those having a substituent, the type and number of the substituent are the same. The same also applies to preferred embodiments.

[0120] R in 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, a pinacolatoboryl group, and the like.

[0121] R in general formula (7) 6a , R 6b , R 6c , R 6d , R 6e and R 6f The aromatic hydrocarbon group or heterocyclic group represented by the formula (I) may be any of those mentioned above. The types and numbers of the substituents are also the same.

[0122] R in general formula (7) 6a , R 6b , R 6c , R 6d , R 6e and R 6fFrom the viewpoints of availability of raw materials, water solubility, etc., preferred are a hydrogen atom, an alkyl group, a (poly)ether group, etc. In the case of an alkyl group, a branched chain alkyl group is more preferred, and an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, an isohexyl group, a 1,1-dimethylbutyl group, a 2,2-dimethylbutyl group, a 3,3-dimethylbutyl group, etc. are further preferred, and a tert-butyl group is particularly preferred.

[0123] R in general formula (7) 6c and R 6d can also be bonded to each other to form a ring. Examples of the ring formed in this case include the above-mentioned aromatic hydrocarbon ring and heterocycle.

[0124] As described above, the GNR of the present invention has at least one constitutional unit represented by general formula (6) and at least one constitutional unit represented by general formula (7), and therefore has general formula (8)

[0125] [ka]

[0126] (In the formula, dotted lines are the same or different and indicate no bond or a single bond. *1 indicates a bonding point. When the dotted line connecting to *2 is a single bond, *2 indicates a bonding point. n indicates an integer of 0 or more. R 1a , R 1b , R 2a' , R 6a , R 6b , R 6c , R 6d , R 6e and R 6f is the same as above. R bonded to the same benzene ring 1a and R 1b may be bonded to each other to form a ring. 6c and R 6d may be bonded to each other to form a ring.) It is preferable that the GNR has a structural unit represented by the following formula (8): 1a , R 1b, R 2a' , R 6a , R 6b , R 6c , R 6d , R 6e and R 6f The above-mentioned can be used for the substituents. The same applies to the type and number of the substituents for those having a substituent. The same also applies to preferred embodiments.

[0127] Specific examples of the structural unit represented by general formula (8) include those represented by the following general formulae (8a1), (8a2), ​​(8a3), (8a4), (8a5), (8a6), (8a7), (8a8), (8a9), (8a10), (8a11), (8a12), (8a13), and (8a14):

[0128] [ka]

[0129] [ka]

[0130] [ka]

[0131] (In the formula, * indicates a bonding point. n indicates an integer of 0 or more. 30a , R 30c , R 30d、 X 30b , R 30f , R 30g and R 30h is the same as above.) More specifically, the structural units represented by the following formulas are included.

[0132] [ka]

[0133] (In the formula, * represents a bonding point, n represents an integer of 0 or more, n-octyl represents an n-octyl group, and Et represents an ethyl group.) Examples include:

[0134] In addition, GNRs having the above-mentioned structural units can be subjected to a ring condensation reaction to obtain GNRs having the following structural units. The ring condensation reaction can be performed by the same method as that described in Patent Document 1 (specifically, for example, the Scholl reaction (dehydrogenation cyclization reaction)).

[0135] Specific examples of GNRs subjected to a ring condensation reaction include those represented by the following general formulae (9a1), (9a2), (9a3), (9a4), (9a5), (9a6), and (9a7):

[0136] [ka]

[0137] [ka]

[0138] (In the formula, * indicates a bonding point. n indicates an integer of 0 or more. 30a , R 30c , R 30d、 X 30b , R 30f , R 30g and R 30h is the same as above. In addition, in general formulas (9a5) and (9a6), R 30h and R 30f is a hydrogen atom, a single bond is formed. More specifically, the structural units represented by the following formulas are included.

[0139] [ka]

[0140] In the formula, * indicates a bonding point, n indicates an integer of 0 or more, n-octyl indicates an n-octyl group, and Et indicates an ethyl group.

