Method for producing cyclic imide compound, composition, and compound

Abstract

A first problem addressed by the present invention is to provide a method for producing a cyclic imide compound, the method being excellent in terms of yield and purity. A second problem addressed by the present invention is to provide a composition usable in the method for producing a cyclic imide compound, the method being excellent in terms of yield and purity. A third problem addressed by the present invention is to provide an intermediate compound usable in the method for producing a cyclic imide compound, the method being excellent in terms of yield and purity.　This method for producing a cyclic imide compound comprises reacting a compound represented by formula (1) with at least one amine compound to obtain a compound represented by formula (2).

Description

[Technical field]

[0001] The present invention relates to a method for producing a cyclic imide compound, a composition, and the compound. [Background technology]

[0002] Because of the potential for weight reduction, cost reduction, and flexibility, the use of organic thin film transistors (organic TFTs: Thin Film Transistors) having an organic semiconductor film (organic semiconductor layer) has been considered for use in FETs (field effect transistors) used in liquid crystal displays and organic EL (electric luminescence) displays, RFIDs (radio frequency identifiers: RF tags), and devices using logic circuits including memories. As an organic semiconductor compound for forming such an organic semiconductor film, Patent Document 1 discloses a cyclic imide compound containing an azaperylene skeleton. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2018-6745 A Summary of the Invention [Problem to be solved by the invention]

[0004] The present inventors have studied the method for producing a cyclic imide compound containing an azaperylene skeleton described in Patent Document 1 and have found that there is room for further improvement in yield and purity.

[0005] Therefore, an object of the present invention is to provide a method for producing a cyclic imide compound with excellent yield and purity. Another object of the present invention is to provide a composition that can be used in a method for producing a cyclic imide compound with excellent yield and purity. Another object of the present invention is to provide an intermediate compound that can be used in the method for producing a cyclic imide compound with excellent yield and purity. [Means for solving the problem]

[0006] As a result of extensive investigations aimed at solving the above problems, the present inventors have found that the above problems can be solved by a specific manufacturing method, and have thus completed the present invention. That is, it has been found that the above problems can be solved by the following configuration.

[0007] [1] A method for producing a cyclic imide compound, comprising reacting a compound represented by the formula (1) described below with at least one amine compound to obtain a compound represented by the formula (2) described below. [2] A step Y1 of reacting the compound represented by the formula (1) with a first amine compound represented by the formula (3) described later to obtain a compound represented by the formula (4) described later; A step Y2 of reacting the compound represented by the formula (4) with a second amine compound represented by the formula (5) described below to obtain a compound represented by the formula (6) described below; The compound represented by the above formula (6) is converted to a protecting group P 31 to obtain a compound represented by formula (7) described below; A process Y4 for obtaining a compound represented by the formula (2) from a compound represented by the formula (7). [3] The method for producing a cyclic imide compound according to [1] or [2], wherein the compound represented by formula (1) above is a compound represented by formula (8) described later, and the compound represented by formula (2) above is a compound represented by formula (9) described later. [4] The method for producing a cyclic imide compound according to [3], wherein the compound represented by the formula (8) above is a compound represented by the formula (10) described below. [5] The method for producing a cyclic imide compound according to [4], wherein the compound represented by the formula (10) above is a compound represented by the formula (10') described below. [6] X 111 ~X 116represents a chlorine atom. [7] A process Y1' of reacting a compound represented by formula (X1) described later with a compound represented by formula (X2) described later to obtain a composition containing a compound represented by formula (11A) described later and a compound represented by formula (11B) described later, and then reacting the composition with a first amine compound represented by formula (12) described later without performing column purification on the composition to obtain a compound represented by formula (13) described later; A process Y2' of reacting the compound represented by the formula (13) with a second amine compound represented by the formula (14) described below to obtain a compound represented by the formula (15) described below; The compound represented by the above formula (15) is reacted with the protecting group P 31 to obtain a compound represented by formula (16) described below; A process Y4' for obtaining a compound represented by formula (9) from a compound represented by formula (16). [8] A method for producing a cyclic imide according to [1], comprising the steps of: reacting a compound represented by formula (X1) described later with a compound represented by formula (X2) described later to obtain a composition containing a compound represented by formula (11A) described later and a compound represented by formula (11B) described later; and then reacting the composition with an amine compound represented by formula (14) described later, without carrying out column purification of the composition, to obtain a compound represented by formula (9') described later. [9] The method for producing a cyclic imide compound according to [7] or [8], further comprising a step Y0′ of purifying the compound represented by the formula (X2) before reacting the compound represented by the formula (X1) with the compound represented by the formula (X2).

[10] A composition used for synthesizing a compound represented by formula (9) described below, Contains at least a compound represented by formula (8) described below, The composition, wherein the total content of a compound represented by formula (17) described below and a compound represented by formula (18) described below is 3.0 mass % or less based on the total solid content of the composition.

[11] A compound represented by formula (4) described below.

[12] A compound represented by formula (6) described below.

[13] A compound represented by formula (7) described below.

[14] A compound represented by formula (11A') described below.

[15] A compound represented by formula (11A″) described below. Effect of the Invention

[0008] According to the present invention, a method for producing a cyclic imide compound excellent in yield and purity can be provided. Furthermore, according to the present invention, it is possible to provide a composition that can be used in a method for producing a cyclic imide compound with excellent yield and purity. Furthermore, according to the present invention, it is possible to provide an intermediate compound that can be used in a method for producing a cyclic imide compound with excellent yield and purity. [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 is a cross-sectional view showing a structure of a bottom-gate-bottom-contact type organic thin-film transistor, which is an example of an organic thin-film transistor. [Diagram 2] FIG. 2 is a cross-sectional view showing a structure of a bottom-gate-top-contact type organic thin-film transistor, which is another example of an organic thin-film transistor. [Diagram 3] 1A to 1C are schematic diagrams illustrating an example of a method for forming an organic semiconductor film of an organic thin film transistor. [Figure 4] 1A to 1C are schematic diagrams illustrating another example of a method for forming an organic semiconductor film of an organic thin film transistor. [Diagram 5] 1A to 1C are schematic diagrams illustrating another example of a method for forming an organic semiconductor film of an organic thin film transistor. [Figure 6] 1 is a schematic diagram showing an example of a substrate and a member used in a method for forming an organic semiconductor film of an organic thin film transistor. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The method for producing the cyclic imide compound, the composition, and the compound of the present invention will be described in detail below. The following description of the constituent elements may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

[0011] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0012] In this specification, (meth)acryloyl means acryloyl or methacryloyl.

[0013] In this specification, the description of a compound includes not only the compound itself, but also its salts and ions. 。

[0014] In this specification, when there are multiple substituents, etc., represented by a specific symbol, or when multiple substituents, etc., are specified at the same time, unless otherwise specified, the respective substituents, etc. may be the same or different from each other. The same applies to the definition of the number of substituents, etc. In addition, when multiple substituents, etc., are adjacent to each other (particularly adjacent), they may be linked to each other to form a ring, unless otherwise specified.

[0015] In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0016] In the present invention, when a group can form both an acyclic skeleton and a cyclic skeleton, the group includes a group having an acyclic skeleton and a group having a cyclic skeleton, unless otherwise specified. For example, aliphatic hydrocarbon groups, alkyl groups, alkenyl groups, and alkynyl groups include groups having any of straight-chain, branched-chain, and cyclic structures, unless otherwise specified. More specific examples of the alkyl group include a straight-chain alkyl group, a branched-chain alkyl group, and a cyclic (cyclo)alkyl group. When a group can form a cyclic skeleton, the lower limit of the number of atoms in the group forming the cyclic skeleton is 3 or more, and preferably 5 or more, regardless of the lower limit of the number of atoms specifically described for the group. The above cycloalkyl group includes a bicycloalkyl group, a tricycloalkyl group, and the like.

[0017] [Method of producing cyclic imide compound] The method for producing a cyclic imide compound of the present invention (hereinafter also referred to as the "production method of the present invention") is a production method in which a compound represented by formula (1) described below is reacted with at least one amine compound to obtain a compound represented by formula (2) described below.

[0018] The present inventors have investigated a method for producing a cyclic imide compound containing an azaperylene skeleton, such as the compound represented by general formula (2), and have found that the reason why the yield and purity do not meet the desired levels in the production methods of the prior art is that the target cyclic imide compound is formed via an acid anhydride intermediate. Specifically, it was believed that an acid anhydride containing an azaperylene skeleton has extremely low solubility in a solvent, making it difficult to handle and to control the quality, and as a result, when the acid anhydride intermediate containing an azaperylene skeleton is modified to a cyclic imide structure to synthesize the target cyclic imide compound, the yield and purity are low. In response to this, the present inventors have now discovered a novel production method that can produce a cyclic imide compound without going through an acid anhydride intermediate. According to the production method of the present invention, a cyclic imide compound containing an azaperylene skeleton, such as a compound represented by general formula (2), can be produced in high yield and high purity. The production method of the present invention will be described in detail below.

[0019] The production method of the present invention includes a step of reacting a compound represented by the following formula (1) with at least one amine compound to obtain a compound represented by the following formula (2). First, the compound represented by formula (1) as the raw material, the compound represented by formula (2) as the target product, and the amine compound will be described. [Compound represented by formula (1)]

[0020] [ka]

[0021] In formula (1), A 11 ~A 18 Each independently represents -N= or -C(R 15 )=. However, A 11 ~A 18 At least one of the groups represents -N=. Among them, A 11 ~A 18 Among these, preferably 1 to 4 represent -N=, more preferably 1 to 3 represent -N=, further preferably 1 or 2 represent -N=, and particularly preferably 2 represent -N=. In addition, A 11 ~A 18 The nitrogen atom of -N= may have a substituent, for example, an N-oxide group (N→O group) and a salt having a counter anion.

[0022] R 15 represents a hydrogen atom or a substituent. R 15 The substituent represented by the following formula (1) is not particularly limited, and examples thereof include groups selected from the following substituent group Z.

[0023] <Substituent group Z> Substituent group Z is a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a silyl group, an alkoxy group, an amino group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfon ... Examples of such groups include phenyl groups, silyloxy groups, heterocyclic oxy groups, carbamoyl groups, carbamoyloxy groups, heterocyclic thio groups, sulfamoyl groups, arylazo groups, heterocyclic azo groups, imido groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, hydrazino groups, imino groups, cyano groups, hydroxy groups, nitro groups, mercapto groups, sulfo groups, carboxy groups, hydroxamic acid groups, sulfino groups, boronic acid groups (-B(OH)2), phosphato groups (-OPO(OH)2), phosphono groups (-PO(OH)2), and sulfato groups (-OSOH). The group selected from the above-mentioned substituent group Z may further have a substituent.

[0024] Examples of the halogen atom contained in the substituent group Z include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom or a chlorine atom is preferable.

[0025] The alkyl group contained in the substituent group Z is not particularly limited, but is preferably an alkyl group having 1 (3) to 30 carbon atoms, and more preferably an alkyl group having 1 (3) to 20 carbon atoms. The number in parentheses indicates the number of carbon atoms in the case of a cycloalkyl group. Examples of the alkyl group which may have a substituent included in the substituent group Z include a methyl group, an ethyl group, a propyl group, a 2-methylpropyl group, a butyl group, an amyl group, a pentyl group, a 1-methylpentyl group, a 2,2-dimethylpropyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a 3,7-dimethyloctyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a 2,6-dimethyloctyl group, an icosyl group, a 2-decyltetradecyl group, a 2-hexyldodecyl group, a 2-ethylhex ... ethyloctyl group, 2-decyltetradecyl group, 2-butyldecyl group, 1-octylnonyl group, 2-ethyloctyl group, 2-octyldecyl group, 2-octyldodecyl group, 7-hexylpentadecyl group, 2-octyltetradecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, benzyl group, 2-cyclohexylethyl group, p-chlorobenzyl group, 2-phenylethyl group, trifluoromethyl group, perfluoroethyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, C5F 11 C2H4-, C6F 13 Examples of such alkyl groups include CH-, a 3-aminopropyl group, a 4-aminobutyl group, a 5-ethoxypentyl group, a (meth)acryloyloxypropyl group, a (meth)acryloyloxypentyl group, a 4-hydroxybutyl group, a 4-sulfobutyl group, a 10-phosphonodecyl group, a 2-hydroxyethoxymethyl group, a 2-imidazolylethoxymethyl group, a 4-(N,N-dimethylamino)butyl group, and a 5-norbornenemethyl group.

[0026] The alkenyl group included in the substituent group Z is not particularly limited, but is preferably an alkenyl group having 2 to 20 carbon atoms, more preferably an alkenyl group having 2 to 12 carbon atoms, and further preferably an alkenyl group having 2 to 8 carbon atoms. Examples of the alkenyl group which may have a substituent included in the substituent group Z include a vinyl group, an allyl group, a 2-butenyl group, a 1-pentenyl group, a 4-pentenyl group, a 2-(2-thiazolyl)vinyl group, a 2-(5-thiazolyl)vinyl group, a styryl group, and a 2-(2-thienyl)vinyl group.

[0027] The alkynyl group included in the substituent group Z is not particularly limited, but is preferably an alkynyl group having 2 to 20 carbon atoms, more preferably an alkynyl group having 2 to 12 carbon atoms, and further preferably an alkynyl group having 2 to 8 carbon atoms. Examples of the alkynyl group which may have a substituent included in the substituent group Z include an ethynyl group, a propargyl group, a 1-pentynyl group, a trimethylsilylethynyl group, a triethylsilylethynyl group, a tri-i-propylsilylethynyl group, a p-propylphenylethynyl group, a 2-thienylethynyl group, a 2-thiazolylethynyl group, a 5-thiazolylethynyl group, and a phenylethynyl group.

[0028] The aryl group included in the substituent group Z is not particularly limited, but is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. Examples of the aryl group which may have a substituent included in the substituent group Z include a phenyl group, a naphthyl group, a 2,4,6-trimethylphenyl group, a p-(t-butyl)phenyl group, a 4-methyl-2,6-dipropylphenyl group, a 4-fluorophenyl group, a 4-trifluoromethylphenyl group, a p-pentylphenyl group, a 3,4-dipentylphenyl group, a p-heptoxyphenyl group, and a 3,4-diheptoxyphenyl group.

[0029] Examples of the heterocyclic group included in the substituent group Z include heterocyclic groups having 3 or more atoms constituting the ring, and containing at least one heteroatom and 1 to 30 carbon atoms as the atoms constituting the ring. The heterocyclic group includes an aromatic heterocyclic group (heteroaryl group) and an aliphatic heterocyclic group. Examples of heteroatoms constituting the ring include a nitrogen atom, an oxygen atom, and a sulfur atom, and the number of atoms is not particularly limited, but is, for example, 1 to 2. The number of carbon atoms constituting the ring is preferably 3 to 20, and more preferably 5 to 12. The heterocyclic group is preferably a 5-membered or 6-membered ring, or a condensed ring thereof. Examples of the heterocyclic group included in the substituent group Z include a thienyl group, a thiazolyl group, an imidazolyl group, a pyridyl group, a pyrimidinyl group, a quinolyl group, a furanyl group, a selenophenyl group, a piperidyl group, a morpholino group, a benzoxazolyl group, a benzimidazolyl group, a benzthiazolyl group, a 2-hexylfuranyl group, and a pyranyl group.

[0030] The silyl group which may have a substituent included in the substituent group Z is not particularly limited, but is preferably a silyl group having a group selected from an alkyl group and an aryl group as a substituent and having 3 to 40 carbon atoms (more preferably 3 to 30, and even more preferably 3 to 24). Examples of the silyl group which may have a substituent included in the substituent group Z include a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, a triisopropylsilyl group, and a dimethylphenylsilyl group.

[0031] The alkoxy group contained in the substituent group Z is not particularly limited, but is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 12 carbon atoms, and further preferably an alkoxy group having 1 to 8 carbon atoms. Examples of the alkoxy group included in the substituent group Z include a methoxy group, an ethoxy group, and a butoxy group.

[0032] The amino group which may have a substituent included in the substituent group Z is not particularly limited, but is preferably an amino group or an amino group having a group selected from an alkyl group and an aryl group as a substituent and having 1 to 20 carbon atoms (more preferably 1 to 10, and even more preferably 1 to 6). Examples of the amino group which may have a substituent and is included in the substituent group Z include an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dibenzylamino group, and an anilino group.

[0033] The aryloxy group included in the substituent group Z is not particularly limited, but is preferably an aryloxy group having 6 to 20 carbon atoms, more preferably an aryloxy group having 6 to 16 carbon atoms, and further preferably an aryloxy group having 6 to 12 carbon atoms. The aryloxy group included in the substituent group Z includes, for example, a phenyloxy group and a 2-naphthyloxy group.

[0034] The acyl group included in the substituent group Z is not particularly limited, but is preferably an acyl group having 1 to 20 carbon atoms, more preferably an acyl group having 1 to 16 carbon atoms, and further preferably an acyl group having 1 to 12 carbon atoms. Examples of the acyl group which may have a substituent included in the substituent group Z include an acetyl group, a hexanoyl group, a benzoyl group, a formyl group, and a pivaloyl group.

[0035] The alkoxycarbonyl group contained in the substituent group Z is not particularly limited, but is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, more preferably an alkoxycarbonyl group having 2 to 16 carbon atoms, still more preferably an alkoxycarbonyl group having 2 to 12 carbon atoms, and particularly preferably a methoxycarbonyl group or an ethoxycarbonyl group. The aryloxycarbonyl group included in the substituent group Z is not particularly limited, but is preferably an aryloxycarbonyl group having 7 to 20 carbon atoms, more preferably an aryloxycarbonyl group having 7 to 16 carbon atoms, still more preferably an aryloxycarbonyl group having 7 to 10 carbon atoms, and particularly preferably a phenyloxycarbonyl group.

[0036] The acyloxy group included in the substituent group Z is not particularly limited, but is preferably an acyloxy group having 2 to 20 carbon atoms, more preferably an acyloxy group having 2 to 16 carbon atoms, and even more preferably an acyloxy group having 2 to 10 carbon atoms. Examples of the acyloxy group which may have a substituent included in the substituent group Z include an acetoxy group, a benzoyloxy group, and a (meth)acryloyloxy group.

[0037] The acylamino group contained in the substituent group Z is not particularly limited, but is preferably an acylamino group having 2 to 20 carbon atoms, more preferably an acylamino group having 2 to 16 carbon atoms, and further preferably an acylamino group having 2 to 10 carbon atoms. The acylamino group included in the substituent group Z includes, for example, an acetylamino group and a benzoylamino group.

[0038] The aminocarbonylamino group included in the substituent group Z is not particularly limited, but is preferably an aminocarbonylamino group having 2 to 20 carbon atoms, more preferably an aminocarbonylamino group having 2 to 16 carbon atoms, further preferably an aminocarbonylamino group having 2 to 12 carbon atoms, and particularly preferably a ureido group.