[0141] In the GNR of the present invention, n in the general formulas (6) and (8) is not particularly limited and is an integer of 0 or more, but can be appropriately selected depending on the required properties, and is preferably 10 to 1000, more preferably 10 to 500. In addition, for example, it is possible to make an oligomer in which n in the general formulas (6) and (8) is 1 to 99, preferably 2 to 49, more preferably 2 to 19, and even more preferably 3 to 9. n of the GNR of the present invention is calculated from the number average molecular weight measured in terms of polystyrene by gel permeation chromatography.

[0142] In the GNR of the present invention, the number average molecular weight is not particularly limited and can be appropriately selected depending on the required characteristics. From the viewpoint of solubility, for example, it is preferably 10,000 or more, more preferably 15,000 to 300,000, even more preferably 20,000 to 200,000, and particularly preferably 30,000 to 150,000. In addition, for example, when it is made into an oligomer, the number average molecular weight of the GNR of the present invention can be, for example, 500 to 5,000. The number average molecular weight of the GNR of the present invention is measured by gel permeation chromatography in terms of polystyrene.

[0143] The length of the GNR of the present invention is preferably 10 nm or more, more preferably 20 to 500 nm, even more preferably 50 to 400 nm, and particularly preferably 100 to 300 nm. 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 required properties. Long GNRs are expected to be applied to semiconductors, solar cells, etc., and short GNRs are expected to be applied to organic EL devices, etc. EXAMPLES

[0144] The present invention will be specifically described below by way of examples, but the present invention is not limited to these in any way.

[0145] (1)NMR measurement 1 H-NMR and 13 C-NMR was performed using tetramethylsilane as an internal standard and deuterated chloroform (CDCl3) as a solvent on a JEOL-ESC600 ( 1 H 600MHz, 13 C 150MHz) or JEOL-ESC400( 1 H 400MHz, 13 C 100MHz, 19 The data was recorded using a F 376 MHz spectrometer. Each data item is described as follows.

[0146] Chemical shifts, multiplicity (s=singlet, d=doublet, dd=doublet of doublets, ddd=doublet of doublet of doublets, t=triplet, td=triplet of doublets, q=quartet, m=multiplet), coupling constant (Hz), and integration.

[0147] (2)Fast atom collision mass spectrometry (FAB-MS) FAB-MS used 3-nitrobenzyl alcohol as a matrix, and high-resolution mass spectra (HRMS) were obtained using a double-focusing mass spectrometer (JEOL JMS-700).

[0148] (3) Molecular weight (Mn) and Mw / Mn (PDI) measurements of GNRs using size exclusion chromatography (SEC) The analysis was performed using the following equipment under the following conditions. Equipment: Shimadzu Prominence 2000 Column: TOSOH TSKgel Multipore H manufactured by Tosoh Corporation XL -M SEC column 7.8mm x 300mm x 2 (connected in series) Measurement temperature: 40℃ Eluent: Tetrahydrofuran containing 0.1% by mass of tetra-n-butylammonium bromide Standard molecular weight: Based on standard polystyrene (TOSOH TSKgel polystyrene standard).

[0149] (4) Regarding analytical / purification materials used in the following examples Analytical thin layer chromatography (TLC): E. Merck silica gel 60 F254 precoated plates (0.25 mm) Silica gel for column chromatography: KANTO silica gel 60N (spherical, neutral, 40-100 μm) Metal scavenger: Biotage Metal Scavenger Si-TMT.

[0150] (5) Preparative size exclusion chromatography (SEC) and preparative conditions: Equipment: JAI LC-9210II NEXT manufactured by Japan Analytical Industry Co., Ltd. Column: JAIGEL-3H / JAIGEL-5H manufactured by Japan Analytical Industry Co., Ltd. Solvent: Chloroform Flow rate: 3.5mL / min.

[0151] <Production Example 1> Example of the production of 3-chloro-3-ethylundecane

[0152] [ka]

[0153] In the formula, Et represents an ethyl group, n-octyl represents an n-octyl group, and THF represents tetrahydrofuran.

[0154] Magnesium turnings (5.8 g, 240 mmol) were placed in a 200 mL two-necked round-bottom flask containing a magnetic stirrer, and stirring was started. The flask was heated with a heat gun under reduced pressure for 10 minutes, and then purged with nitrogen. After nitrogen replacement, the flask was cooled to room temperature, and n-octylbutamide (37.1 mL, 225 mmol) and THF (100 mL) were added to the flask at the same temperature, and 1,2-dibromoethane (2 drops, for activating the magnesium turnings) 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 containing a magnetic stirrer. To this mixture of 3-pentanone and THF, the Grignard reagent solution prepared as above was added dropwise with vigorous stirring at 0° C., and the temperature was then raised to 40° C. and the mixture was stirred at the same temperature for 14 hours.

[0155] After checking the progress of the reaction by TLC, the reaction mixture was quenched with water. The organic layer was washed with saturated NH4Cl aqueous solution and water, dried over Na2SO4, filtered off Na2SO4, and the solvent was removed under reduced pressure to obtain a crude product of 3-ethyl-3-hydroxylundecane (compound S2).

[0156] Next, concentrated hydrochloric acid (35 mL) was added to a 200 mL two-necked round-bottom flask containing the crude product of compound S2 obtained by the above operation and a magnetic stirrer, and the mixture was stirred at room temperature for 1 hour. The organic matter was extracted from the mixture three times using diethyl ether (100 mL). The extracted organic layers were combined, washed with brine, and then dried over Na2SO4. The Na2SO4 was then 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-ethylundecane (compound S3; 17.0 g, 76% yield).

[0157] <Production Example 2> Preparation of Substituted Naphthols

[0158] [ka]

[0159] In the formula, Et represents an ethyl group, and n-octyl represents an n-octyl group.

[0160] In a 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 CHCl (120 mL) were placed in a 200 mL two-necked round-bottom flask equipped with a magnetic stirrer, and stirring was started. Then, AlCl (11.0 g, 83.2 mmol) was added at room temperature. The mixture was then heated to 40°C and stirred at the same temperature overnight, after which the reaction was quenched by adding methanol (30 mL).

[0161] The organic layer was then washed with water, dried over Na2SO4, filtered off, and the solvent was removed under reduced pressure to obtain a crude product, which was purified by open column chromatography on silica gel (eluent: CH2Cl2 / hexane=4:1) to obtain 6-(3-ethyl-undecyl)-2-naphthol (compound S5) as a colorless oil (13.0 g, yield 48%).

[0162] <Example 1> Preparation of the compound represented by formula (4)

[0163] [ka]

[0164] In the formula, NBS represents N-bromosuccinimide, DMF represents N,N-dimethylformamide, Et represents an ethyl group, and n-octyl represents an n-octyl group.

[0165] Under nitrogen atmosphere, S5 (17.00 g, 52.1 mmol) and DMF (112 ml) were placed in a 1 L two-necked round bottom flask equipped with a magnetic stirrer, and after stirring was started, NBS (10.19 g, 57.3 mmol) dissolved in DMF (200 ml) was slowly added dropwise at room temperature for 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 layers were washed with brine and then dried over Na2SO4, after which the Na2SO4 was filtered and the solvent was removed under reduced pressure to obtain the 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) as a colorless oil (17.16 g, 81% yield).