[0039] The alkoxycarbonylamino group contained in the substituent group Z is not particularly limited, but is preferably an alkoxycarbonylamino group having 2 to 20 carbon atoms, more preferably an alkoxycarbonylamino group having 2 to 16 carbon atoms, still more preferably an alkoxycarbonylamino group having 2 to 12 carbon atoms, and particularly preferably a methoxycarbonylamino group, a tert-butoxycarbonylamino group, an allyloxycarbonylamino group, a 2,2,2-trichloroethoxycarbonylamino group, a 9-fluorenylmethyloxycarbonylamino group, a 2-trimethylsilethyloxycarbonylamino group, or a benzyloxycarbonylamino group. The aryloxycarbonylamino group included in the substituent group Z is not particularly limited, but is preferably an aryloxycarbonylamino group having 7 to 20 carbon atoms, more preferably an aryloxycarbonylamino group having 7 to 16 carbon atoms, still more preferably an aryloxycarbonylamino group having 7 to 12 carbon atoms, and particularly preferably a phenyloxycarbonylamino group.

[0040] The alkylthio group contained in the substituent group Z is not particularly limited, but is preferably an alkylthio group having 1 to 20 carbon atoms, more preferably an alkylthio group having 1 to 16 carbon atoms, and further preferably an alkylthio group having 1 to 12 carbon atoms. Examples of the alkylthio group contained in the substituent group Z include a methylthio group, an ethylthio group, and an octylthio group. The arylthio group included in the substituent group Z is not particularly limited, but is preferably an arylthio group having 6 to 20 carbon atoms, more preferably an arylthio group having 6 to 16 carbon atoms, further preferably an arylthio group having 6 to 12 carbon atoms, and particularly preferably a phenylthio group.

[0041] The above-mentioned group selected from the substituent group Z may further have a substituent. Examples of such a substituent include the groups selected from the substituent group Z. In a group having a further substituent (also referred to as a group formed by a combination), the number of the further substituents which may be possessed is not particularly limited, but for example, 1 to 6 are preferable, and 1 to 3 are more preferable. The group formed by combining is not particularly limited, and examples thereof include groups in which each of the above-mentioned groups preferred as groups selected from the above-mentioned substituent group Z is substituted with another group selected from the substituent group Z. Specific examples thereof include alkyl groups, alkenyl groups, or alkynyl groups having a group selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a heterocyclic group (heteroaryl group), an alkoxy group (including a hydroxyalkoxy group, a halogenated alkoxy group, and a heteroarylalkoxy group), an amino group, an acyloxy group, a hydroxy group, a sulfato group, a silyl group, and a phosphono group as a substituent, an alkynyl group having a halogenated aryl group or a (fluorinated) alkylaryl group as a substituent, and the like. Further examples thereof include a group in which one hydrogen atom has been removed from a compound represented by formula (1). As the combined group, among the above, an alkyl group having a halogen atom as a substituent (halogenated alkyl group), an alkyl group having an aryl group as a substituent, an alkyl group having a heterocyclic group as a substituent, an alkenyl group having an aryl group as a substituent, an alkenyl group having a heterocyclic group as a substituent, an alkynyl group having an aryl group as a substituent, an alkynyl group having a heterocyclic group as a substituent, an alkyl group having an alkoxy group as a substituent, or an alkynyl group having a silyl group as a substituent is preferred.

[0042] Also, R 15The substituent represented by the following formula may form a ring. The embodiment in which the substituent forms a ring includes an embodiment in which the substituents are bonded to each other to form a ring, and an embodiment in which a plurality of substituents share one atom to form a ring. An example of a ring formed by bonding the substituents to each other is when two vinyl groups are bonded to each other to form R 15 is bonded to a carbon atom to form a benzene ring. In addition, an example of a ring formed by multiple substituents sharing one atom is a case where two substituents are united to form a sulfur atom (-S- group).

[0043] R 15 Among them, a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkenyl group (an unsubstituted alkenyl group, a silyl group, an aryl group, or an alkenyl group having a heterocyclic group as a substituent, etc.), an alkynyl group (an unsubstituted alkynyl group, a silyl group, an aryl group, or an alkynyl group having a heterocyclic group as a substituent, etc.), an aryl group, a heterocyclic group, a nitro group, an alkoxy group, an alkoxycarbonyl group, or a carboxy group is preferred, and a hydrogen atom, a halogen atom, a cyano group, an alkenyl group (an unsubstituted alkenyl group, a silyl group, an aryl group, or an alkenyl group having a heterocyclic group as a substituent, etc.), an alkynyl group (an unsubstituted alkynyl group, a silyl group, an aryl group, or an alkynyl group having a heterocyclic group as a substituent, etc.), an aryl group, or a heterocyclic group is more preferred.

[0044] R 11 ~R 14 each independently represents an aliphatic hydrocarbon group, an aryl group, or a heteroaryl group. 11 and R 14 One of these represents an aliphatic hydrocarbon group, and the other represents an aryl group or a heteroaryl group. 12 and R 13 One of R represents an aliphatic hydrocarbon group, and the other represents an aryl group or a heteroaryl group. 12 and R 14 represents an aliphatic hydrocarbon group, R 11 and R 13It is preferred that represents an aryl group or a heteroaryl group.

[0045] R 11 ~R 14 The aliphatic hydrocarbon group represented by the formula (I) is not particularly limited and may be linear, branched, or cyclic. It may be saturated or unsaturated. It may contain a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom, and may be halogenated. R 11 ~R 14 Of the aliphatic hydrocarbon groups represented by the formula (I), preferred are linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), linear, branched, or cyclic alkenyl groups having 2 to 20 carbon atoms (preferably 2 to 10 carbon atoms), and linear, branched, or cyclic alkynyl groups having 2 to 20 carbon atoms (preferably 2 to 10 carbon atoms). R 11 ~R 14 When the aliphatic hydrocarbon group represented by R has 2 or more carbon atoms, the solubility of the compound represented by formula (1) is improved, which is advantageous in synthesis in that the amount of reaction solvent can be reduced and the reaction can be carried out at a low temperature. In addition, the yield may be better. 11 ~R 14 Of these, the aliphatic hydrocarbon group represented by the following formula is more preferably a linear, branched, or cyclic alkyl group having 2 to 20 carbon atoms (preferably 2 to 10 carbon atoms).

[0046] R 11 ~R 14 The number of carbon atoms in the aryl group represented by the following formula is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 12. The aryl group may have a monocyclic structure or a condensed ring structure (condensed ring structure) in which two or more rings are condensed. The aryl group is, for example, preferably a phenyl group, a naphthyl group, or an anthryl group, more preferably a phenyl group or a naphthyl group, and even more preferably a phenyl group.

[0047] R 11 ~R 14The number of carbon atoms in the heteroaryl group represented by the following formula is not particularly limited, but is preferably 3 to 30, and more preferably 3 to 18. The heteroaryl group has a heteroatom other than carbon and hydrogen atoms, such as a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, and is preferably a sulfur atom, an oxygen atom, or a nitrogen atom. The number of heteroatoms contained in the heteroaryl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 4, and further preferably 1 or 2. The number of ring members of the heteroaryl group is not particularly limited, but is preferably 3 to 8, more preferably 5 to 7, and even more preferably 5 to 6. The heteroaryl group may have a monocyclic structure or a condensed ring structure in which two or more rings are condensed. In the case of a condensed ring structure, an aromatic hydrocarbon ring (e.g., a benzene ring) having no heteroatom may be included. The heteroaryl group is preferably, for example, a furyl group, a thienyl group, a thiazolyl group, a pyridyl group, a quinolyl group, an isoquinolyl group, or a carbazolyl group.

[0048] R 11 ~R 14 The aliphatic hydrocarbon group, aryl group, and heteroaryl group represented by the formula (I) may further have a substituent. Examples of the substituent include groups selected from the above-mentioned substituent group Z. Specific examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, a thioalkyl group, an acyl group, -C(=O)NR 1X R 2X , -NR 3X C(=O)R 4X , -S(=O)2NR 5X R 6X , -NR 7X S(=O)2R 8X , a silyl group, a nitro group, a cyano group, or a halogen atom is preferred. In addition, R 1X ~R 8X represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, or a heteroaryl group. R 1X ~R8X The aliphatic hydrocarbon group, aryl group, and heteroaryl represented by the formula: 11 ~R 14 The meanings and preferred embodiments of the aliphatic hydrocarbon group, aryl group, and heteroaryl represented by the following formula (I) are the same as those of the aliphatic hydrocarbon group, aryl group, and heteroaryl represented by the following formula (I), respectively.

[0049] Of the compounds represented by formula (1), a compound represented by the following formula (8) is preferable, a compound represented by formula (10) is more preferable, and a compound represented by formula (10') is even more preferable.

[0050] [ka]

[0051] In formula (8), R 11 ~R 14 are R in formula (1), 11 ~R 14 In formula (8), R 12 and R 14 represents an aliphatic hydrocarbon group, R 11 and R 13 Preferably, R represents an aryl group or a heteroaryl group. 81 ~R 86 Each independently represents a hydrogen atom or a substituent. 81 ~R 86 The substituent represented by the formula (I) is the same as the above-mentioned R 15 The meaning and preferred embodiments of the substituent are also the same as those of the substituent represented by the following formula:

[0052] [ka]

[0053] In formula (10), X 101 and X 102 each independently represents an electron-withdrawing group. Here, the "electron-withdrawing group" refers to a group having a positive Hammett substituent constant. For specific examples of electron-withdrawing groups, see Chem. Rev. 1BBl. 97, 165-195. X 101 and X 102 Examples of the electron-withdrawing group represented by the formula (I) include a halogen atom, an acyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a halogenated alkyl group, a halogenated alkyloxy group, an aminocarbonyl group, an alkanesulfonyl group, an arylsulfonyl group, a cyano group, a nitro group, and a formyl group. Among these, a halogen atom is preferable, a fluorine atom or a chlorine atom is more preferable, and a chlorine atom is even more preferable. Each of n1 and n2 independently represents an integer of 1 to 5. n1 and n2 are preferably 3 or less in terms of further improving the yield. R 12 and R 14 Each of R independently represents an aliphatic hydrocarbon group. 12 and R 14 As the aliphatic hydrocarbon group represented by the formula (1), R 12 and R 14 The meaning and preferred form of the aliphatic hydrocarbon group represented by R 81 ~R 86 are R in formula (8), 81 ~R 86 is synonymous with.

[0054] [ka]

[0055] In formula (10'), X 111 ~X 116 Each of X independently represents a halogen atom. 111 ~X 116 The halogen atom represented by the formula (I) is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a chlorine atom. 81 ~R 86 are R in formula (8), 81 ~R 86 The same definition and preferred embodiments are also the same. R 12 and R 14 Each of R independently represents an aliphatic hydrocarbon group.12 and R 14 As the aliphatic hydrocarbon group represented by the formula (1), R 12 and R 14 The meaning and preferred embodiments are also the same as those of the aliphatic hydrocarbon group represented by the following formula:

[0056] In the following, examples of the compound represented by formula (1) will be given, but the compound represented by formula (1) is not limited thereto. In the table below, (1)-1 to (1)-52 are R 11 , R 12 , R 13 , and R 14 In other words, if we take the following basic skeleton as an example, R in the following basic skeleton 11 , R 12 , R 13 , and R 14 It is intended that the combination may be any of (1)-1 to (1)-52 in the table below.

[0057] [ka]

[0058] In addition, R in each basic skeleton shown below 81 and R 82 each independently represents a substituent selected from the group consisting of a hydrogen atom, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, a trifluoromethoxy group, a trichloromethyl group, a trichloromethoxy group, a phenyl group, a 2-thiazolyl group, a 5-thiazolyl group, a 2-thienyl group, a 3-thienyl group, a styryl group, a 2-thiazolylvinyl group, a 5-thiazolylvinyl group, a 2-thienylvinyl group, a 3-thienylvinyl group, a phenylethynyl group, a 2-thiazolylethynyl group, a 5-thiazolylethynyl group, a 2-thienylethynyl group, a 3-thienylethynyl group, a trimethylsilylethynyl group, a triethylsilylethynyl group, a triisopropylethynyl group, and a 1-octynyl group. 81 and R 82 At least one of the groups is a substituent other than hydrogen.

[0059] In the following tables, "Me" represents a methyl group, and "Et" represents an ethyl group.

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] [Table 1]

[0064] [Compound represented by formula (2)] [ka]

[0065] In formula (2), A 11 ~A 18 is A in formula (1). 11 ~A 18 The same definition and preferred embodiments are also the same.

[0066] R 31 and R 51 each independently represents a substituent. R 31 and R 51The substituent represented by is not particularly limited, but is preferably a group selected from the above-mentioned substituent group Z. Specifically, an alkyl group (preferably having 1 to 30 carbon atoms, more preferably having 4 to 20 carbon atoms, and may be linear, chain, or cyclic), an alkenyl group, an alkynyl group, an aryl group (preferably having 6 to 20 carbon atoms), or a heterocyclic group (containing at least one of the above-mentioned heteroatoms as ring-constituting atoms, preferably a 5-membered ring, a 6-membered ring, or a condensed ring thereof, preferably having 3 to 20 ring-constituting carbon atoms), is preferable, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group is more preferable, an alkyl group, an aryl group, or a heteroaryl group is further preferable, and an alkyl group is particularly preferable. The above-mentioned alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, and heteroaryl group may further have a substituent. When the above-mentioned substituent has a substituent, examples of the substituent include a group selected from the substituent group Z.

[0067] Among them, R 31 and R 51 The substituent represented by the formula (I) is preferably an unsubstituted alkyl group, a halogenated alkyl group, an alkyl group having an aryl group as a substituent, an alkyl group having a heterocycle (preferably a heteroaryl group) as a substituent, an unsubstituted aryl group, an aryl group substituted with an alkyl group, an unsubstituted heterocyclic group, a heterocyclic group substituted with an alkyl group, an alkyl group substituted with a silyl group, or an alkyl group substituted with one or more alkoxy groups. In the alkyl group having an aryl group as a substituent and the alkyl group having a heterocycle as a substituent, the aryl group and the heterocycle may further have a substituent. When further having a substituent, the above-mentioned substituent may be a group selected from the substituent group Z, and a halogen atom is preferable.

[0068] Of the compounds represented by formula (2), a compound represented by the following formula (9) is preferred.

[0069] [ka]

[0070] In formula (9), R 31 and R 51 are R in formula (2), 31 and R 51 The same meaning and preferred form are also the same. 81 ~R 86 are R in formula (8), 81 ~R 86 The same definition and preferred embodiments are also the same.

[0071] An example of the compound represented by formula (2) will be shown below, but the compound represented by formula (2) is not limited thereto.

[0072] [ka]

[0073] [ka]

[0074] [ka]

[0075] [ka]

[0076] [ka]

[0077] [ka]

[0078] [ka]

[0079]

change

[0080]

change

[0081]

change

[0082]

change

[0083]

change

[0084]

change

[0085]

change

[0086]

change

[0087]

change

[0088]

change

[0089]

change

[0090] [ka]

[0091] [ka]

[0092] [Amine Compound] In the production method of the present invention, the amine compound to be reacted with the compound represented by the above formula (1) is not particularly limited, but is preferably a primary amine or a protected primary amine. The primary amine is not particularly limited, but examples thereof include amine compounds represented by the following formula (Y1). Formula (Y1) R Y1 -NH2

[0093] In formula (Y1), R Y1 represents a substituent. R Y1 The substituent represented by is not particularly limited, but is preferably a group selected from the above-mentioned substituent group Z. Specifically, an alkyl group (preferably having 1 to 20 carbon atoms. From the viewpoint of carrier mobility when used as an organic semiconductor compound, the lower limit of the carbon number is more preferably 4 or more. The upper limit of the carbon number is more preferably 15 or less, and even more preferably 8 or less. It may be linear, branched, or cyclic.), an alkenyl group, an alkynyl group, an aryl group (preferably having 6 to 20 carbon atoms), or a heterocyclic group (containing at least one or more of the above-mentioned heteroatoms as ring-constituting atoms. It is preferably a 5-membered ring, a 6-membered ring, or a condensed ring thereof. It is preferably a ring-constituting carbon atom number of 3 to 20.), more preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, even more preferably an alkyl group, an aryl group, or a heteroaryl group, and particularly preferably an alkyl group. The above-mentioned alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, and heteroaryl group may further have a substituent. When the above-mentioned substituent has a substituent, examples of the substituent include a group selected from the substituent group Z.

[0094] Among them, R Y1 As the substituent represented by the formula (I), an unsubstituted alkyl group, a halogenated alkyl group, an alkyl group having an aryl group as a substituent, an alkyl group having a heterocycle (preferably a heteroaryl group) as a substituent, an unsubstituted aryl group, an aryl group substituted with an alkyl group, an unsubstituted heterocyclic group, a heterocyclic group substituted with an alkyl group, an alkyl group substituted with a silyl group, or an alkyl group substituted with one or more alkoxy groups is more preferable. In the alkyl group having an aryl group as a substituent and the alkyl group having a heterocycle as a substituent, the aryl group and the heterocycle may further have a substituent. When further having a substituent, the above-mentioned substituent includes a group selected from the substituent group Z, and a halogen atom is preferable.

[0095] Specific examples of the amine compound represented by the formula (Y1) include methylamine, ethylamine, 2-trimethylsilethylamine, propylamine, isopropylamine, cyclopropylamine, butylamine, isobutylamine, tert-butylamine, sec-butylamine, cyclobutylamine, 3-methylbutylamine, pentylamine, neopentylamine, 2-methylbutylamine, cyclopentylamine, hexylamine, cyclohexylamine, 1-methylpentylamine, heptylamine, octylamine, 2-ethylhexylamine, 1-methyloctylamine, decylamine, dodecylamine, benzylamine, phenylethylamine, phenylpropylamine, phenylbutylamine, cyclohexylethylamine, 2-thienylethylamine, 2-thiazolylethylamine, 5-thiazolylethylamine, 2-(trimethylsilyl)ethylamine, butadiene ... Examples of suitable amines include methoxypropylamine, methoxybutylamine, methylpentylamine, aniline, p-octylaniline, p-octylphenylethylamine, p-ethylphenylethylamine, p-hexylphenylethylamine, p-decylphenylethylamine, 3,7-dimethyloctylamine, perfluorophenylethylamine, 2-thienylethylamine, 2-thiazolylethylamine, 5-thiazolylethylamine, 2-hexyldecylamine, 2-octyldodecylamine, 1H,1H-heptafluorobutylamine, 1H,1H-undecafluorobutylamine, 1H,1H,2H,2H-tridecafluorooctylamine, p-fluorophenylamine, 2-(4-pyridyl)ethylamine, 2,4-dimethoxymethylamine, 2-(3-pyridyl)ethylamine, toluidine, butoxypropylamine, and 3,6,9,12-tetraoxadecaneamine.

[0096] The protected primary amine refers to a compound having a structure in which one of the hydrogen atoms bonded to the nitrogen atom in the above formula (Y1) is protected with a protecting group. A specific example of the protected primary amine is a first amine compound represented by formula (3) that can be used in the production method of the second embodiment described later. The protected primary amine is described below in the preparation method of the second embodiment.

[0097] [Method for producing cyclic imide compound] The production method of the present invention includes a step of reacting a compound represented by the above formula (1) with at least one amine compound to obtain a compound represented by the above formula (2). In the following, R in formula (2) 31 and R 51 The first embodiment will be described below with reference to the case where the substituents represented by the formula (2) are the same. 31 and R 51 A case where the substituents represented by the following formula (I) are not identical will be described as a second embodiment.

[0098] <Manufacturing Method of First Embodiment> The manufacturing method according to the first embodiment includes the following step X. Step X: A step of heating a composition containing a compound represented by formula (1) and at least one amine compound to obtain a compound represented by formula (2). The compound represented by formula (1), the compound represented by formula (2), and the amine compound are as described above.

[0099] In the above step X, two adjacent ester groups in the compound represented by formula (1) are subjected to an amidation / imidization reaction with an amine compound (specifically, -COOR 11 and -COOR 14 Amidation / imidization reaction of -COOR with amine compounds 12 and -COOR 13 and an amine compound) respectively occur to form a cyclic imide compound represented by formula (2).

[0100] The amine compound may be either a primary amine or a protected primary amine. However, a primary amine is preferred from the viewpoint that a deprotection step is not required to obtain the target cyclic imide compound represented by formula (2). The amount of the amine compound used is preferably 2.0 to 10 molar equivalents, and more preferably 2.0 to 6.0 molar equivalents, relative to 1 molar equivalent of the compound represented by formula (1).

[0101] The composition may include a solvent. The solvent may be used alone or in combination of two or more. The solvent is not particularly limited, but examples thereof include hydrocarbon solvents, ether solvents, amide solvents, alcohol solvents, nitrile solvents, and sulfoxide solvents. Examples of the hydrocarbon solvent include pentane, hexane, heptane, octane, decane, toluene, ethylbenzene, xylene, diethylbenzene, fluorobenzene, trifluoromethylbenzene, chloroform, dichloromethane, 1,1,2,2-tetrachloroethane, 1,1,2-trichloroethane, chlorobenzene, dichlorobenzene, trichlorobenzene, mesitylene, amylbenzene, decalin, 1-methylnaphthalene, 1-ethylnaphthalene, 1-chloronaphthalene, 1-fluoronaphthalene, 1,6-dimethylnaphthalene, nitrobenzene, and tetralin. Ether solvents include anisole, diethyl ether, dibutyl ether, diisopropyl ether, cyclopentyl methyl ether, diphenyl ether, tetrahydropyran, dioxane, dimethoxyethane, diethoxyethane, and tetrahydrofuran. Examples of the amide solvent include N,N-dimethylformamide, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, and N,N-dimethylacetamide. Examples of the alcohol solvent include methanol, ethanol, propanol, isopropanol, amyl alcohol, benzyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, and glycerin. Examples of the nitrile solvent include acetonitrile and benzonitrile. Sulfoxide solvents include dimethyl sulfoxide, sulfolane, and the like.

[0102] Of the above solvents, those having a boiling point of 70° C. or higher are preferred, and those having a boiling point of 90° C. or higher are more preferred. Examples of solvents having a boiling point of 90° C. or higher include heptane, octane, decane, toluene, ethylbenzene, xylene, diethylbenzene, fluorobenzene, trifluoromethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, mesitylene, amylbenzene, decalin, 1-methylnaphthalene, 1-ethylnaphthalene, 1-chloronaphthalene, 1-fluoronaphthalene, 1,6-dimethylnaphthalene, nitrobenzene, 1,1,2,2-tetrachloroethane, 1,1,2-trichloroethane, benzonitrile, tetralin, Examples of the solvent include anisole, dibutyl ether, cyclopentyl methyl ether, diphenyl ether, dioxane, diethoxyethane, N,N-dimethylformamide, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylacetamide, 1-propanol, 1-butanol, isobutyl alcohol, 2-butanol, amyl alcohol, benzyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, glycerin, dimethyl sulfoxide, and sulfolane.

[0103] When the composition contains a solvent, the content of the solvent is preferably 75.0 to 99.9 mass %, more preferably 80.0 to 98.0 mass %, based on the total mass of the composition.

[0104] The reaction temperature is not particularly limited, but is preferably from 20 to 250°C, more preferably from 50 to 200°C. The reaction time varies depending on reaction conditions including the solvent used and the reaction temperature, but is usually 1 to 24 hours, preferably 1 to 20 hours. After completion of the heating reaction, the obtained compound represented by formula (2) may be purified, if necessary, by a separation and purification means including washing, extraction, drying, filtration, concentration, recrystallization, reprecipitation, crystallization, centrifugation, adsorption, column purification, and / or sublimation purification, and is preferably purified by a separation and purification means including sublimation purification.

[0105] As described above, the compound represented by formula (1) is preferably a compound represented by formula (8), and the compound represented by formula (2) is preferably a compound represented by formula (9). In the following, the compound represented by formula (8) (the latter formula (11A) corresponds to formula (8)) to the compound represented by formula (9) (the latter formula (9') corresponds to formula (9) with R 31 and R 51 A preferred embodiment (hereinafter, also referred to as "First embodiment-1") of the method for producing a compound in which and are the same substituent will be described.

[0106] (Preferred embodiment of the method for producing the compound represented by formula (9) (first embodiment-1)) The manufacturing method of the first embodiment-1 includes the following step X'. Step X': a step of reacting a compound represented by the following formula (X1) with a compound represented by the following formula (X2) to obtain a composition containing a compound represented by the following formula (11A) and a compound represented by the following formula (11B), and then reacting the composition with a first amine compound represented by the following formula (14) without subjecting the composition to column purification to obtain a compound represented by the following formula (9'). The compound represented by the following formula (9') is a compound included in the compound represented by the above formula (9). Specifically, the compound represented by the following formula (9') is a compound represented by the above formula (9) in which R 31 Substituents represented by R 51 The compound represented by the formula (11A) corresponds to the compound represented by the formula (8) above.

[0107] The manufacturing method of the above-mentioned first embodiment-1 preferably further includes the following step Y0′. Step Y0': A step of purifying the compound represented by the formula (X2) before reacting the compound represented by the formula (X1) with the compound represented by the formula (X2).

[0108] The compounds represented by formula (X1), formula (X2), formula (11A), and formula (11B) in step X' have the same meanings as the compounds represented by formula (X1), formula (X2), formula (11A), and formula (11B) in step Y1' described below, and preferred embodiments are also the same. The compounds represented by formula (X1), formula (X2), formula (11A), and formula (11B) will be described later in the production method of the second embodiment.

[0109] The first amine compound represented by formula (14) in step X' has the same meaning as the second amine compound represented by formula (14) in step Y1' described below, and the preferred embodiments are also the same. The first amine compound represented by formula (14) will be described later in the production method of the second embodiment.

[0110] In step X', the procedure for reacting a compound represented by formula (X1) with a compound represented by formula (X2) to obtain a composition containing a compound represented by formula (11A) and a compound represented by formula (11B) is the same as that of step Y1' described later, and preferred embodiments are also the same. The above procedure will be explained later in the manufacturing method of the second embodiment.

[0111] In step X', the compound represented by formula (11B) is a by-product in the synthesis reaction in which the compound represented by formula (X1) and the compound represented by formula (X2) are reacted to obtain the compound represented by formula (11A). It is presumed that the compound represented by formula (11B) is produced as a by-product due to formic acid that may be contained as an impurity in the compound represented by formula (X2) (for example, 2,4,6-trichlorophenyl formate, etc., as the compound represented by formula (X2)). In step X', the by-production of the compound represented by formula (11B) can be suppressed by carrying out a step (step Y0') of purifying the compound represented by formula (X2) before reacting the compound represented by formula (X1) and the compound represented by formula (X2). In addition, the step Y0' which may be included in the manufacturing method of the first embodiment-1 is the same as the step Y0' which may be included in the manufacturing method of the second embodiment-1 described later, and the preferred embodiments are also the same. The procedure of the above-mentioned step Y0' will be explained later in the manufacturing method of the second embodiment.

[0112] In step X', the composition obtained by the coupling reaction between the compound represented by formula (X1) and the compound represented by formula (X2) is not subjected to column purification, and the composition is reacted with the first amine compound represented by formula (14). In order to further improve the purity of the target compound (9'), the composition contains at least the compound represented by formula (11A), and the content of the compound represented by formula (11B) is preferably 3.0 mass% or less, more preferably 1.0 mass% or less, based on the total solid content of the composition. By carrying out step Y0', the content of the compound represented by formula (11B) in the composition of step X' can be adjusted to 3.0 mass% or less, based on the total solid content of the composition. The lower limit of the content of the compound represented by formula (11B) is often 0 mass % or more, and often 0.01 mass % or more, based on the total solid content of the composition. The term "solid content" refers to the components in the composition excluding the solvent. Even if the components in the composition other than the solvent are in a liquid state, they are considered to be solid content.

[0113] In addition, if necessary, the composition may be purified by separation and purification means other than column purification (washing, extraction, drying, filtration, concentration, recrystallization, reprecipitation, crystallization, adsorption, centrifugation, etc.) after completion of the coupling reaction.

[0114] Specifically, the step of reacting the above composition with the first amine compound represented by formula (14) is preferably a step of adding the first amine compound represented by formula (14) to the above composition and heating to obtain the compound represented by formula (9'). The specific procedure is the same as step X of the manufacturing method of the above-mentioned first embodiment, and the preferred embodiments are also the same.

[0115] Second Embodiment The manufacturing method according to the second embodiment includes the following steps Y1 to Y4. Step Y1: A step of reacting the compound represented by the above formula (1) with a first amine compound represented by the following formula (3) to obtain a compound represented by the following formula (4): Step Y2: A step of reacting the compound represented by the above formula (4) with a second amine compound represented by the following formula (5) to obtain a compound represented by the following formula (6): Step Y3: Removal of the protecting group P from the compound represented by formula (6) 31 to obtain a compound represented by the following formula (7): Step Y4: A step of obtaining the compound represented by the above formula (2) from the compound represented by the above formula (7).

[0116] By the manufacturing method of the second embodiment, R 31 and R 51 The compound (2) having mutually different substituents represented by the following formula (2) can be produced with high purity. In the following, first, the compounds represented by formulas (3) to (7) will be explained, and then the procedures of steps Y1 to Y4 will be explained. (Compounds represented by formulas (3) to (7))

[0117] [ka]

[0118] In formula (3), R 31 represents a substituent. 31 represents a protecting group. In formula (3), R 31 The substituent represented by the formula (2) is R 31 and R 51 It has the same meaning as the substituent represented by the following formula: R of the first amine compound represented by formula (3) 31 The substituent represented by the formula (I) is R Y1 The same examples as those of the substituent represented by the following formula can be given, and the preferred embodiments are also the same.

[0119] P 31 The protecting group represented by the formula (I) is not particularly limited, and examples thereof include a (hetero)arylmethyl group (the (hetero)arylmethyl group refers to an arylmethyl group and a heteroarylmethyl group, and specific examples thereof include a benzyl group, a naphthylmethyl group, a 2-methoxybenzyl group, a p-methoxybenzyl group, a 2,4-dimethoxybenzyl group, a 3,4,5-trimethoxybenzyl group, a 3,4-dimethoxybenzyl group, a 2-thienylmethyl group, and a 2-furylmethyl group), a nitrobenzenesulfonyl group, a dinitrobenzenesulfonyl group, a tert-butoxycarbonyl group, an allyloxycarbonyl group, a benzyloxycarbonyl group, a methoxycarbonyl group, a 2,2,2-trichloroethoxycarbonyl group, a 9-fluorenylmethoxycarbonyl group, a trimethylsilylethoxycarbonyl group, and a (2-trimethylsilyl)ethanesulfonyl group, and the like, with a (hetero)arylmethyl group being preferred.

[0120] The first amine compound represented by formula (3) corresponds to the above-mentioned protected primary amine.

[0121] In formula (4), A 11 ~A 18 , and R 12 ~R 14are A in formula (1), 11 ~A 18 , and R 12 ~R 14 The same definition and preferred embodiment are also the same. 31 and P 31 are R in formula (3), 31 and P 31 The same definition and preferred embodiments are also the same.

[0122] In formula (5), R 51 The substituent represented by the formula (2) is R 51 The meaning and preferred embodiments of the substituent are also the same as those of the substituent represented by the following formula: The second amine compound represented by formula (5) has the same meaning as the primary amine represented by formula (Y1) described above, and the preferred embodiments are also the same.

[0123] In formula (6), A 11 ~A 18 , and R 14 are A in formula (1), 11 ~A 18 , and R 14 The same definition and preferred embodiment are also the same. 31 and P 31 are R in formula (3), 31 and P 31 The same definition and preferred embodiment are also the same. 51 is R in Eq. (5). 51 The same definition and preferred embodiments are also the same.

[0124] In formula (7), A 11 ~A 18 , and R 14 are A in formula (1), 11 ~A 18 , and R 14 The same definition and preferred embodiment are also the same. 31 is R in Eq. (3). 31 The same definition and preferred embodiment are also the same. 51 is R in Eq. (5). 51 The same definition and preferred embodiments are also the same.

[0125] Examples of the compound represented by formula (4), the compound represented by formula (6), and the compound represented by formula (7) are given below.

[0126] ≪Formula (4)≫ An example of the compound represented by formula (4) will be shown below, but the compound represented by formula (4) is not limited thereto. In the table below, (4)-1 to (4)-71 are R 11 , R 12 , R 13 , R 14 , R 31 , and P 31 In the table below, "Me" represents a methyl group, and "Et" represents an ethyl group. In addition, R shown in the basic structure below 81 and R 82 each independently represents a substituent selected from the group consisting of a hydrogen atom, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, a trifluoromethoxy group, a trichloromethyl group, a trichloromethoxy group, a 2-thiazolyl group, a 5-thiazolyl group, a 2-thienyl group, a 3-thienyl group, a styryl group, a 2-thiazolylvinyl group, a 5-thiazolylvinyl group, a 2-thienylvinyl group, a 3-thienylvinyl group, a phenylethynyl group, a 2-thiazolylethynyl group, a 5-thiazolylethynyl group, a 2-thienylethynyl group, a 3-thienylethynyl group, a trimethylsilylethynyl group, a triethylsilylethynyl group, a triisopropylethynyl group, and a 1-octynyl group. 81 and R 82 At least one of the groups is a substituent other than hydrogen.

[0127] [ka]

[0128] [ka]

[0129] [ka]

[0130] [Table 2]

[0131] ≪Formula (6)≫ An example of the compound represented by formula (6) is shown below, but the compound represented by formula (6) is not limited thereto. In the table below, (6)-1 to (6)-59 are R 11 , R 14 , R 31 , R 51 , and P 31 In the table below, "Me" represents a methyl group, and "Et" represents an ethyl group. In addition, R shown in the basic structure below 81 and R 82 each independently represents a substituent selected from the group consisting of a hydrogen atom, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, a trifluoromethoxy group, a trichloromethyl group, a trichloromethoxy group, a 2-thiazolyl group, a 5-thiazolyl group, a 2-thienyl group, a 3-thienyl group, a styryl group, a 2-thiazolylvinyl group, a 5-thiazolylvinyl group, a 2-thienylvinyl group, a 3-thienylvinyl group, a phenylethynyl group, a 2-thiazolylethynyl group, a 5-thiazolylethynyl group, a 2-thienylethynyl group, a 3-thienylethynyl group, a trimethylsilylethynyl group, a triethylsilylethynyl group, a triisopropylethynyl group, and a 1-octynyl group. 81 and R 82 At least one of the groups is a substituent other than hydrogen.

[0132] [ka]

[0133] [ka]

[0134] [ka]

[0135] [Table 3]

[0136] ≪Formula (7)≫ In the following, an example of the compound represented by formula (7) is shown, but the compound represented by formula (7) is not limited thereto. In addition, (7)-1 to (7)-54 in the following table represent R 11 , R 14 , R 31 , and R 51 In the table below, "Me" represents a methyl group, and "Et" represents an ethyl group. In addition, R shown in the basic structure below 81 and R 82 each independently represents a substituent selected from the group consisting of a hydrogen atom, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, a trifluoromethoxy group, a trichloromethyl group, a trichloromethoxy group, a 2-thiazolyl group, a 5-thiazolyl group, a 2-thienyl group, a 3-thienyl group, a styryl group, a 2-thiazolylvinyl group, a 5-thiazolylvinyl group, a 2-thienylvinyl group, a 3-thienylvinyl group, a phenylethynyl group, a 2-thiazolylethynyl group, a 5-thiazolylethynyl group, a 2-thienylethynyl group, a 3-thienylethynyl group, a trimethylsilylethynyl group, a triethylsilylethynyl group, a triisopropylethynyl group, and a 1-octynyl group. 81 and R 82 At least one of the groups is a substituent other than hydrogen.

[0137] [ka]

[0138] [ka]

[0139] [ka]

[0140] [Table 4]

[0141] (Process Y1) Step Y1 is a step of reacting a compound represented by formula (1) with a first amine compound represented by formula (3) to obtain a compound represented by formula (4). Specifically, step Y1 is preferably a step of heating a composition containing the compound represented by formula (1) and the first amine compound represented by formula (3) to obtain a compound represented by formula (4).

[0142] In the above step Y1, -COOR in the compound represented by formula (1) 11 , -COOR 12 , -COOR 13 , and / or -COOR 14 An amidation reaction between the first amine compound and the second amine compound may occur. If necessary, the resulting crude product is purified by a separation and purification means including washing, extraction, drying, filtration, concentration, recrystallization, reprecipitation, crystallization, centrifugation, adsorption, and / or column purification to obtain the compound represented by formula (4).

[0143] The amount of the first amine compound represented by formula (3) used is preferably 1.0 to 10 molar equivalents, and more preferably 1.0 to 5.0 molar equivalents, relative to 1 molar equivalent of the compound represented by formula (1).