[0166] Compound S6 (17.16 g, 42.3 mmol) and CH2Cl2 (84 ml) were placed in a 100 ml two-necked round-bottom flask containing a magnetic stirrer under a nitrogen atmosphere, and stirring was started. After that, the mixture was cooled to 0°C, pyridine (4.11 ml, 50.8 mmol) was added at the same temperature, and the mixture was stirred at the same temperature for 10 minutes. Then, trifluoromethanesulfonic anhydride (7.83 ml, 46.6 mmol) was added, and the mixture was stirred at 0°C for 2 hours, after which the reaction was quenched by adding water. The organic matter was extracted from the resulting reaction mixture three times with ethyl acetate (30 ml), and the combined organic layer was washed with brine, then dried over Na2SO4, 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) to give 1-bromo-6-(3-ethyl-3-undecyl)-2-naphthyl trifluoromethanesulfonate (compound 4-1) as a yellow oil (16.9 g, yield 74%). The analytical values ​​of the compound (4-1) obtained are as follows: 1H NMR(400 MHz,CDCl3):δ8.23 (d, J = 8.7 Hz, 1H), 7.85 (d, J = 8.7 Hz, 1H), 7.68-7.73 (m (dd, d), 2H), 7.40 (d, J = 8.7 Hz, 1H), 1.78 (q, J = 7.3 Hz, 4H), 1.68-1.75 (m, 2H), 1.17-1.31 (m, 10H), 0.85 (t, J = 6.9 Hz, 3H), 0.67 (t, J = 7.3 Hz, 6H); 19 F NMR (382MHz, CDCl3): δ-73.2.

[0167] <Example 2> Preparation Example (1) of Compound Represented by General Formula (1)

[0168] [ka]

[0169] In the formula, Ph represents a phenyl group, dba represents dibenzylideneacetone, dppp represents 1,3-bis(diphenylphosphino)propane, Et represents an ethyl group, and n-octyl represents an n-octyl group.

[0170] In a 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 placed in a 100 ml two-necked round bottom flask containing a magnetic stirrer, and stirring was started. After cooling to 0°C, phenylmagnesium bromide (3.0 M in Et2O, 7.01 ml) was added dropwise while stirring at the same temperature. The mixture was warmed to room temperature and further stirred at the same temperature for 20 hours, after which it 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, after which the Na2SO4 was filtered and the solvent was removed under reduced pressure to obtain the 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) as a pale yellow oil (5.14 g, 79% yield). The analytical values ​​of the obtained compound (1-1) are as follows. 1 HNMR(400 MHz, 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). 13CNMR(100 MHz, 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). HRMS(FAB+)m / z calcd for C 29 H 37 Br[M+H] + ;464.2079,found 464.2073.

[0171] <Example 3> Preparation Example (2) of Compound Represented by General Formula (1)

[0172] [ka]

[0173] In the formula, dba represents dibenzylideneacetone, dppp represents 1,3-bis(diphenylphosphino)propane, Et represents an ethyl group, and n-octyl represents an n-octyl group.

[0174] Magnesium turnings (90.4 mg, 3.72 mmol) were placed in a Schlenk flask containing a magnetic stirrer, stirring was started, and the Schlenk flask was heated with a heat gun under reduced pressure and then purged with nitrogen. After nitrogen purge, the flask was cooled to room temperature, and diethyl ether (1 ml) was placed in the Schlenk flask at the same temperature. 2-Bromo-5-methylthiophene (0.139 ml, 2.79 mmol) was further added dropwise at room temperature, and the mixture was stirred at the same temperature for 1 hour to prepare a Grignard reagent of 2-bromo-5-methylthiophene.

[0175] In another capped test tube, (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 placed, and stirring was started. The mixture was cooled to 0°C, and the separately prepared Grignard reagent of 2-bromo-5-methylthiophene was added dropwise at 0°C using a syringe. After the addition, the mixture was warmed to room temperature and stirred at the same temperature for 15 hours.

[0176] After the reaction was completed, the reaction mixture was quenched with 1M hydrochloric acid, and the oil layer and the aqueous layer were separated by liquid separation. Ethyl acetate was added to the separated aqueous layer, and organic matter was extracted from the aqueous layer. The separated oil layer and the organic layer obtained by extracting organic matter from the aqueous layer were then combined and dried over Na2SO4. The Na2SO4 was 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: hexane) to quantitatively obtain 2-(1-bromo-6-(3-ethylundecane-3-yl)naphthalen-2-yl)-5-methylthiophene (compound 1-2) (0.982 g).

[0177] <Example 4> Preparation Example (1) of Compound Represented by General Formula (3)

[0178] [ka]

[0179] In the formula, nBu represents an n-butyl group, THF represents tetrahydrofuran, Me represents a methyl group, Et represents an ethyl group, and n-octyl represents an n-octyl group.