[0144] The composition may include a solvent. The solvent may be used alone or in combination of two or more. The solvent is not particularly limited, but examples thereof include hydrocarbon solvents, ether solvents, amide solvents, alcohol solvents, nitrile solvents, and sulfoxide solvents. Examples of the hydrocarbon solvent include pentane, hexane, heptane, octane, decane, toluene, ethylbenzene, xylene, diethylbenzene, fluorobenzene, trifluoromethylbenzene, chlorobenzene, chloroform, dichloromethane, 1,1,2,2-tetrachloroethane, 1,1,2-trichloroethane, dichlorobenzene, trichlorobenzene, mesitylene, amylbenzene, decalin, 1-methylnaphthalene, 1-ethylnaphthalene, 1-chloronaphthalene, 1-fluoronaphthalene, 1,6-dimethylnaphthalene, benzonitrile, nitrobenzene, and tetralin. Ether solvents include anisole, diethyl ether, dibutyl ether, diisopropyl ether, cyclopentyl methyl ether, diphenyl ether, tetrahydropyran, dioxane, dimethoxyethane, diethoxyethane, and tetrahydrofuran. Examples of the amide solvent include N,N-dimethylformamide, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, and N,N-dimethylacetamide. Examples of the alcohol solvent include methanol, ethanol, propanol, isopropanol, amyl alcohol, benzyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, and glycerin. Examples of the nitrile solvent include acetonitrile, propylonitrile, and benzonitrile. Sulfoxide solvents include dimethyl sulfoxide, sulfolane, and the like.

[0145] Of the above solvents, those having a boiling point of 70° C. or higher are preferred, and those having a boiling point of 90° C. or higher are more preferred. Examples of solvents having a boiling point of 90° C. or higher include heptane, octane, decane, toluene, ethylbenzene, xylene, diethylbenzene, fluorobenzene, trifluoromethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, mesitylene, amylbenzene, decalin, 1-methylnaphthalene, 1-ethylnaphthalene, 1-chloronaphthalene, 1-fluoronaphthalene, 1,6-dimethylnaphthalene, 1,1,2,2-tetrachloroethane, 1,1,2-trichloroethane, nitrobenzene, benzonitrile, tetralin, Examples of the solvent include anisole, dibutyl ether, cyclopentyl methyl ether, diphenyl ether, dioxane, diethoxyethane, N,N-dimethylformamide, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylacetamide, 1-propanol, 1-butanol, isobutyl alcohol, 2-butanol, amyl alcohol, benzyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, glycerin, dimethyl sulfoxide, and sulfolane.

[0146] When the composition contains a solvent, the content of the solvent is preferably 75.0 to 99.9 mass %, more preferably 80.0 to 98.0 mass %, based on the total mass of the composition.

[0147] The reaction temperature is not particularly limited, but is preferably from 20 to 250°C, more preferably from 50 to 200°C. The reaction time varies depending on reaction conditions including the solvent used and the reaction temperature, but is usually 1 to 24 hours, preferably 1 to 20 hours.

[0148] (Process Y2) Step Y2 is a step of reacting a compound represented by formula (4) with a second amine compound represented by formula (5) to obtain a compound represented by formula (6). Specifically, step Y2 is preferably a step of heating a composition containing a compound represented by formula (4) and a second amine compound represented by formula (5) to obtain a compound represented by formula (6).

[0149] In step Y2, two adjacent ester groups (-COOR 12 and -COOR 13 An amidation / imidization reaction occurs between the amine compound and a second amine compound to form an imide bond.

[0150] The amount of the second amine compound represented by formula (5) used is preferably 1.0 to 10.0 molar equivalents, and more preferably 1.0 to 5.0 molar equivalents, relative to 1 molar equivalent of the compound represented by formula (4).

[0151] The composition may include a solvent. The solvent may be used alone or in combination of two or more. The solvent is not particularly limited, and examples thereof include the solvents listed in step Y1, and the preferred embodiments are also the same.

[0152] When the composition contains a solvent, the content of the solvent is preferably 75.0 to 99.9 mass %, more preferably 80.0 to 98.0 mass %, based on the total mass of the composition.

[0153] The reaction temperature is not particularly limited, but is preferably from 20 to 250°C, more preferably from 50 to 200°C. The reaction time varies depending on reaction conditions including the solvent used and the reaction temperature, but is usually 1 to 24 hours, preferably 1 to 20 hours. After completion of the reaction, the obtained compound represented by formula (6) may be purified, if necessary, by a separation and purification means including washing, extraction, drying, filtration, concentration, recrystallization, reprecipitation, crystallization, centrifugation, column purification, adsorption, and / or sublimation purification.

[0154] (Process Y3) In step Y3, a protecting group P is reacted with the compound represented by formula (6). 31 (deprotection) to obtain a compound represented by formula (7). Examples of the deprotection method include a method using a deprotection reagent under acidic or basic conditions, a method using an oxidizing agent, a method using a Lewis acid, a method using a nucleophile, a method of performing a reductive deprotection reaction (hydrogenolysis) in the presence of a metal catalyst, and a method using zinc under acidic conditions. Examples of deprotection reagents under acidic conditions include acids such as hydrochloric acid, hydrogen bromide / acetic acid, sulfuric acid, formic acid, methanesulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid. 31 When the protecting group represented by the formula: is a (hetero)arylmethyl group such as a methoxybenzyl group, sulfonic acids such as sulfuric acid, methanesulfonic acid, or p-toluenesulfonic acid are preferred. The deprotection reagent under basic conditions may be either an inorganic base or an organic base. Examples of the inorganic base include hydroxides of alkali metals and alkaline earth metals, as well as carbonates and hydrogen carbonates. Examples of the organic base include amines such as triethylamine, diisopropylethylamine, piperidine, N-methylmorpholine, dimethylaminopyridine, DBU (1,8-diazabicyclo[5.4.0]-7-undecene), and DBN (1,5-diazabicyclo[4.3.0]non-5-ene), pyridine, and imidazole. The oxidizing agent includes 2,3-dichloro-5,6-dicyano-p-benzoquinone. Lewis acids include trimethylsilyl trifluoromethanesulfonate, iodotrimethylsilane, boron trichloride, and tin(IV) chloride. Nucleophiles include thiol compounds (such as benzenethiol), cesium fluoride, and fluoride ions such as tetraalkylammonium fluorides. Examples of metal catalysts used as deprotection reagents include palladium catalysts (e.g., palladium on carbon, palladium hydroxide on carbon, palladium oxide, etc.), platinum catalysts (e.g., platinum on carbon, platinum oxide, etc.), rhodium catalysts (e.g., rhodium on carbon), and ruthenium catalysts (e.g., ruthenium on carbon).

[0155] The deprotection reaction is preferably carried out in the presence of a solvent. The solvent may be used alone or in combination of two or more. The solvent is not particularly limited, and examples thereof include the solvents listed in step Y1. Ester solvents (methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, etc.) and ketone solvents (acetone, 2-butanone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, isophorone, acetophenone, etc.) may also be used. When an acid or base is used, water alone or a mixture of water and the solvent may be used. In addition, the step Y3 and the step Y4 described later may be carried out simultaneously. Specifically, for example, a method of heating a composition containing a deprotection reagent, a compound represented by formula (6), and a solvent may be mentioned.

[0156] (Process Y4) Step Y4 is a step of obtaining a compound represented by formula (2) from a compound represented by formula (7). Specifically, step Y4 is preferably a step of obtaining a compound represented by formula (2) by heating a composition containing a compound represented by formula (7).

[0157] In the above step Y4, -COOR in the compound represented by formula (7) 14 An imidization reaction occurs between the amide group and the compound represented by formula (2).

[0158] The composition may include a solvent. The solvent may be used alone or in combination of two or more. The solvent is not particularly limited, and examples thereof include the solvents listed in step Y1, and the preferred embodiments are also the same.

[0159] When the composition contains a solvent, the content of the solvent is preferably 75.0 to 99.9 mass %, more preferably 80.0 to 98.0 mass %, based on the total mass of the composition.

[0160] The reaction temperature is not particularly limited, but is preferably from 20 to 250°C, more preferably from 50 to 200°C. The reaction time varies depending on reaction conditions including the solvent used and the reaction temperature, but is usually 1 to 24 hours, preferably 1 to 20 hours. After completion of the reaction, if necessary, the obtained compound represented by formula (7) may be purified by a separation and purification means including washing, extraction, drying, filtration, concentration, recrystallization, reprecipitation, crystallization, centrifugation, column purification, adsorption, and / or sublimation purification, and is preferably purified by a separation and purification means including sublimation purification.

[0161] As described above, the compound represented by formula (1) is preferably a compound represented by formula (8), and the compound represented by formula (2) is preferably a compound represented by formula (9). In the following, a preferred embodiment (hereinafter also referred to as "second embodiment-1") of the production method for producing a compound represented by formula (9) from a compound represented by formula (8) (the latter formula (11A) corresponds to formula (8)) will be described.

[0162] (Preferred embodiment of the method for producing the compound represented by formula (9) (Second embodiment-1)) The manufacturing method of the second embodiment-1 includes the following steps Y1' to Y4'. Step Y1': A step of reacting a compound represented by the following formula (X1) with a compound represented by the following formula (X2) to obtain a composition containing a compound represented by the following formula (11A) and a compound represented by the following formula (11B), and then reacting the composition with a first amine compound represented by the following formula (12) without performing column purification on the composition to obtain a compound represented by the following formula (13). Step Y2': A step of reacting the compound represented by the above formula (13) with a second amine compound represented by the following formula (14) to obtain a compound represented by the following formula (15): Step Y3': Removal of the protecting group P from the compound represented by the above formula (15) 31 to obtain a compound represented by the following formula (16): Step Y4': A step of obtaining a compound represented by the above formula (9) from a compound represented by the above formula (16).

[0163] The manufacturing method of the above-mentioned second embodiment-1 preferably further includes the following step Y0′. Step Y0': A step of purifying the compound represented by the formula (X2) before reacting the compound represented by the formula (X1) with the compound represented by the formula (X2).

[0164] In the following, first, the compounds represented by formula (X1), formula (X2), formula (11A), formula (11B), and formula (12) to formula (16) will be explained, and then the procedures of each of steps Y0' to Y4' will be explained. (Compounds represented by formula (X1), formula (X2), formula (11A), formula (11B), formula (12) to formula (16))

[0165] [ka]

[0166] [ka]

[0167] In formula (X1), X 1 ~X 4 are each a halogen atom or -CO-OR 101 Represents R 101 represents an aliphatic hydrocarbon group, an aryl group, or a heteroaryl group. 1 and X 4 One of these represents a halogen atom, and the other represents -CO-OR 101 Also, X 2 and X 3 One of these represents a halogen atom, and the other represents -CO-OR 101 Represents. Furthermore, from the viewpoint of ease of production of raw materials, X of the compound represented by formula (X1) 2 and X 4 -CO-OR 101 represents X1 and X 3 It is preferred that represents a halogen atom.

[0168] The two R's present in formula (X1) 101 Preferably, each of the groups represents an aliphatic hydrocarbon group, or each of the groups represents an aryl group or a heteroaryl group, and more preferably, each of the groups represents an aliphatic hydrocarbon group. R in formula (X1) 101 The aliphatic hydrocarbon group, aryl group, and heteroaryl group represented by the formula (1) are 11 ~R 14 The meanings and preferred embodiments of the aliphatic hydrocarbon group, aryl group, or heteroaryl group are the same as those of the aliphatic hydrocarbon group, aryl group, or heteroaryl group represented by the following formula: R 81 ~R 86 are R in formula (8), 81 ~R 86 The same definition and preferred embodiments are also the same.

[0169] In formula (X2), R 101 R in formula (X2) represents an aliphatic hydrocarbon group, an aryl group, or a heteroaryl group. 101 The aliphatic hydrocarbon group, aryl group, and heteroaryl group represented by the formula (1) are 11 ~R 14 The meanings and preferred embodiments of the aliphatic hydrocarbon group, aryl group, or heteroaryl group represented by the following formula (I) are the same as those of the aliphatic hydrocarbon group, aryl group, or heteroaryl group represented by the following formula (I), and the preferred embodiments are also the same. R in formula (X2) 101 More preferably, represents an aryl group or a heteroaryl group. The compound represented by formula (X2) is preferably an aryl formate or a heteroaryl formate, and more preferably an aryl formate substituted with an electron-withdrawing group.

[0170] In formula (11A), X 5 ~X 8 Each independently represents -CO-OR 101 However, X 5 R in 101 And, X 8 R in 101That is, X 5 R in 101 and X 8 R in 101 One of X represents an aliphatic hydrocarbon group, and the other represents an aryl group or a heteroaryl group. 6 R in 101 and X 7 R in 101 That is, X 6 R in 101 and X 7 R in 101 One of these represents an aliphatic hydrocarbon group, and the other represents an aryl group or a heteroaryl group. X 5 ~X 8 R in 101 The aliphatic hydrocarbon group, aryl group, and heteroaryl group represented by the formula (1) are 11 ~R 14 The meanings and preferred embodiments of the aliphatic hydrocarbon group, aryl group, or heteroaryl group represented by the following formula (I) are the same as those of the aliphatic hydrocarbon group, aryl group, or heteroaryl group represented by the following formula (I), and the preferred embodiments are also the same. R 81 ~R 86 are R in formula (8), 81 ~R 86 The same definition and preferred embodiments are also the same. In the formula (11A), X 6 and X 8 R in 101 represents an aliphatic hydrocarbon group, and X 5 and X 7 R in 101 Preferably, represents an aryl or heteroaryl group. R 81 ~R 86 are R in formula (8), 81 ~R 86 The same definition and preferred embodiments are also the same.

[0171] In formula (11B), X 9 and X 10 One of the groups represents a hydrogen atom, and the other group represents -CO-OR 101 Represents R 101 is R in formula (X1). 101The same definition and preferred form are also the same. 6 and X 7 Each of them represents X in formula (11A). 6 and X 7 The same definition and preferred embodiments are also the same. R 81 ~R 86 are R in formula (8), 81 ~R 86 The same definition and preferred embodiments are also the same. As the formula (11B), X 9 represents a hydrogen atom, and X 10 -CO-OR 101 It is preferable that X represents 10 R in 101 and X 6 R in 101 Preferably, each of the groups represents an aliphatic hydrocarbon group, or each of the groups represents an aryl group or a heteroaryl group, and more preferably, each of the groups represents an aliphatic hydrocarbon group.

[0172] Formula (12) has the same meaning as the above-mentioned formula (3), and the preferred embodiments are also the same. 31 represents a substituent. 31 represents a protecting group.

[0173] In formula (13), X 11 and X 12 On the other hand, -CO-OR 101 and the other represents -CO-N(R 31 )(P 31 ) stands for R 101 is R in formula (X1). 101 The same meaning and preferred form are also the same. 31 and P 31 are R in formula (12), 31 and P 31 X 6 and X 7 Each of them represents X in formula (11A). 6 and X 7 The same definition and preferred embodiment are also the same. 81 ~R 86 are R in formula (8), 81~R 86 The same definition and preferred embodiments are also the same. As for formula (13), X 11 -CO-N(R 31 )(P 31 ), and X 12 -CO-OR 101 It is preferred that

[0174] Formula (14) has the same meaning as the above-mentioned formula (5), and the preferred embodiments are also the same. 51 represents a substituent.

[0175] In formula (15), X 11 and X 12 are X in formula (13), 11 and X 12 Synonymous with R. 51 is R in Eq. (14). 51 Synonymous with R. 81 ~R 86 are R in formula (8), 81 ~R 86 The same definition and preferred embodiments are also the same.

[0176] In formula (16), X 13 and X 14 On the other hand, -CO-OR 101 and the other represents -CO-N(R 31 )(H). R 51 is R in Eq. (14). 51 Synonymous with R. 101 is R in formula (X1). 101 The same meaning and preferred form are also the same. 81 ~R 86 are R in formula (8), 81 ~R 86 The same definition and preferred embodiments are also the same. As for formula (16), X 13 -CO-N(R 31 )(H), X 14 -CO-OR 101 It is preferred that

[0177] (Process Y1') Step Y1' is a step of reacting a compound represented by formula (X1) with a compound represented by formula (X2) to obtain a composition containing a compound represented by formula (11A) and a compound represented by formula (11B), and then reacting the composition with a first amine compound represented by formula (12) without column purification to obtain a compound represented by formula (13). The compound represented by formula (11A) corresponds to the compound represented by formula (8) described above.

[0178] In step Y1', the compound represented by formula (11B) is a by-product in the synthesis reaction in which the compound represented by formula (X1) and the compound represented by formula (X2) are reacted to obtain the compound represented by formula (11A). It is presumed that the compound represented by formula (11B) is produced as a by-product due to formic acid that may be contained as an impurity in the compound represented by formula (X2) (for example, 2,4,6-trichlorophenyl formate, etc., as the compound represented by formula (X2)). In step Y1', the by-production of the compound represented by formula (11B) can be suppressed by carrying out a step (step Y0') of purifying the compound represented by formula (X2) before reacting the compound represented by formula (X1) and the compound represented by formula (X2). The purification method in step Y0' is not particularly limited, but examples of the purification method include separation and purification means including washing, extraction, drying, filtration, concentration, recrystallization, reprecipitation, crystallization, centrifugation, column purification, adsorption, and / or sublimation purification. Among these, recrystallization, reprecipitation, and crystallization are preferred, and recrystallization is particularly preferred.

[0179] The reaction between the compound represented by formula (X1) and the compound represented by formula (X2) is not particularly limited, and a cross-coupling method in the presence of a transition metal catalyst can be applied.

[0180] The amounts of the compound represented by formula (X1) and the compound represented by formula (X2) used in the coupling reaction are not particularly limited, and the amount of the compound represented by formula (X2) used relative to 1 molar equivalent of the halogen atom in the compound represented by formula (X1) is preferably 1.0 to 15.0 molar equivalents, more preferably 1.0 to 10.0 molar equivalents, and even more preferably 1.0 to 5.0 molar equivalents.

[0181] The transition metal catalyst is not particularly limited, but examples thereof include palladium catalysts (palladium (0) catalysts or palladium (II) catalysts), nickel catalysts (nickel (0) catalysts), iron catalysts (iron (III) catalysts), cobalt catalysts (cobalt (II) catalysts), and iridium catalysts (iridium (0) catalysts). Among these, palladium catalysts or nickel catalysts are preferred, and palladium catalysts are more preferred. The palladium catalyst is not particularly limited, but examples thereof include palladium acetate, tris(dibenzylideneacetone)dipalladium(0) chloroform complex, tetrakis(triphenylphosphine)palladium(0), and dichlorobis[di-tert-butyl(4-dimethylaminophenyl)phosphine]palladium(II).

[0182] The amount of the transition metal catalyst used in the coupling reaction is not particularly limited as long as it is an amount that acts as a catalyst, but is preferably 0.001 to 1.0 molar equivalent, and more preferably 0.01 to 0.5 molar equivalent, relative to 1 molar equivalent of the halogen atom of the compound represented by formula (X1).

[0183] The coupling reaction may be carried out by adding a ligand. The ligand is not particularly limited, and for example, the ligands described in ACCOUNTS OF CHEMICAL RESEARCH 2008, 41, 1461-1473, Angew. Chem. Int. Ed. 2008, 47, 6338-6361Angew. Chem. Int. Ed. 2008, 47, 6338-6361, Journal of the Society of Organic Synthesis Chemistry 2001, 59, 607-616, Aldrichimica Acta 2006,39, 17. (b) Schlummer, B.; Scholz, U. Adv. Synth. Catal. 2004, 346, 1599. can be used. The coupling reaction may be carried out in the presence of a base. Examples of the base include organic bases and inorganic bases, and organic bases are preferred. Examples of the organic base include tertiary amines (e.g., trimethylamine, dimethylisopropylamine, N,N,N',N'-Tetramethyldiaminomethane, N,N,N',N'-Tetramethylethylenediamine, triethylamine, diisopropylethylamine, tripropylamine, tributylamine, tripentylamine, triheptylamine, trioctylamine, diazabicycloundecene, diazabicyclononene, and 1,4-diazabicyclo[2.2.2]octane, etc.), and pyridines (e.g., pyridine, 2,6-lutidine, quinoline, and isoquinoline, etc.). Examples of the inorganic base include hydroxides, carbonates, phosphates, and acetates. More specifically, examples include sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium phosphate, potassium phosphate, and sodium acetate.

[0184] The base may be used alone or in combination of two or more kinds. The amount of the base used is not particularly limited, but is preferably 1.0 to 15 molar equivalents, more preferably 1.0 to 10 molar equivalents, and even more preferably 1.1 to 2.0 molar equivalents relative to 1 molar equivalent of the compound represented by formula (X2).

[0185] The coupling reaction may be carried out in the presence of a solvent. The solvent may be used alone or in combination of two or more. The solvent is not particularly limited, and any solvent that is used in transition metal catalyzed reactions can be used, such as hydrocarbon solvents, ether solvents, amide solvents, ester solvents, nitrile solvents, ketone solvents, and sulfoxide solvents. Examples of the hydrocarbon solvent include pentane, hexane, heptane, octane, decane, toluene, ethylbenzene, xylene, diethylbenzene, fluorobenzene, trifluoromethylbenzene, chloroform, dichloromethane, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, dichlorobenzene, trichlorobenzene, mesitylene, amylbenzene, decalin, 1-methylnaphthalene, 1-ethylnaphthalene, 1-chloronaphthalene, 1-fluoronaphthalene, 1,6-dimethylnaphthalene, nitrobenzene, benzonitrile, and tetralin. Examples of the ether solvent include anisole, diethyl ether, dibutyl ether, diisopropyl ether, cyclopentyl methyl ether, diphenyl ether, tetrahydropyran, dioxane, dimethoxyethane, diethoxyethane, and tetrahydrofuran. Examples of the amide solvent include N,N-dimethylformamide, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, and N,N-dimethylacetamide. Ester solvents include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and isobutyl acetate. Nitrile solvents include acetonitrile, propylonitrile, and benzonitrile. Ketone solvents include acetone, 2-butanone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, isophorone, and acetophenone. Sulfoxide solvents include dimethyl sulfoxide, sulfolane, and the like.

[0186] The coupling reaction may be carried out under an inert gas atmosphere, including nitrogen, helium, and argon. The reaction temperature for the coupling reaction is not particularly limited, but is preferably 0 to 200°C, more preferably 50 to 150°C. The reaction time for the coupling reaction varies depending on reaction conditions including the solvent used and the reaction temperature, but is usually 1 to 24 hours, preferably 3 to 20 hours.

[0187] In step Y1', the composition obtained by the coupling reaction of the compound represented by formula (X1) and the compound represented by formula (X2) is not subjected to column purification, and the composition is reacted with a first amine compound represented by formula (12). In order to further improve the purity of the target compound (9), the composition contains at least a compound represented by formula (11A), and the content of the compound represented by formula (11B) is preferably 3.0 mass% or less, more preferably 1.0 mass% or less, based on the total solid content of the composition. By carrying out step Y0', the content of the compound represented by formula (11B) in the composition in step Y1' can be adjusted to 3.0 mass% or less, based on the total solid content of the composition. The lower limit of the content of the compound represented by formula (11B) is often 0 mass % or more, and often 0.01 mass % or more, based on the total solid content of the composition. The term "solid content" refers to the components in the composition excluding the solvent. Even if the components in the composition other than the solvent are in a liquid state, they are considered to be solid content.

[0188] In addition, if necessary, the composition may be purified by separation and purification means other than column purification (washing, extraction, drying, filtration, concentration, recrystallization, reprecipitation, crystallization, adsorption, centrifugation, etc.) after completion of the coupling reaction.

[0189] Specifically, the step of reacting the above composition with the first amine compound represented by formula (12) is preferably a step of adding the first amine compound represented by formula (12) to the above composition and heating the mixture to obtain a compound represented by formula (13). The specific procedure is similar to step Y1 of the manufacturing method of the second embodiment described above, and the preferred embodiments are also similar.

[0190] (Process Y2') Step Y2' is similar to step Y2 of the manufacturing method of the second embodiment described above, and the preferred embodiments are also similar.

[0191] (Process Y3') Step Y3' is similar to step Y3 in the manufacturing method of the second embodiment described above, and the preferred embodiments are also similar.

[0192] (Process Y4') Step Y4' is similar to step Y4 in the manufacturing method of the second embodiment described above, and the preferred embodiments are also similar.

[0193] [Composition] The present invention also relates to a composition. The composition of the present invention is a composition used for synthesizing a compound represented by the above formula (9), Contains at least a compound represented by the above formula (8), In the above composition, the total content of the compound represented by the following formula (17) and the compound represented by the following formula (18) is 3.0 mass % or less based on the total solid content of the composition. The term "solid content" refers to the components in the composition excluding the solvent. Even if the components in the composition other than the solvent are in a liquid state, they are considered to be solid content.

[0194] [ka]

[0195] In formula (17) and formula (18), R 11 ~R 14each independently represents an aliphatic hydrocarbon group, an aryl group, or a heteroaryl group. 12 and R 13 One of these represents an aliphatic hydrocarbon group, and the other represents an aryl group or a heteroaryl group. R 81 ~R 86 are R in formula (8), 81 ~R 86 The same definition and preferred embodiments are also the same.

[0196] The above composition is the same as the composition obtained by reacting the compound represented by formula (X1) with the compound represented by formula (X2) in step X' in the manufacturing method of the first embodiment-1 described above, and the composition obtained by reacting the compound represented by formula (X1) with the compound represented by formula (X2) in step Y1' in the manufacturing method of the second embodiment-1 described above. That is, the compound represented by formula (8) above corresponds to the compound represented by formula (11A) above. In addition, the compounds represented by formulas (17) and (18) above are compounds included in the compound represented by formula (11B) above, and the compound represented by formula (17) above corresponds to the compound represented by formula (11B) with X. 9 represents a hydrogen atom, and X 10 -CO-OR 101 The compound represented by the above formula (18) corresponds to the compound represented by the formula (11B) in which X 9 -CO-OR 101 represents X 10 represents a hydrogen atom.

[0197] The preferred embodiment of the compound represented by formula (8) is the same as the preferred embodiment of the compound represented by formula (11A). The preferred embodiment of the compound represented by formula (17) is the same as the preferred embodiment of the compound represented by formula (11B).

[0198] In addition, in formula (18), R 11 and R 13Preferably, each of the groups represents an aliphatic hydrocarbon group, or each of the groups represents an aryl group or a heteroaryl group, and more preferably, each of the groups represents an aliphatic hydrocarbon group.

[0199] In addition, the lower limit of the total content of the compound represented by formula (17) and the compound represented by formula (18) in the above composition is often 0 mass% or more, and often 0.01 mass% or more, based on the total solid content of the composition. In the composition, the content of the compound represented by formula (8) is preferably 94.0% by mass or more, more preferably more than 97.0% by mass, and even more preferably 98.0% by mass or more, based on the total amount of the composition. The upper limit of the content of the compound represented by formula (8) in the composition is not particularly limited, but is 100% by mass or less, and preferably 99.99% by mass or less.

[0200] [Compound] The present invention also relates to novel compounds. The compounds of the present invention are a compound represented by the above formula (4), a compound represented by the above formula (6), and a compound represented by the above formula (7), as well as a compound represented by the following formula (11A') and a compound represented by the following formula (11A''), and any of the compounds can be used as an intermediate compound for obtaining a compound represented by the above formula (2).

[0201] [Compound represented by formula (11A')] The compound represented by formula (11A') will be described below. The compound represented by formula (11A') is a compound included in the compound represented by the above formula (11A). That is, in the compound represented by the above formula (11A), R 81 ~R 86 Among these, at least one of them corresponds to a form representing a substituent. 81 and R 82 At least one of R preferably represents a substituent. 81 and R 82 It is more preferred that both of the groups represent substituents. The preferred embodiments of the compound represented by formula (11A') are the same as the preferred embodiments of the compound represented by formula (11A) described above.

[0202] [ka]

[0203] An example of the compound represented by formula (11A') will be shown below, but the compound represented by formula (11A') is not limited thereto. In the table below, (8)-1 to (8)-43 are the X's shown in each basic skeleton shown below. 5 , X 6 , X 7 , X 8 , R 81 , and R 82 In the table below, "Me" represents a methyl group, and "Et" represents an ethyl group. In the table below, "ester" and "CO2" refer to an oxycarbonyl group. That is, "2,4,6-trichlorophenylester" refers to "2,4,6-trichlorophenyloxycarbonyl," and "CO2Me" refers to "methoxycarbonyl."

[0204] [ka]

[0205] [ka]

[0206] [Compound represented by formula (11A″)] The compound represented by formula (11A″) will be described below. The compound represented by formula (11A″) is a compound included in the compound represented by formula (11A) described above.

[0207] [ka]

[0208] In formula (11A''), X 5 ~X 8 Each independently represents -CO-OR 101 Represents R 101 each independently represents an aliphatic hydrocarbon group, an aryl group, or a heteroaryl group. However, X 5 R in 101 And, X 8 R in 101 One represents an aliphatic hydrocarbon group and the other represents an aryl group or a heteroaryl group. 6 R in 101 and X 7 R in 101 where one represents an aliphatic hydrocarbon group and the other represents an aryl group or a heteroaryl group. 101 When the aliphatic hydrocarbon group of is an aliphatic hydrocarbon group having one carbon atom, R 101 The aryl group represents an unsubstituted or substituted aryl group with two or less substituents. R 83 ~R 86 each independently represents a hydrogen atom or a substituent.

[0209] R 101 When the aliphatic hydrocarbon group of R has 2 or more carbon atoms, 101 It has been confirmed that, compared to when the aliphatic hydrocarbon group has one carbon atom, the solubility of the compound is superior, which has synthetic advantages such as the ability to reduce the amount of reaction solvent, and that the yield can be superior in some cases.

[0210] The preferred embodiments of the compound represented by formula (11A″) are the same as the preferred embodiments of the compound represented by formula (11A) described above.

[0211] An example of the compound represented by formula (11A'') will be shown below, but the compound represented by formula (11A'') is not limited thereto. In the table below, (9)-1 to (9)-38 are the X's shown in each basic skeleton shown below.5 , X 6 , X 7 , and X 8 In the table below, "Me" represents a methyl group, and "Et" represents an ethyl group. In the table below, "ester" and "CO2" refer to an oxycarbonyl group. That is, "2,4,6-trichlorophenylester" refers to "2,4,6-trichlorophenyloxycarbonyl," and "CO2Me" refers to "methoxycarbonyl."

[0212] [ka]

[0213] [ka]

[0214] [Application] The cyclic imide compound obtained by the production method of the present invention is used as a material for forming an organic semiconductor film in an electronic device such as an organic thin film transistor, as described below. Examples of such devices include organic thin-film transistors that control the amount of current or voltage, organic photoelectric conversion elements that convert light energy into electricity (for example, solid-state imaging elements used as photosensors, and solar cells used for energy conversion), organic thermoelectric conversion elements that convert thermal energy into electricity, organic electroluminescence elements, (gas) sensors, organic rectifying elements, organic inverters, and information recording elements.

[0215] [Composition for organic thin film transistors] Next, the composition for an organic thin film transistor will be described. The composition for organic thin film transistors (also referred to simply as "organic semiconductor composition" in this specification) contains a cyclic imide compound (hereinafter also referred to as a "specific cyclic imide compound") obtained by the manufacturing method of the present invention, and is used for forming an organic semiconductor film of an organic thin film transistor. The specific cyclic imide compound contained in the organic semiconductor composition is as described above, and one type may be used alone, or two or more types may be used in combination. The content of the specific cyclic imide compound in the organic semiconductor composition can be expressed as the content in the solid content excluding the solvent described later, and it is preferable that the content of the specific cyclic imide compound relative to the total mass of the solid content in the organic semiconductor composition is within a suitable range of the content of the specific cyclic imide compound relative to the total mass of the organic semiconductor film described later, for example.

[0216] [Binder Polymer] The organic semiconductor composition may contain a binder polymer. In terms of obtaining an organic semiconductor film with high film quality, the organic semiconductor composition preferably contains a binder polymer. The type of binder polymer is not particularly limited, and known binder polymers can be used. Examples of binder polymers include insulating polymers including polystyrene, poly(α-methylstyrene), polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose, polyethylene, and polypropylene, and copolymers thereof. In addition to these, examples of the rubber include ethylene-propylene rubber, acrylonitrile-butadiene rubber, hydrogenated nitrile rubber, fluororubber, perfluoroelastomer, tetrafluoroethylene propylene copolymer, ethylene-propylene-diene copolymer, styrene-butadiene rubber, polychloroprene, polyneoprene, butyl rubber, methylphenyl silicone resin, methylphenylvinyl silicone resin, methylvinyl silicone resin, fluorosilicone resin, acrylic rubber, ethylene acrylic rubber, chlorosulfonated polyethylene, chloropolyethylene, epichlorohydrin copolymer, polyisoprene-natural rubber copolymer, polyisoprene rubber, styrene-isoprene block copolymer, polyester urethane copolymer, polyether urethane copolymer, polyether ester thermoplastic elastomer, and rubber containing polybutadiene rubber, as well as thermoplastic elastomer polymers. Further examples include photoconductive polymers including polyvinylcarbazole and polysilane, conductive polymers including polythiophene, polypyrrole, polyaniline, and polyparaphenylenevinylene, and semiconducting polymers described in Chemistry of Materials, 2014, 26, 647.

[0217] Considering the charge mobility, the binder polymer preferably has a structure that does not contain a polar group. Here, the polar group refers to a functional group that has a heteroatom other than carbon and hydrogen atoms. Since it has a structure that does not contain a polar group, the binder polymer is preferably polystyrene or poly(α-methylstyrene). Semiconductor polymers are also preferred.

[0218] The glass transition temperature of the binder polymer is not particularly limited and is appropriately set depending on the application. For example, when imparting strong mechanical strength to the organic semiconductor film, it is preferable to increase the glass transition temperature. On the other hand, when imparting flexibility to the organic semiconductor film, it is preferable to decrease the glass transition temperature.

[0219] The binder polymer may be used alone or in combination of two or more kinds. The content of the binder polymer in the organic semiconductor composition is not particularly limited, but from the viewpoint of further improving the carrier mobility and durability of the organic semiconductor film of the organic thin film transistor, it is preferable that the content of the binder polymer relative to the total mass of the solid contents in the organic semiconductor composition is within a suitable range of the content of the binder polymer relative to the total mass of the organic semiconductor film described below. The weight average molecular weight of the binder polymer is not particularly limited, but is preferably from 1,000 to 10 million, more preferably from 3,000 to 5 million, and even more preferably from 5,000 to 3 million. The weight average molecular weight of the binder polymer can be determined by gel permeation chromatography (GPC).

[0220] In the organic semiconductor composition, the specific cyclic imide compound may be uniformly mixed with the binder polymer, or a part or all of the specific cyclic imide compound may be phase-separated from the binder polymer. From the viewpoint of ease of application or uniformity of application, it is preferable that the specific cyclic imide compound and the binder polymer are uniformly mixed at least during application.

[0221] 〔solvent〕 The organic semiconductor composition may contain a solvent, and preferably contains a solvent from the viewpoint of improving the coating property. Such a solvent is not particularly limited as long as it dissolves or disperses the above-mentioned compound, and includes inorganic solvents or organic solvents, and organic solvents are preferred. The solvent may be used alone or in combination of two or more kinds.

[0222] The organic solvent is not particularly limited, but may be hydrocarbon solvents including hexane, octane, decane, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, amylbenzene, decalin, 1-methylnaphthalene, 1-ethylnaphthalene, 1,6-dimethylnaphthalene, and tetralin; ketone solvents including acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, propiophenone, and butyrophenone; dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetra ... Halogenated hydrocarbon solvents including chloroethane, chlorobenzene, 1,2-dichlorobenzene, trifluoromethyltoluene, 1,2,4-trichlorobenzene, chlorotoluene, 1-chloronaphthalene, and 1-fluoronaphthalene; heterocyclic solvents including pyridine, picoline, quinoline, thiophene, 3-butylthiophene, and thieno[2,3-b]thiophene; 2-chlorothiophene, 3-chlorothiophene, 2,5-dichlorothiophene, 3,4-dichlorothiophene, 2-bromothiophene, 3-bromothiophene, 2,3-dibromothiophene; Halogenated heterocyclic solvents including 2,4-dibromothiophene, 2,5-dibromothiophene, 3,4-dibromothiophene, and 3,4-dichloro-1,2,5-thiadiazole; ester solvents including ethyl acetate, butyl acetate, amyl acetate, 2-ethylhexyl acetate, gamma-butyrolactone, and phenyl acetate; alcohol solvents including methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, and ethylene glycol; dibutyl ether, tetrahydrofuran, dioxane, diisopropyl ether, and ethyl acetate; Methoxyethane, anisole, ethoxybenzene, dimethoxybenzene, propoxybenzene, isopropoxybenzene, butoxybenzene, 2-methylanisole, 3-methylanisole, 4-methylanisole, 4-ethylanisole, dimethylanisole (any of 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5- and 3,6-), and ether solvents including 1,4-benzodioxane, N,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone, and 1,Examples of suitable solvents include amide or imide solvents, such as 3-dimethyl-2-imidazolidinone, sulfoxide solvents, such as dimethyl sulfoxide, phosphate solvents, such as trimethyl phosphate, nitrile solvents, such as acetonitrile and benzonitrile, and nitro solvents, such as nitromethane and nitrobenzene.

[0223] Among these, a hydrocarbon solvent, a ketone solvent, a halogenated hydrocarbon solvent, a heterocyclic solvent, a halogenated heterocyclic solvent, or an ether solvent is preferred, and toluene, xylene, mesitylene, amylbenzene, tetralin, acetophenone, propiophenone, butyrophenone, dichlorobenzene, anisole, ethoxybenzene, propoxybenzene, isopropoxybenzene, butoxybenzene, dimethoxybenzene, chlorobenzene, dichlorobenzene, diethylbenzene, 2-methylanisole, 3-methylanisole, 4- Methylanisole, 1-fluoronaphthalene, 1-chloronaphthalene, 3-chlorothiophene, or 2,5-dibromothiophene is more preferred, and toluene, xylene, tetralin, acetophenone, propiophenone, butyrophenone, anisole, ethoxybenzene, propoxybenzene, butoxybenzene, 2-methylanisole, 3-methylanisole, 4-methylanisole, 1-fluoronaphthalene, 1-chloronaphthalene, 3-chlorothiophene, or 2,5-dibromothiophene is even more preferred.