[0180] Under nitrogen atmosphere, 0.6M hexane solution of LaCl3·2LiCl (11.92mL, 7.15mmol) and THF (6mL) were placed in a Schlenk flask containing a magnetic stirrer, and stirring was started and cooled to -50℃. After cooling, 1.6M hexane solution of n-BuLi (9.0mL, 14.3mmol) was added dropwise at -50℃, and the mixture was stirred at the same temperature for 30 minutes to prepare lanthanide and lithium-containing ate complexes. Next, (1-1) (3.03g, 6.5mmol) was added at -50℃, and stirring was continued at the same temperature for 5 minutes after the addition.

[0181] Thereafter, 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. The temperature was then raised further to room temperature, and stirring was continued at the same temperature for 1 hour.

[0182] After the reaction was completed, water was added, and the oil layer and the aqueous layer were separated by separation. Ethyl acetate was added to the separated aqueous layer, and the organic matter was extracted from the aqueous layer. This extraction operation was performed a total of three times. The separated oil layer and the organic layer obtained by extracting the organic matter from the aqueous layer were then combined and dried with Na2SO4, after which the Na2SO4 was filtered and the solvent was removed under reduced pressure to obtain a crude product. The crude product was 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%).

[0183] <Example 5> Preparation Example (2) of Compound Represented by General Formula (3)

[0184] [ka]

[0185] In the formula, nBu represents an n-butyl group, THF represents tetrahydrofuran, Me represents a methyl group, Et represents an ethyl group, and n-octyl represents an n-octyl group.

[0186] Under nitrogen atmosphere, 0.6M hexane solution of LaCl3·2LiCl (1.51mL, 0.906mmol) and THF (0.8mL) were placed in a Schlenk flask containing a magnetic stirrer, and stirring was started and cooled to -50℃. After cooling, 1.6M hexane solution of n-BuLi (1.13mL, 1.81mmol) was added dropwise at -50℃, and the mixture was stirred at the same temperature for 30 minutes to prepare lanthanide and lithium-containing ate complexes. Next, (1-2) (0.40g, 0.824mmol) was added at -50℃, and stirring was continued at the same temperature for 5 minutes after the addition.

[0187] Thereafter, the temperature was raised to 0° C. over 30 minutes while stirring, and after the temperature was raised, dichlorodimethylsilane (0.120 mL, 1.24 mmol) was added at the same temperature, after which the temperature was further raised to room temperature and stirring was continued at the same temperature for 1 hour.

[0188] After the reaction was completed, water was added, and the oil layer and the water layer were separated by separation. Ethyl acetate was added to the separated water layer, and the organic matter was extracted from the water layer. This extraction operation was performed a total of three times. Then, the separated oil layer and the organic layer obtained by extracting the organic matter from the water layer were combined and dried with 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 using 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]silole[3,2-b]thiophene (compound 3-2) (69.3 mg, yield 18%). The analytical values ​​of the obtained compound (3-2) are as follows. 1 H NMR (600 MHz, CDCl3): δ 7.671 (d, J = 8.4 Hz, 1H), δ 7.646 (s, 1H), δ 7.565 (d, J = 9.0 Hz, 1H), δ 7.4703 (dd, J = 4.5 Hz, J = 1.8 Hz 1H), δ 6.829 (s, 1H), δ 2.554 (s, 3H) δ 0.545 (s, 6H) HRMS(FAB+) m / z=462.

[0189] <Example 6> Preparation Example (3) of Compound Represented by General Formula (3)

[0190] [ka]

[0191] In the formula, nBu represents an n-butyl group, THF represents tetrahydrofuran, and Me represents a methyl group.