[0224] The solvent contained in the organic semiconductor composition is preferably a solvent having a boiling point of 100° C. or higher, from the viewpoint of film quality and the ability to grow large crystals of the above-mentioned compound. Examples of the solvent having a boiling point of 100° C. or more include toluene, xylene, diethylbenzene, mesitylene, tetralin, acetophenone, propiophenone, butyrophenone, chlorobenzene, dichlorobenzene, anisole, dimethoxybenzene, ethoxybenzene, propoxybenzene, isopropoxybenzene, butoxybenzene, 2-methylanisole, 3-methylanisole, 1-methylnaphthalene, 1-fluoronaphthalene, 1-chloronaphthalene, and 4-methylanisole. Among them, toluene, xylene, diethylbenzene, chlorobenzene, dichlorobenzene, tetralin, acetophenone, propiophenone, butyrophenone, anisole, dimethoxybenzene, ethoxybenzene, propoxybenzene, butoxybenzene, 2-methylanisole, 3-methylanisole, 1-methylnaphthalene, 1-fluoronaphthalene, 1-chloronaphthalene, and 4-methylanisole are more preferred. In terms of environmental impact and toxicity to humans, a non-halogen solvent (a solvent having no halogen atoms in the molecule) is preferred as a solvent having a boiling point of 100° C. or higher.

[0225] When the organic semiconductor composition contains a solvent, the content of the solvent is preferably from 90 to 99.99 mass %, more preferably from 95 to 99.98 mass %, and even more preferably from 96 to 99.98 mass %, based on the total mass of the organic semiconductor composition.

[0226] [Other ingredients] The organic semiconductor composition may contain components other than the specific cyclic imide compound, the binder polymer, and the solvent. Examples of such components include various additives. The additives can be additives that are commonly used in organic semiconductor compositions, more specifically, surfactants, antioxidants, crystallization control agents, and crystal orientation control agents.For surfactants and antioxidants, paragraphs 0136 and 0137 of JP 2015-195362 A can be cited, and the contents of these are incorporated herein. The content of the additives in the organic semiconductor composition is not particularly limited, but in terms of excellent film formability and further improved carrier mobility and heat resistance, it is preferable that the content of the additives relative to the total mass of the solid content in the organic semiconductor composition is within a suitable range of the content of the additives relative to the total mass of the organic semiconductor film described below.

[0227] From the viewpoint of printability, the viscosity of the organic semiconductor composition is preferably 10 mPa·s or more.

[0228] [Preparation method] The method for preparing the organic semiconductor composition is not particularly limited, and a conventional preparation method can be used. For example, the organic semiconductor composition can be prepared by adding a predetermined amount of each component to an organic solvent and appropriately stirring the mixture. If necessary, the components can be heated during or after stirring. The heating temperature is not particularly limited and is determined, for example, within the range of 40 to 150° C. When a solvent is used, the temperature is determined to be within the above range and below the boiling point of the solvent.

[0229] [Organic thin-film transistor] Next, an organic thin film transistor (hereinafter also referred to as "organic TFT"), which is a preferred embodiment among the above-mentioned organic semiconductor devices using the specific cyclic imide compound, will be described. The organic TFT includes an organic semiconductor film, which will be described later. This allows the organic TFT to exhibit high carrier mobility, and to effectively suppress deterioration over time even in the atmosphere, allowing for stable operation. The ambient temperature and humidity in the atmosphere are not particularly limited as long as they are the temperature and humidity in the environment in which the organic TFT is used, and examples of the temperature include room temperature (20°C) and humidity of 10 to 90 RH%. The organic TFT is preferably used as an organic field effect transistor (FET), and more preferably used as an insulated gate FET in which the gate and channel are insulated from each other. The thickness of the organic TFT is not particularly limited, but in the case of making a thinner transistor, the thickness of the entire organic TFT is preferably set to, for example, 0.1 to 0.5 μm.

[0230] The organic TFT has an organic semiconductor film (also called an organic semiconductor layer or a semiconductor active layer) containing a specific cyclic imide compound, and may further have a source electrode, a drain electrode, a gate electrode, and a gate insulating film. The organic TFT preferably has, on a substrate, a gate electrode, an organic semiconductor film, a gate insulating film provided between the gate electrode and the organic semiconductor film, and a source electrode and a drain electrode provided in contact with the organic semiconductor film and connected via the organic semiconductor film. In this organic TFT, the organic semiconductor film and the gate insulating film are provided adjacent to each other. The organic TFT is not particularly limited in structure as long as it has the above-mentioned layers. For example, it may have any of the structures of bottom gate-bottom contact type, top gate-bottom contact type, bottom gate-top contact type, and top gate-top contact type. The organic TFT is preferably a bottom gate type (bottom gate-bottom contact type or bottom gate-top contact type) in which a gate electrode is provided between a substrate and an organic semiconductor film. An example of an organic TFT will be described below with reference to the drawings.

[0231] [Bottom-gate-bottom-contact organic TFT] FIG. 1 is a schematic cross-sectional view showing the structure of a bottom-gate-bottom-contact type organic TFT 10, which is an example of an organic TFT. As shown in FIG. 1, the organic TFT 10 includes a substrate (base material) 1, a gate electrode 2, a gate insulating film 3, a source electrode 4A, a drain electrode 4B, an organic semiconductor film 5, and a sealing layer 6, in this order. Hereinafter, the substrate (base material), the gate electrode, the gate insulating film, the source electrode, the drain electrode, the organic semiconductor film, and the sealing layer, as well as the methods for fabricating each will be described.

[0232] <Substrate> The substrate serves to support the gate electrode, source electrode, drain electrode, and other layers. The type of substrate is not particularly limited, and examples thereof include a plastic substrate, a silicon substrate, a glass substrate, and a ceramic substrate. Among these, a glass substrate or a plastic substrate is preferred from the viewpoints of applicability to each device and cost. The thickness of the substrate is not particularly limited. The upper limit of the thickness of the substrate is preferably 10 mm or less, more preferably 2 mm or less, and even more preferably 1.5 mm or less. The lower limit of the thickness of the substrate is preferably 0.01 mm or more, and more preferably 0.05 mm or more.

[0233] <Gate electrode> The gate electrode can be any ordinary electrode used as the gate electrode of an organic TFT without any particular limitation. The material (electrode material) for forming the gate electrode is not particularly limited, and examples thereof include metals including gold, silver, aluminum, copper, chromium, nickel, cobalt, titanium, platinum, magnesium, calcium, barium, and sodium, conductive oxides including InO2, SnO2, and indium tin oxide (ITO), conductive polymers including polyaniline, polypyrrole, polythiophene, polyacetylene, and polydiacetylene, semiconductors including silicon, germanium, and gallium arsenide, and carbon materials including fullerene, carbon nanotube, and graphite.Among these, the above metals are preferred, and silver or aluminum is more preferred. The thickness of the gate electrode is not particularly limited, but is preferably 20 to 200 nm. The gate electrode may function as the substrate, in which case the substrate may be omitted.

[0234] The method for forming the gate electrode is not particularly limited, and examples thereof include a method of vacuum-depositing (hereinafter also simply referred to as "deposition") or sputtering the above-mentioned electrode material on a substrate, and a method of applying or printing an electrode-forming composition containing the above-mentioned electrode material, etc. In addition, in the case of patterning the gate electrode, examples of the patterning method include printing methods including inkjet printing, screen printing, offset printing, and relief printing (flexographic printing), photolithography, and mask deposition.

[0235] <Gate insulating film> The gate insulating film is not particularly limited as long as it is a layer having insulating properties, and may be a single layer or a multilayer. The material for forming the gate insulating film is not particularly limited, and examples thereof include polymers including polymethyl methacrylate, polystyrene, polyvinylphenol, melamine resin, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinyl acetate, polyurethane, polysulfone, polybenzoxazole, polysilsesquioxane, epoxy resin, and phenol resin, inorganic oxides including silicon dioxide, aluminum oxide, and titanium oxide, and nitrides including silicon nitride. Among them, the above-mentioned polymers are preferred in terms of compatibility with the organic semiconductor film, and the above-mentioned inorganic oxides are preferred in terms of film uniformity, with silicon dioxide being more preferred. These materials may be used alone or in combination of two or more. The thickness of the gate insulating film is not particularly limited, but is preferably 100 to 1000 nm. The method for forming the gate insulating film is not particularly limited, and examples thereof include a method of applying a composition for forming a gate insulating film containing the above-mentioned material onto a substrate on which a gate electrode has been formed, and a method of depositing or sputtering the above-mentioned material.

[0236] <Source and drain electrodes> In an organic TFT, the source electrode is an electrode into which current flows from the outside via wiring, and the drain electrode is an electrode that sends out current to the outside via wiring. The source electrode and the drain electrode may be formed from the same material as the electrode material for forming the gate electrode described above. Among these, metal is preferable, and gold or silver is more preferable. The thickness of the source electrode and the drain electrode is not particularly limited, but is preferably 1 nm or more, more preferably 10 nm or more, and the upper limit of the thickness of the source electrode and the drain electrode is preferably 500 nm or less, more preferably 300 nm or less. The distance between the source electrode and the drain electrode (gate length L) can be determined as appropriate, but is preferably 200 μm or less, more preferably 100 μm or less. The gate width W can be determined as appropriate, but is preferably 5000 μm or less, more preferably 1000 μm or less. The ratio of the gate width W to the gate length L is not particularly limited, but for example, the ratio W / L is preferably 10 or more, more preferably 20 or more. The method for forming the source electrode and the drain electrode is not particularly limited, and examples thereof include a method of vacuum depositing or sputtering an electrode material on a substrate on which a gate electrode and a gate insulating film have been formed, and a method of applying or printing an electrode-forming composition. The patterning method for patterning the source electrode and the drain electrode is the same as the patterning method for the gate electrode described above.

[0237] <Organic semiconductor film> As the organic semiconductor film in the organic TFT, an organic semiconductor film containing a specific cyclic imide compound is used. The specific cyclic imide compound contained in the organic semiconductor film may be one type or two or more types. When an organic semiconductor film contains a specific cyclic imide compound, the carrier mobility of the organic semiconductor film can be improved, and the high carrier mobility can be maintained even when the organic semiconductor film is used or stored (left) under air. Although the reason is unclear, it is thought that this is because the orbital energy of the lowest unoccupied orbital of the specific cyclic imide compound is low.

[0238] The content of the specific cyclic imide compound in the organic semiconductor film is not particularly limited and can be appropriately set. For example, the content of the specific cyclic imide compound relative to the total mass of the organic semiconductor film is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more. There is no particular upper limit, and the content of the specific cyclic imide compound relative to the total mass of the organic semiconductor film may be 100% by mass. When the organic semiconductor film contains a binder polymer or other components, the upper limit of the content of the specific cyclic imide compound relative to the total mass of the organic semiconductor film is preferably 90% by mass or less, more preferably 80% by mass or less.

[0239] The organic semiconductor film may contain the above-mentioned binder polymer in addition to the specific cyclic imide compound. The binder polymer may be used alone or in combination of two or more. In the organic semiconductor film, the states of the specific cyclic imide compound and the binder polymer are not particularly limited, but in terms of carrier mobility, it is preferable that the specific cyclic imide compound and the binder polymer are phase-separated from each other along the film thickness direction.

[0240] The content of the binder polymer in the organic semiconductor film is not particularly limited and can be appropriately set. When the organic semiconductor film contains a binder polymer, the content of the binder polymer relative to the total mass of the organic semiconductor film is preferably 90 mass% or less, more preferably 70 mass% or less. There is no particular lower limit, and the content of the binder polymer relative to the total mass of the organic semiconductor film can be 0 mass% or more, preferably 10 mass% or more, more preferably 20 mass% or more.

[0241] The organic semiconductor film may contain the above-mentioned additives in addition to the specific cyclic imide compound. The additives may be used alone or in combination of two or more. When the organic semiconductor film contains an additive, the content of the additive relative to the total mass of the organic semiconductor film is preferably 10 mass % or less, more preferably 5 mass % or less, and even more preferably 1 mass % or less.

[0242] The thickness of the organic semiconductor film is appropriately determined depending on the organic TFT to which it is applied, but is preferably 10 to 500 nm, and more preferably 20 to 200 nm.

[0243] The organic semiconductor film can be formed by applying the organic semiconductor composition described above. The method for forming the organic semiconductor film will be described in detail later.

[0244] The use of the organic semiconductor film containing the specific cyclic imide compound is not limited to an organic semiconductor film for an organic TFT, but can be used as an organic semiconductor film provided in each of the above-mentioned organic semiconductor devices.

[0245] <Sealing layer> Since the organic TFT having the above-mentioned organic semiconductor film operates stably even in the atmosphere, it is not necessary to seal the entire organic TFT and block either the atmosphere (oxygen gas) or moisture. However, for the purpose of stable operation for a longer period of time, the entire organic TFT may be sealed in a metal sealing can or a sealing layer may be formed using a sealant. The sealing layer may be made of a sealant (composition for forming a sealing layer) that is generally used for organic TFTs. Examples of the sealant include inorganic materials including glass and silicon nitride, polymeric materials including parylene, and low molecular weight materials. The sealing layer can be formed by a common method such as coating and drying using the above-mentioned sealing agent. The thickness of the sealing layer is not particularly limited, but is preferably 0.2 to 10 μm.

[0246] [Bottom-gate-top-contact organic TFT] FIG. 2 is a schematic cross-sectional view showing the structure of a bottom-gate-top-contact type organic TFT 20, which is an example of an organic TFT. As shown in FIG. 2, the organic TFT 20 includes a substrate 1, a gate electrode 2, a gate insulating film 3, an organic semiconductor film 5, a source electrode 4A, a drain electrode 4B, and a sealing layer 6 in this order. The organic TFT 20 is the same as the organic TFT 10 except for the layer configuration (lamination mode). Therefore, the substrate, gate electrode, gate insulating film, source electrode, drain electrode, organic semiconductor film, and sealing layer are the same as those in the bottom-gate-bottom-contact type organic TFT described above, and therefore the description thereof will be omitted.

[0247] [Method of manufacturing organic TFT] The method for producing an organic TFT is not particularly limited as long as it is a method that includes a step of applying an organic semiconductor composition onto a substrate to form an organic semiconductor film.

[0248] The gate electrode, the gate insulating film, the source electrode, the drain electrode, and the sealing layer can all be produced or formed by the methods described above.

[0249] The process for forming the organic semiconductor film will be described below. In this step, the organic semiconductor composition described above is used. In the present invention, "coating an organic semiconductor composition on a substrate" includes not only an embodiment in which the organic semiconductor composition is directly coated on the substrate, but also an embodiment in which the organic semiconductor composition is coated above the substrate via another layer provided on the substrate. The other layer to which the organic semiconductor composition is coated (the layer in contact with the organic semiconductor film and serving as the base of the organic semiconductor film) is inevitably determined by the structure of the organic TFT. For example, when the organic TFT is a bottom-gate type, the organic semiconductor composition is coated on at least the surface of the gate insulating film.

[0250] When forming the organic semiconductor film, the substrate may be heated or cooled. By changing the temperature of the substrate, the film quality or the packing of the specific cyclic imide compound in the film can be controlled. The temperature of the substrate is not particularly limited. For example, the substrate temperature is preferably set within the range of 0 to 200°C, more preferably within the range of 15 to 100°C, and further preferably within the range of 20 to 95°C.

[0251] The method for forming the organic semiconductor film is not particularly limited as long as it is possible to form an organic semiconductor film containing the specific cyclic imide compound. Examples of the method include a vacuum process and a solution process, and among these, the solution process is preferred.

[0252] Examples of the vacuum process include physical vapor deposition methods including vacuum deposition, sputtering, ion plating, and molecular beam epitaxy (MBE), and chemical vapor deposition (CVD) methods including plasma polymerization. Among these, vacuum deposition is preferred.

[0253] For the solution process, it is preferable to use the above-mentioned organic semiconductor composition. As described above, the specific cyclic imide compound is stable even in the atmosphere, so that the solution process can be carried out in the atmosphere and the organic semiconductor composition can be applied over a large area. The organic semiconductor composition can be applied by a conventional method in the solution process. For example, the application method includes a drop cast method, a cast method, a dip coat method, a die coater method, a roll coater method, a bar coater method, and a spin coat method, various printing methods including an inkjet method, a screen printing method, a gravure printing method, a flexographic printing method, an offset printing method, and a microcontact printing method, and a Langmuir-Blodgett (LB) method. Among them, the drop cast method, the cast method, the spin coat method, the inkjet method, the gravure printing method, the flexographic printing method, the offset printing method, and the microcontact printing method are preferred. In a preferred embodiment of the solution process described below, the method for applying the organic semiconductor composition is preferably an inkjet method, a gravure printing method, a flexographic printing method, an offset printing method, or a microcontact printing method, and more preferably a flexographic printing method, a microcontact printing method, or an inkjet method.

[0254] In the solution process, it is preferable to dry the organic semiconductor composition applied on the substrate, and more preferably to dry gradually. By drying the organic semiconductor composition applied on the substrate, crystals of the specific cyclic imide compound are precipitated, and an organic semiconductor film can be formed. As a method for drying the organic semiconductor composition, from the viewpoint of film quality, natural drying or heat drying on a heated substrate followed by reduced pressure drying is preferred. The temperature of the substrate during natural drying or heat drying is preferably 20 to 100° C., more preferably 50 to 80° C. The time for natural drying or heat drying is preferably 0.5 to 20 hours, more preferably 1 to 10 hours. The temperature of the substrate during reduced pressure drying is preferably 20 to 100° C., more preferably 40 to 80° C. The time for reduced pressure drying is preferably 1 to 20 hours, more preferably 2 to 10 hours. -6 ~10 4Pa is preferred, 10 -5 ~10 -3 Pa is more preferred. The organic semiconductor composition thus dried may be shaped into a predetermined shape or pattern, if necessary.

[0255] <Solution process aspects> A preferred embodiment of the solution process will be described below with reference to the drawings, but the solution process is not limited to the following embodiment.