[0192] Under a nitrogen atmosphere, a 0.6 M hexane solution of LaCl3·2LiCl (48 mL, 28.8 mmol) and THF (30 mL) were placed in a Schlenk flask containing a magnetic stirrer, and stirring was started and cooled to -50°C. After cooling, a 1.6 M hexane solution of n-BuLi (36 mL, 57.6 mmol) was added dropwise at -50°C, and the mixture was stirred at the same temperature for 30 minutes to prepare lanthanide and lithium-containing ate complexes. 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.

[0193] Thereafter, 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. The temperature was then raised further to room temperature, and stirring was continued at the same temperature for 1 hour.

[0194] After the reaction was completed, water was added, and the oil layer and the water layer were separated by separation. Toluene was added to the separated water layer, and the organic matter was extracted from the water layer. This extraction operation was performed a total of three times. The separated oil layer and the organic layer obtained by extracting the organic matter from the water layer were then combined and dried with Na2SO4. The Na2SO4 was then filtered, and the solvent was removed under reduced pressure to obtain a crude product. The crude product was 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%).

[0195] <Example 7> Example of the preparation of GNRs with heteroaromatic rings

[0196] [ka]

[0197] In the formula, Et represents an ethyl group, and n-octyl represents an n-octyl group.

[0198] In a 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-chloranil (31.2 mg, 127 μmol) were placed in a 5 mL Schlenk flask containing 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 the wall of the Schlenk flask was washed with 1,2-dichloroethane (0.57 mL). The mixture was then heated to 80°C and stirred at the same temperature for 21.5 hours to obtain a reaction mixture.

[0199] The reaction mixture was cooled to room temperature and passed through a short pad column of silica gel and a metal scavenger while washing with CH2Cl2, and then the solvent was removed from the reaction mixture under reduced pressure to obtain GNR1.

[0200] The resulting GNR1 was analyzed by size exclusion chromatography (SEC) and found to have an Mn of 2.9×10 4 and Mw / Mn(PDI)=1.14.

[0201] <Example 8> Preparation Example (3) of Compound Represented by General Formula (1)

[0202] [ka]

[0203] In the formula, dba represents dibenzylideneacetone, dppp represents 1,3-bis(diphenylphosphino)propane, Et represents an ethyl group, and n-Bu represents an n-butyl group.

[0204] 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 placed in a 100 mL two-necked round bottom flask equipped with a magnetic stir bar, and stirring was started. After cooling to 0°C, 4-butylphenylmagnesium bromide (3.0 M in Et2O, 7.01 mL) was added dropwise with stirring at the same temperature. The mixture was warmed to room temperature and further stirred at the same temperature for 20 hours, after which it 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, the Na2SO4 was filtered, and the solvent was removed under reduced pressure to obtain the 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) as a pale yellow oil (4.08 g, yield 86%). The analytical values ​​of the obtained compound (1-4) are as follows.

[0205] 1 HNMR (400 MHz, CDCl3): δ8.41 (d, J = 8.7Hz, 1H), 7.86 (d, J = 8.7Hz, 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 = 7.8 Hz, 2H), 1.69 (quin, J = 7.8Hz, 2H), 1.46 (sext, J = 7.8Hz, 2H), 0.96 (t, J = 7.8Hz, 3H). 13CNMR(100MHz, CDCl3): δ142.2, 140.7, 139.5, 133.5, 132.5, 129.5(2C), 128.7, 128.04, 127.98(2C), 127.92, 127.6, 127.4, 126.4, 122.5, 35.5, 33.5, 22.5, 14.0.

[0206] <Example 9> Preparation Example (4) of Compound Represented by General Formula (3)

[0207] [ka]

[0208] In the formula, nBu represents an n-butyl group, THF represents tetrahydrofuran, and Me represents a methyl group.

[0209] Under nitrogen atmosphere, 0.6M hexane solution of LaCl3·2LiCl (27.0 mL, 16.2 mmol) and THF (30 mL) were placed in a Schlenk flask containing a magnetic stirrer, and stirring was started and cooled to -50℃. After cooling, 1.6M hexane solution of n-BuLi (20.3 mL, 32.4 mmol) was added dropwise at -50℃, and the mixture was stirred at the same temperature for 30 minutes to prepare lanthanide and lithium-containing ate complexes. Next, (1-4) (5.0 g, 14.7 mmol) was added at -50℃, and stirring was continued at the same temperature for 5 minutes after the addition.