[0256] As one embodiment of the solution process, an organic semiconductor composition (hereinafter also referred to as "coating liquid") is dropped (coated) onto a part of the surface of a substrate so as to be in contact with the substrate and a member (hereinafter also simply referred to as "member") arranged on the substrate, and then the dropped coating liquid is dried. The substrate and member used in this embodiment will be described later. In this embodiment, the member maintains a state in which it is in contact with the substrate, or is not fixed to the substrate and maintains a constant distance from the substrate. As long as the substrate and the member maintain the above-mentioned state, the relative positional relationship between the substrate and the member may be fixed or changed when the coating liquid is dropped or dried. From the viewpoint of production efficiency, it is preferable to move the member relative to the substrate to change the relative positional relationship between the substrate and the member. Also, from the viewpoint of the film quality and crystal size of the obtained organic semiconductor film, it is preferable to keep the member stationary with respect to the substrate to fix the relative positional relationship between the substrate and the member.

[0257] The method of dropping the coating liquid in this embodiment is not particularly limited. In terms of the fact that the thickness of the coating liquid film on the substrate is easily thin and drying easily proceeds from the edge of the coating liquid film, it is preferable to drop the coating liquid one drop at a time, or when dropping two or more drops, to drop one drop at a time. When dropping the coating liquid, the volume of one drop of the coating liquid is preferably 0.01 to 0.2 mL, more preferably 0.02 to 0.1 mL. By dropping the coating liquid onto a portion of the surface of the substrate so as to be in contact with both the substrate and the member, the thickness of the coating liquid film at the edge portion can be made thinner. The contact angle (25°C) of the coating liquid to the substrate is not particularly limited, but is preferably 0 to 90°, more preferably 10 to 20°. The contact angle of the coating liquid to the substrate is obtained by dropping the coating liquid (solid content concentration: 0.1 mass%, solvent: anisole) and measuring the angle between the droplet and the substrate after 1 second has elapsed. Specifically, the liquid volume is set to 1.0 μL or more, and the static contact angle is measured by the droplet method using a Teflon (registered trademark) needle. In this way, measurements are taken multiple times (usually 5 times) for different substrates obtained by similar treatment, and the average value is calculated, and this value is taken as the contact angle. The coating liquid preferably forms a meniscus on the member, and from the viewpoint of film quality, it is more preferable that the coating liquid forms a concave meniscus on the member.

[0258] Hereinafter, the method of applying the coating liquid while keeping the distance between the substrate and the member constant in this embodiment will be described with reference to Fig. 3. Fig. 3 is a schematic diagram showing an example of a method of forming an organic semiconductor film of an organic TFT. In this method, first, the substrate 42 and the member 43 are placed in a predetermined position. Specifically, before the coating liquid 41 is dropped onto the substrate, the substrate 42 and the member 43 are placed in the positions shown in Fig. 3(A). At this time, the distance between the substrate 42 and the member 43 that is not in contact with the substrate 42 is kept constant. The distance between the substrate 42 and the member 43 cannot be determined in general because it differs depending on the amount of coating liquid applied, the viscosity, etc., but it can be set appropriately. Next, as shown in FIG. 3(B), the coating liquid 41 is dropped onto a part of the surface of the substrate 42 (near the opposing portion between the substrate 42 and the member 43) so as to be in contact with both the substrate 42 and the member 43. Thereafter, while the relative positional relationship between the substrate 42 and the member 43 is fixed, the coating liquid 41 is dried (FIG. 3(C)). The drying method is not particularly limited, but the above-mentioned drying method for the organic semiconductor composition is preferable. As a result, the coating liquid 41 dries from both ends (edges) where the film thickness is thin on the substrate 42 toward the inside, and the specific cyclic imide compound crystallizes. This allows the specific cyclic imide compound to be arranged at a predetermined position as a large-sized crystal. After the coating liquid 41 is dried, the member 43 is separated from the substrate 42, for example, by lifting the member 43 vertically relative to the main surface of the substrate 42. This makes it possible to form an organic semiconductor film with good film quality without leaving any trace of the member 43 on the formed crystals. In this manner, an organic semiconductor film made of crystals of the specific cyclic imide compound can be formed.

[0259] Hereinafter, the method of applying the coating liquid in a state in which the substrate and the member are in contact with each other in this embodiment will be described with reference to Fig. 4. Fig. 4 is a schematic diagram for explaining another example of the method of forming an organic semiconductor film of an organic TFT. In this method, first, the substrate 42 and the member 43 are placed in contact with each other. Specifically, before the coating liquid 41 is dropped onto the substrate 42, the substrate 42 and the member 43 are placed at the positions shown in FIG. Next, as shown in Figures 4(B1) and 4(B2), the coating liquid 41 is dropped onto a part of the surface of the substrate 42 (near the contact part between the substrate 42 and the member 43) so as to contact both the substrate 42 and the member 43. At this time, as shown in Figure 4(B2), it is preferable that the coating liquid 41 surrounds the contact part between the substrate 42 and the member 43. Note that Figure 4(B1) is a front view of the substrate coated with the coating liquid, and Figure 4(B2) is a plan view of the substrate coated with the coating liquid. Three-dimensional coordinates (X, Y, Z) are written in Figures 4(B1) and 4(B2). Thereafter, while the relative positional relationship between the substrate 42 and the member 43 is fixed, the coating liquid 41 is dried, preferably as described above (FIG. 4(C)). The drying method is not particularly limited, but the drying method for the organic semiconductor composition described above is preferred. This causes the coating liquid 41 to dry from the edge where the film thickness is thin on the substrate 42 toward the inside, and the specific cyclic imide compound crystallizes. This allows the specific cyclic imide compound to be arranged at a predetermined position as a large-sized crystal. After drying the coating liquid 41, the member 43 is separated from the substrate 42, for example, by lifting the member 43 vertically relative to the main surface of the substrate 42. This makes it possible to form an organic semiconductor film 5 made of crystals of the specific cyclic imide compound and having good film quality, without leaving any trace of the member 43 on the crystals of the specific cyclic imide compound, as shown in FIG. The method of applying the coating liquid while the substrate 42 and the member 43 are in contact with each other is preferable to the method of applying the coating liquid while keeping the distance between the substrate 42 and the member 43 constant, in terms of film quality, in that a mechanism for holding the member 43 is not required, and in that the distance (contact state) of the member 43 relative to the substrate 42 can be maintained.

[0260] Another method for applying the coating liquid while the substrate and the member are in contact with each other in this embodiment will be described below with reference to Fig. 5. Fig. 5 is a schematic diagram for explaining another example of the method for forming an organic semiconductor film of an organic TFT. This method differs from the method shown in FIG. 4 in that the crystallization of the specific cyclic imide compound is promoted by moving the member 43 relative to the substrate 42 while keeping the distance between the substrate 42 and the member 43 constant. In this method, first, the substrate 42 and the member 43 are placed in contact with each other. Specifically, before the coating liquid 41 is dropped onto the substrate 42, the substrate 42 and the member 43 are placed at the positions shown in FIG. 5(B), the coating liquid 41 is dropped onto a part of the surface of the substrate 42 (in the vicinity of the contact portion between the substrate 42 and the member 43) so as to be in contact with both the substrate 42 and the member 43. At this time, it is preferable that the coating liquid 41 surrounds the contact portion between the substrate 42 and the member 43 as shown in FIG. Thereafter, while maintaining a constant distance between the substrate 42 and the member 43, the member 43 is moved relative to the substrate 42 to dry the coating liquid 41. For example, the member 43 is moved relative to the substrate 42 in the direction of the arrow in FIG. 5C (negative direction of the X-axis). Drying of the coating liquid 41 progresses from the end (positive direction of the X-axis) on the opposite side to the moving direction of the member 43 toward the moving direction (negative direction of the X-axis), and the specific cyclic imide compound crystallizes. This allows the specific cyclic imide compound to be arranged at a predetermined position as a large-sized crystal. After drying the coating liquid 41, the member 43 is separated from the substrate 42, for example, by lifting the member 43 vertically relative to the main surface of the substrate 42. This makes it possible to form an organic semiconductor film made of the specific cyclic imide compound and having good film quality, without leaving any trace of the member 43 on the crystals of the specific cyclic imide compound.

[0261] The substrate 42 used in this embodiment corresponds to a substrate for an organic TFT, and is preferably a substrate on which a gate insulating film is formed.

[0262] The member 43 used in this embodiment is not particularly limited, but the material of the member 43 is preferably an inorganic material (more preferably glass, quartz, or silicon) or a plastic (more preferably Teflon (registered trademark), polyethylene, or polypropylene), and more preferably glass. The shape of the member 43 used in this embodiment is not particularly limited as long as it has a smooth surface facing the substrate 42, but a rectangular parallelepiped is preferable.

[0263] 6 is a schematic diagram showing an example of the substrate 42 and the member 43 used in this embodiment. In Fig. 6, the shape of the member 43 is a rectangular parallelepiped, d and w respectively represent the lengths of one side and the other side of the surface of the member 43 facing the substrate 42, and h represents the height of the member 43. The size of the member 43 used in this embodiment is not particularly limited. When the member 43 is a rectangular parallelepiped as shown in FIG. 6, the lower limit of the length of one side and the other side of the surface of the member 43 facing the substrate 42 (d and W in FIG. 6) is preferably 0.1% or more, more preferably 1% or more, even more preferably 10% or more, and particularly preferably 20% or more, relative to the length of one side of the main surface of the substrate 42 (the surface to which the coating liquid is applied). The upper limit of the length of the one side and the other side is preferably 80% or less, more preferably 70% or less, and even more preferably 50% or less, relative to the length of one side of the main surface of the substrate 42. The height of the member 43 (h in FIG. 6) is preferably 1 to 50 mm, and more preferably 5 to 20 mm. Furthermore, the ratio h / d of the height h to the length d of the member 43 is preferably 0.01 to 10, and more preferably 0.1 to 5 in terms of the arrangement stability of the member 43. The ratio w / d of the length w of the member 43 to the length d is preferably 1 to 1000, and more preferably 5 to 100, in that the specific cyclic imide compound can be crystallized over a wide range.

[0264] In this way, crystals of the specific cyclic imide compound are precipitated to form an organic semiconductor film. Whether or not crystals of the specific cyclic imide compound are precipitated can be confirmed by observing the organic semiconductor film using a polarizing microscope (product name: Eclipse LV100N POL (transmission / reflection illumination type), manufactured by Nikon Corporation, eyepiece lens: magnification 10x, objective lens: magnification 5-20x).

[0265] [Applications of organic TFT] The applications of the above-mentioned organic TFTs are not particularly limited, and they can be used in, for example, electronic paper, display devices, sensors, and electronic tags. EXAMPLES

[0266] The present invention will be described in more detail below based on examples. The materials, amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples.

[0267] [Example 1: Synthesis of compound (1-1)]

[0268] [ka]

[0269] [Purification of compound (1-3)] Compound (1-3) was purified by recrystallization from hexane-ethyl acetate.

[0270] [Synthesis of composition (raw material composition) containing compound (1-4)] In a glass reaction vessel equipped with a pressure-resistant balloon, 20 g (37.9 mmol) of compound (1-2), 200 mL of toluene, 0.851 g (3.79 mmol) of palladium acetate, 4.39 g (7.58 mmol) of Xantphos, and 51.0 g (227 mmol) of compound (1-3) were placed, and the atmosphere in the reaction vessel was replaced with nitrogen. 37.0 mL (265 mmol) of triethylamine was added dropwise with a syringe, and the mixture was stirred at 75°C to 85°C for 7 hours. After cooling to room temperature, the precipitated solid was filtered. The obtained solid was dispersed in methanol, stirred at room temperature for 30 minutes, and then filtered. The filtrate was dissolved in chloroform, silica gel was added, and the mixture was filtered. The filtrate was concentrated under reduced pressure and recrystallized from o-dichlorobenzene to obtain 23.2 g (28.4 mmol, yield 69.6%) of a composition containing compound (1-4). The content of compound (1-4) in the obtained composition was 98.6 mass % based on the total solid content of the composition, and the content of compound (1-4') was 0.1 mass % or less based on the total solid content of the composition. The "raw material composition" in the Example 1 column in Table 1 below means a composition containing the compound (1-4) obtained here.

[0271] [Synthesis of compound (1-1)] In a glass reaction vessel, 1.00 g (1.22 mmol) of a composition containing compound (1-4), 40 mL of o-dichlorobenzene, and 593 mg (4.89 mmol) of phenethylamine were placed and stirred at 150°C for 2 hours. After cooling to room temperature, methanol was added and the solid was filtered. The obtained solid was vacuum dried and purified by sublimation to obtain 466 mg (0.776 mmol, yield 63.6%) of compound (1-1).

[0272] [Example 2: Synthesis of compound (1-1)] [Production of composition (raw material composition) containing compound (1-4)] A composition containing compound (1-4) was obtained in the same manner as in Example 1, except that compound (1-3) was not purified by recrystallization. The content of compound (1-4) in the obtained composition was 94.9 mass% based on the total solid content of the composition, and the content of compound (1-4') was 3.0 mass% based on the total solid content of the composition. The "raw material composition" in the Example 2 column in Table 1 below means a composition containing the compound (1-4) obtained here.

[0273] [Synthesis of compound (1-1)] In the same manner as in Example 1, 451 mg (0.751 mmol, yield 61.5%) of compound (1-1) was obtained.

[0274] [Example 3: Synthesis of compound (3-1)]

[0275] [ka]

[0276] [Synthesis of compound (3-1)] The same procedure as in Example 1 was repeated except that phenethylamine was replaced with 631 mg (4.89 mmol) of n-octylamine, to obtain 452 mg (0.733 mmol, yield 60.1%) of compound (3-1).

[0277] [Example 4: Production of compound (4-1)]

[0278] [ka]

[0279] The same procedure as in Example 1 was repeated except that phenethylamine was replaced with 661 mg (4.89 mmol) of 3-phenylpropylamine, to obtain 480 mg (0.764 mmol, yield 62.6%) of compound (4-1).

[0280] [Example 5: Synthesis of compound (1-1)]

[0281] [ka]

[0282] [Production of compound (1-1)] The same procedure as in Example 1 was repeated except that the composition containing compound (1-4) was replaced with 745 mg (1.22 mmol) of a composition containing the following compound (5-2), and 447 mg (0.745 mmol, yield 61.1%) of compound (1-1) was obtained. In addition, in the composition containing compound (5-2), the content of compound (5-2) was 98.1 mass% based on the total solid content of the composition containing compound (5-2), and the content of compound (5-2') was 0.1 mass% or less based on the total solid content of the composition containing compound (5-2). In addition, the "raw material composition" in the Example 5 column in Table 1 below means a composition containing the above compound (5-2).

[0283] [Example 6: Synthesis of compound (1-1)]

[0284] [ka]

[0285] [Synthesis of compound (1-1)] The same procedure as in Example 1 was repeated except that the composition containing compound (1-4) was changed to 829 mg (1.22 mmol) of a composition containing compound (6-2), to obtain 462 mg (0.770 mmol, yield 63.1%) of compound (1-1). In addition, in the composition containing compound (6-2), the content of compound (6-2) was 98.2 mass% based on the total solid content of the composition containing compound (6-2), and the content of compound (6-2') was 0.1 mass% or less based on the total solid content of the composition containing compound (6-2). In addition, the "raw material composition" in the Example 6 column in Table 1 below means a composition containing the above compound (6-2).

[0286] [Example 7: Synthesis of compound (1-1)] [Purification of compound (1-3)] Compound (1-3) was washed with cold hexane.

[0287] [Synthesis of composition (raw material composition) containing compound (1-4)] A composition containing compound (1-4) was obtained in the same manner as in Example 1, except that compound (1-3) was used. The content of compound (1-4) in the obtained composition was 97.8 mass% based on the total solid content of the composition, and the content of compound (1-4') was 1.0 mass% based on the total solid content of the composition. The "raw material composition" in the Example 7 column in Table 1 below means a composition containing the compound (1-4) obtained here.

[0288] [Synthesis of compound (1-1)] In the same manner as in Example 1, 445 mg (0.741 mmol, yield 60.7%) of compound (1-1) was obtained.

[0289] [Comparative Example 1: Synthesis of compound (1-1)]

[0290] [ka]

[0291] [Synthesis of compound (C1-1)] Compound (1-4) (410 mg, 0.502 mmol), p-toluenesulfonic acid monohydrate (477 mg, 2.51 mmol), and o-dichlorobenzene (40 mL) were placed in a glass reaction vessel and stirred at 120°C for 12 hours. The reaction solution was concentrated under reduced pressure, and the solid was dispersed in hexane and collected by filtration. The resulting solid was dispersed in ethyl acetate, collected by filtration, and washed with ethyl acetate to obtain compound (C1-1) (95 mg, 0.240 mmol, 47.8% yield).

[0292] [Synthesis of compound (1-1)] In a glass reaction vessel, 500 mg (1.27 mmol) of compound (C1-1), 615 mg (5.07 mmol) of 2-phenylethylamine, and 20 mL of o-dichlorobenzene were placed and stirred at 150° C. for 3 hours. After cooling with water, 40 mL of methanol was added and filtered. The solid obtained was dried under reduced pressure and purified by sublimation to obtain 375 mg (0.624 mmol, yield 49.1%) of compound (1-1). The yield of the final target compound (1-1) from compound (1-4) was 23.5%.

[0293] [Comparative Example 2: Production of compound (1-1)]

[0294] [ka]

[0295] The same procedure as in Comparative Example 1 was followed except that purification by sublimation was not performed, and 611 mg (1.02 mmol, yield 80.1%) of compound (1-1) was obtained. The yield of the final target compound (1-1) from compound (1-4) was 38.3%.