[0210] Thereafter, 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. The temperature was then raised further to room temperature, and stirring was continued at the same temperature for 1 hour.

[0211] After the reaction was completed, water was added, and the oil layer and the water layer were separated by separation. Toluene was added to the separated water layer, and the organic matter was extracted from the water layer. This extraction operation was performed a total of three times. The separated oil layer and the organic layer obtained by extracting the organic matter from the water layer were then combined and dried with Na2SO4, after which the Na2SO4 was filtered and the solvent was removed under reduced pressure to obtain a crude product. The crude product was 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. 1 H-NMR (400 MHz, CDCl3) δ 7.95 (d, J = 8.7 Hz, 1H), 7.91 (d, J = 8.7 Hz, 1H), 7.87-7.82 (m, 2H), 7.80 (d, J = 7.8 Hz, 1H), 7.53-7.47 (m, 2H), 7.46-7.40 m, 1H), 7.28 (dd, J = 1.8, 7.8 Hz, 1H), 2.68 (t, J = 7.3 Hz, 2H), 1.71-1.62 (m, 2H), 1.42 (sext, J = 7.3 Hz, 2H), 0.97 (t, J = 7.3 Hz, 3H), 0.58 (s, 6H). 13 C-NMR (100 MHz, CDCl3) δ 146.9, 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. General formula (3) 【Chemistry 1】 (In the formula, R 1a and R 1b R may be the same or different and represents 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. 1a and R 1b may be bonded to each other to form a ring. 2' R represents an aromatic hydrocarbon ring or a heterocycle. 3a and R 3b are the same or different, and each represents an alkyl group having 1 to 4 carbon atoms or a phenyl group which may be branched.) A method for producing a compound represented by the following formula: General formula (1) 【Chemistry 2】 (In the formula, R 1a and R 1b is the same as above. 2 represents an aromatic hydrocarbon group or a heterocyclic group. X represents a bromine atom or an iodine atom. with a lanthanoid and lithium-containing ate complex to produce a lanthanoid complex of the compound represented by formula (1); The lanthanide complex and a compound represented by the general formula (2) R 3a R 3b SiCl 2 (2) (In the formula, R 3a and R 3b is the same as above.) With a silyl compound represented by the formula: The manufacturing method comprises, in this order:

2. General formula (6) 【Chemistry 3】 (In the formula, * indicates a bonding point. n indicates an integer of 0 or more. R 1a and R 1b are the same or different and each represents 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. 1a and R 1b may be bonded to each other to form a ring. 2a' represents a heteroaromatic ring.) Graphene nanoribbons having at least one constitutional unit represented by:

3. Furthermore, the general formula (7) 【Chemistry 4】 (In the formula, a dotted line indicates no bond or a single bond. * indicates a bonding point. R 6a , R 6b , R 6c , R 6d , R 6e and R 6f R may be 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 boronic acid or an ester group thereof, an aromatic hydrocarbon group, or a heterocyclic group. 6c and R 6d may be bonded to each other to form a ring.) Graphene nanoribbons according to claim 2, having at least one constitutional unit represented by:

4. General formula (8) 【Chemistry 5】 (In the formula, dotted lines are the same or different and indicate no bond or a single bond. *1 indicates a bonding point. When the dotted line connecting to *2 is a single bond, *2 indicates a bonding point. n indicates an integer of 0 or more. R 1a and R 1b are the same or different and each represents 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. 1a and R 1b may be bonded to each other to form a ring. 2a' R represents a heteroaromatic ring. 6a , R 6b , R 6c , R 6d , R 6e and R 6f R may be 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 boronic acid or an ester group thereof, an aromatic hydrocarbon group, or a heterocyclic group. 6c and R 6d may be bonded to each other to form a ring.) Graphene nanoribbons according to claim 2 or 3, having at least one constitutional unit represented by:

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