[0296] [evaluation] [Purity analysis by liquid chromatography] The cyclic imide compounds finally obtained by each of the production methods of the Examples and Comparative Examples were analyzed by liquid chromatography under the following conditions and evaluated according to the following criteria. Column: Tosoh TSKgel Silica-150 (particle size: 5 μm, inner diameter: 4.6 mm, length: 25 cm) Eluent: chloroform / hexafluoroisopropanol=9 / 1 Flow rate: 0.8mL / min Injection volume: 10μL Column temperature: 25℃ Detection wavelength: 254nm Sample: 50 w / v ppm (solvent: chloroform / hexafluoroisopropanol = 4 / 1)

[0297] - Evaluation Criteria - A: The area ratio of the target object is 99% or more B: The area ratio of the target object is 97.5% or more and less than 99% C: The area ratio of the target object is 95% or more and less than 97.5% D: The area ratio of the target object is less than 95%

[0298] [Fabrication and Evaluation of Organic Thin-Film Transistors] <Fabrication of organic thin-film transistors> A substrate (size: 25 mm x 25 mm) having a thermally oxidized SiO2 film (thickness: 200 nm) on the surface of an n-type silicon substrate (thickness: 0.4 mm, equivalent to substrate 1 equipped with a gate electrode 2) 1 was prepared as a substrate for measuring FET characteristics. The surface of the thermally oxidized film (gate insulating film 3) of this substrate was cleaned with ultraviolet (UV)-ozone, and then treated with β-phenethyltrimethoxysilane. A glass member having dimensions of 10 mm length × 2 mm width × 5 mm height was prepared. This member, designated member 43 in Fig. 4, was placed in contact with the central portion of the β-phenethyltrimethoxysilane-treated surface of substrate 1 as shown in Fig. 4(A). Next, on a substrate 1 (indicated by reference symbol 42 in FIG. 4) heated to 100° C., one drop (about 0.05 mL) of a 1-methylnaphthalene solution (0.03 mass%) of the compound obtained by the manufacturing method of each Example and Comparative Example was dropped using a pipette from the side of the member 43 so as to come into contact with the substrate 42 and the member 43, as shown in FIG. 4(A). As shown in FIG. 4(B1) and FIG. 4(B2), the coating liquid surrounded the contact portion and formed a concave meniscus at the interface with the member 43. The contact angle (25° C.) of the coating liquid 41 with respect to the substrate 42 was 10°. As shown in FIG. 4C, while the substrate 42 and the member 43 were kept in contact with each other, and while the positional relationship between the substrate 42 and the member 43 was kept stationary, the coating liquid 41 was dried at 150° C. Then, the coating liquid 41 was dried at 60° C. for 8 hours and at 10° C. for 10 hours. -3 A crystal film of the organic semiconductor film was produced by drying under reduced pressure at a pressure of 100 Pa. Next, the member 43 was pulled up vertically relative to the substrate 42 and separated from the substrate 42. This resulted in the formation of the annular organic semiconductor film 5 shown in FIG. 4(D) having the uniform film thickness (film thickness: 10 to 50 nm). The obtained organic semiconductor film 5 was observed using a polarizing microscope (Eclipse LV100N POL (transmissive / reflective illumination type), manufactured by Nikon Corporation, eyepiece lens: magnification 10x, objective lens: magnification 5-20x) and it was found that crystals of the above compound were precipitated. A mask having a predetermined opening was placed on the organic semiconductor film 5 thus obtained, and gold was evaporated to form a source electrode 4A and a drain electrode 4B (both thickness: 40 nm, gate width W=2 mm, gate length L=50 μm, ratio W / L=40). In this way, an organic thin film transistor for measuring FET characteristics was produced. For the purpose of the evaluation described below, ten organic thin film transistors were fabricated for each of the examples and comparative examples using the compounds obtained by the manufacturing methods described below.

[0299] <Evaluation of organic thin-film transistors> 1. How to measure carrier mobility μ The carrier mobility of each of the prepared organic thin film transistors was measured under normal atmospheric pressure (temperature: room temperature) of 1 atm using a semiconductor parameter analyzer (Agilent, 4156C) connected to a semi-automatic prober (Vector Semicon, AX-2000). The specific details are as follows.

[0300] A voltage of -80 V was applied between the source and drain electrodes of each organic thin-film transistor, and the gate voltage was changed in the range of +20 V to -100 V. The drain current I d The following formula is used to express the carrier mobility μ (cm 2 / Vs) was calculated. I d =(w / 2L)μC i (V g -V th ) 2 In the formula, L is the gate length, w is the gate width, μ is the carrier mobility, and C i is the capacitance per unit area of ​​the gate insulating film, V g is the gate voltage, V th represents the threshold voltage.

[0301] 2. Evaluation of Relative Mobility The carrier mobility was calculated for each of the organic thin-film transistors fabricated in 10 units for each Example and Comparative Example, and the average mobility was calculated. Next, the relative mobility was calculated using the average mobility of Example 1 as a reference according to the following formula, and evaluated according to the following criteria. The higher the relative mobility, the more preferable. In this test, rank C or higher is preferable, rank B or higher is more preferable, and rank A is even more preferable. Relative mobility = (average mobility of each Example or Comparative Example) / (average mobility of Example 1) - Evaluation Criteria - A: Relative mobility is 1.0 or more B: Relative mobility is 0.6 or more and less than 1.0 C: Relative mobility is 0.2 or more and less than 0.6 D: Relative mobility is less than 0.2

[0302] 3.Evaluation of variability Ten organic thin-film transistors were fabricated for each of the Examples and Comparative Examples. The mobility ratio of each was calculated from the following formula and evaluated according to the following criteria. Mobility ratio = (highest mobility among 10 organic thin-film transistors) / (lowest mobility among 10 organic thin-film transistors) - Evaluation Criteria - A: Mobility ratio is less than 1.5 B: Mobility ratio is 1.5 or more and less than 1.8 C: Mobility ratio is 1.8 or more and less than 2.1 D: Mobility ratio is 2.1 or more

[0303] The results are shown in Table 1. In Table 1, "raw material composition" refers to a composition containing a compound represented by formula (8) and a compound represented by formula (17) used to obtain a compound represented by formula (9) in the above-mentioned production method (note that the compound represented by formula (18) was not contained in the above-mentioned composition). Specifically, taking Example 1 as an example, the "composition containing compound (1-4)" obtained by [synthesis of a composition (raw material composition) of compound (1-4)] corresponds to the "raw material composition" referred to here. Note that in the raw material composition of Example 1, compound (1-4) corresponds to the compound represented by formula (8), and compound (1-4') corresponds to the compound represented by formula (17). In addition, the "content of the compound represented by formula (8)" in the "raw material composition" column refers to the content (mass%) of the compound represented by formula (8) contained in the raw material composition relative to the total solid content of the raw material composition. In addition, the "content of the compound represented by formula (17)" in the "raw material composition" column refers to the content (mass%) of the compound represented by formula (17) contained in the raw material composition relative to the total solid content of the raw material composition.

[0304] The synthesis methods of Examples 1 to 7 correspond to the synthesis method of the first embodiment-1 described above.

[0305] [Table 5]

[0306] It is clear from the results in Table 1 that the cyclic imide compounds obtained by the production methods of the Examples are excellent in yield and purity. Furthermore, from the results of Examples 1 to 7, it is clear that when the content of the compound represented by formula (17), which is an impurity, in the raw material composition is a predetermined value or less (which applies to all cases except for Example 2), the target cyclic imide compound can be obtained with a higher purity. Furthermore, a comparison of Examples 1, 5, and 6 reveals that when the raw material component, the compound represented by formula (8), is a compound represented by formula (10) (preferably a compound represented by formula (10')), the desired cyclic imide compound can be produced in a higher yield.

[0307] [Example 8: Production of compound (8-1)]

[0308] [ka]

[0309] [Synthesis of compound (8-3)] A composition containing compound (1-4) was used, which was purified in the same manner as in Example 1. The content of compound (1-4) in the composition containing compound (1-4) was 98.6 mass% based on the total solid content of the composition, and the content of compound (1-4') was 0.1 mass% or less based on the total solid content of the composition.

[0310] Next, 1.60 g (1.96 mmol) of a composition containing compound (1-4), 1.65 g (6.85 mmol) of compound (8-2), and 32 mL of o-dichlorobenzene were placed in a glass reaction vessel and stirred for 1 hour at 180° C. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography to obtain 580 mg (0.674 mmol, yield 34.4%) of compound (8-3). Compound (8-3): 1 H NMR (400MHz, TCE-d 2, 100℃): δ 2.87-3.08 (brm, 2H, Ph-C H 2-CH2), 3.62-3.75 (brm, 2H, Ph-CH2-21C H 2-), 3.82 (s, 3H, C H 3-O-Ph), 3.89 (s, 3H, C H 3-OC=O (ester of the Cl3Ph side)), 3.93-4.08 (brm, 3H, C H 3-OC=O (ester of the PMB group side)), 4.08-5.55 (brm, 2H, Ph-C H 2-N), 6.82-7.43 (brm, 9H, Ar H ), 7.46(s, 2H, Ar H of Cl3Ph), 7.65-8.73 (brm, 1H, Ar H ), 8.84-9.23 (m, 5H, Ar H ). Note that TCE stands for 1,1,2,2-tetrachloroethane.

[0311] [Synthesis of compound (8-4)] 300 mg (0.348 mmol) of compound (8-3), 60.8 mg (0.697 mmol) of n-pentylamine, and 3 mL of o-dichlorobenzene were placed in a glass reaction vessel and reacted at 110° C. for 1 hour. The solvent was removed under reduced pressure, and the residue was dispersed in acetonitrile, filtered, and dried under reduced pressure to obtain 221 mg (0.307 mmol, yield 88.3%) of compound (8-4). Compound (8-4): 1 H NMR (400MHz, TCE-d 2 , 100℃): δ 0.94 (t, J = 6.8 MHz, 3H, CH2-C H 3), 1.37-1.45 (m, 4H, N-CH2-CH2-(C H 2)2-CH3), 1.78 (q, J = 6.8 Hz, 2H, N-CH2-C H2-C3H7), 2.89-3.10 (brm, 2H, Ph-C H 2-CH2), 3.63-3.75 (brm, 2H, Ph-CH2-C H 2-), 3.82 (s, 3H, C H 3-O-Ph), 3.97-4.01 (brm, 3H, C H 3-OC=O), 4.19 (t, J = 7.2 Hz, 2H, NC H 2-C4H9), 4.30-5.55 (brm, 2H, Ph-C H 2-N), 6.84-7.41 (brm, 10H, Ar H ), 8.68-9.57 (m, 5H, Ar H ).

[0312] [Synthesis of compound (8-1)] 164 mg (0.228 mmol) of compound (8-4), 8.6 mL of o-dichlorobenzene, and 54.8 mg (0.570 mmol) of methanesulfonic acid were placed in a glass reaction vessel and stirred at 150° C. for 3 hours. After cooling with water, the mixture was filtered and dried under reduced pressure. The resulting solid was purified by sublimation to obtain 35 mg (0.0618 mmol, yield 27.1%) of compound (8-1). Compound (8-1): 1 H NMR (400MHz, TCE-d 2 , 100℃): δ 0.94 (t, J = 7.0Hz, 3H, -CH2-C H 3), 1.44-1.40 (m, 4H, N-CH2-CH2-(C H 2)2-CH3), 1.79 (q, 2H, J = 7.2 Hz, N-CH2-C H 2-C3H7), 3.07 (t, J= 7.8Hz, 2H, Ph-C H 2-), 4.20 (t, J = 7.4Hz, 2H, NC H 2-C4H9), 4.45 (t, J = 7.8Hz, 2H, Ph-CH2-C H 2-), 7.34-7.18 (m, 5H, Ar Hof phenyl), 8.84 (d, J = 7.6Hz, 2H, Ar H ), 9.27 (d, J= 8.0Hz, 2H, Ar H ), 9.64 (s, 2H, Ar H ) .

[0313] [Example 9] [ka]

[0314] [Synthesis of compound (9-2)] Compound (8-1) was obtained in the same manner as in Example 8, except that compound (8-2) was changed to compound (9-1) and pentylamine was changed to phenethylamine.

[0315] [Example 10] [ka]

[0316] [Production of compound (10-1)] Compound (10-1) was obtained in the same manner as in Example 8, except that pentylamine was changed to octylamine.

[0317] Compound (10-2): 1 H NMR (400MHz, TCE-d 2 , 100℃): δ 0.83 (t, J = 6.6 MHz, 3H, CH2-C H 3), 1.19-1.38 (m, 10H, CH2-(C H 2)5-CH3), 1.69 (q, J = 6.4 Hz, 2H, N-CH2-C H 2-C6H 13 ), 2.85-3.14 (m, 2H, Ph-C H 2-CH2), 3.53-3.74 (m, 2H, Ph-CH2-C H 2-), 3.79-3.83 (m, 3H, C H3-O-Ph), 3.92-4.02 (m, 3H, C H 3-OC=O), 4.13 (t,J= 7.2 Hz,2H, NC H 2-C7H 15 ), 4.31-5.24 (m, 2H, Ph-C H 2-N), 6.87-7.41 (m, 9H, Ar H ), 7.53-8.20 (m, 1H, Ar H ), 8.64-9.47 (m, 5H, Ar H ).

[0318] Compound (10-1): 1 H NMR (400MHz, TCE-d 2 , 100℃): δ 0.88 (t, J = 7.0Hz, 3H, CH2-C H 3), 1.50-1.30 (m, 10H, N-CH2-CH2-(C H 2)5-CH3), 1.78 (q, J = 7.2 Hz, 2H, N-CH2-C H 2-C6H 13 ), 3.07 (t, J = 7.8Hz, 2H, Ph-C H 2-), 4.19 (t, J = 7.4Hz, 2H, NC H 2-C7H 15 ), 4.44 (t, J = 7.8Hz, 2H, Ph-CH2-C H 2-), 7.18-7.34 (m, 5H, Ar H of phenyl), 8.85 (d, J = 7.6Hz, 2H, Ar H ), 9.28 (d, J = 8.0Hz, 2H, Ar H ), 9.64 (s, 2H, Ar H ).

[0319] [evaluation] Using the compounds obtained by the manufacturing methods of Examples 8 to 10, [purity analysis by liquid chromatography] and [fabrication and evaluation of organic thin film transistors] were carried out in the same manner as in Example 1. The results are shown in Table 2.

[0320] In Table 2, "raw material composition" refers to a composition containing a compound represented by formula (8) and a compound represented by formula (17), which is used to obtain a compound represented by formula (9) in the above-mentioned production method (note that the compound represented by formula (18) was not contained in the above-mentioned composition). Specifically, the "composition containing compound (1-4)" in Examples 8 to 10 corresponds to the "raw material composition" referred to here. Note that, in the raw material compositions of Examples 8 to 10, compound (1-4) corresponds to the compound represented by formula (8), and compound (1-4') corresponds to the compound represented by formula (17). In addition, the "content of the compound represented by formula (8)" in the "raw material composition" column refers to the content (mass%) of the compound represented by formula (8) contained in the raw material composition relative to the total solid content of the raw material composition. In addition, the "content of the compound represented by formula (17)" in the "raw material composition" column refers to the content (mass%) of the compound represented by formula (17) contained in the raw material composition relative to the total solid content of the raw material composition. The numerical value in the "Yield" column indicates the yield from compound (1-4) to the final target compound (for example, compound (8-1) in the case of Example 8).

[0321] The manufacturing method of Examples 8 to 10 corresponds to the manufacturing method of the second embodiment described above.

[0322] [Table 6]

[0323] Furthermore, by using the production method of the present invention, the following derivatives can be synthesized. [Example 11]

[0324] [ka]

[0325] [Synthesis of compound (11-2)] In a glass reaction vessel, 1 g (1.14 mmol) of the composition containing the compound (1-4) prepared in Example 1, 25.5 mg (0.114 mmol), 205 mg (0.567 mmol) of copper (II) trifluoromethanesulfonate, 609 mg (3.42 mmol), 33 mL of 1,1,2-trichloroethane, and 5 mL of N,N-dimethylformamide were placed and reacted at 60°C for 2 hours under a nitrogen atmosphere. The mixture was allowed to cool to room temperature, poured into 80 mL of methanol, and the precipitated solid was collected by filtration. The obtained solid was purified by silica gel column chromatography to obtain 0.887 g (0.910 mmol, yield 79.8%) of compound (11-2). Compound (11-2): 1 H NMR(CDCl3)δ 3.95(6H,s), 7.48(4H,s), 9.18(2H,s), 9.27(2H,s).

[0326] [Synthesis of compound (11-3)] In a glass reaction vessel, 224 mg (0.229 mmol) of compound (11-2), 370 g (4.13 mmol) of copper cyanide, and 9.2 mL of N,N-dimethylformamide were placed and reacted at 100°C for 1 hour under a nitrogen atmosphere. After cooling to room temperature, the mixture was added to 200 mL of methanol, and the precipitated solid was collected by filtration. The obtained solid was purified by silica gel column chromatography to obtain 168 mg (0.194 mmol, yield 84.7%) of compound (11-3).

[0327] Compound (11-3): 1 H NMR(CDCl3) δ 3.99(6H,s), 7.51(4H,s), 9.16(2H,s), 9.45(2H,s).

[0328] [Production of compound (11-1)] In a glass reaction vessel, 140 mg (0.161 mmol) of compound (11-3), 45.8 mg (0.354 mmol) of octylamine, and 5.6 mL of o-dichlorobenzene were placed and reacted at 150°C for 6 hours under a nitrogen atmosphere. After cooling, the mixture was filtered. The resulting solid was purified by silica gel column chromatography to obtain 60.3 mg (0.0905 mmol, yield 56.2%) of compound (11-1). Compound (11-1): 1 H NMR (TCE-d 2 , 100℃)δ 0.90 (t, J = 7.0 Hz, 6H), 1.25-1.48 (m, 20H), 1.78 (m, 4H), 4.23 (t, J = 7.8 Hz, 4H), 9.12 (s, 2H), 9.37 (s, 2H).

[0329] [Example 12]

[0330] [ka]

[0331] [Synthesis of compound (12-3)] In a glass reaction vessel, 0.900 g (0.923 mmol) of compound (11-2), 0.863 g (2.31 mmol) of compound (12-2), 0.0472 g (0.0923 mmol) of bis(tri-tert-butylphosphine)palladium(0), 0.0352 g (0.185 mmol) of copper iodide(I), and 46 mL of tetrahydrofuran were added and reacted at 60°C for 1 hour under a nitrogen atmosphere. After cooling to room temperature, 100 mL of methanol was added and the precipitated solid was filtered. The obtained solid was purified by silica gel column chromatography to obtain 0.853 g (0.868 mmol, yield 94.0%) of compound (12-3). Compound (12-3): 1 H NMR(CDCl3)δ 3.89(6H,s), 7.44(4H,s), 7.57(2H,d,J = 4Hz), 7.99(2H,d,J = 4Hz), 8.77(2H,s), 9.07(2H,s).

[0332] [Synthesis of compound (12-1)] In a glass reaction vessel, 0.620 g (0.630 mmol) of compound (12-3), 0.384 g (3.15 mmol) of phenethylamine, and 31 mL of o-dichlorobenzene were placed and reacted at 80°C for 2 hours. After cooling to room temperature, the mixture was added to 100 mL of ice-cold methanol and stirred for 20 minutes under ice cooling. The precipitated solid was collected by filtration and dried under reduced pressure to obtain 0.452 g (0.590 mmol, yield 93.7%) of compound (12-1). Compound (12-1): 1 H NMR(CDCl3) δ3.02-3.06(4H, m), 4.40-4.44(4H, m), 7.23-7.34(10H, m), 7.67(2H, d, J = 4Hz), 8.04(2H, d, J = 4Hz), 8.92(2H, s), 9.27(2H, s).

[0333] [Example 13]

[0334] [ka]

[0335] [Synthesis of compound (13-3)] In a glass reaction vessel, 50 mg (0.0513 mmol) of compound (11-2), 23.4 mg (0.128 mmol) of compound (13-2), 0.977 mg (0.00513 mmol) of copper (I) iodide, 26.0 mg (0.257 mmol) of triethylamine, and 2.5 mL of tetrahydrofuran were placed and reacted at 60°C for 1 hour under a nitrogen atmosphere. After cooling to room temperature, the mixture was poured into 5 mL of methanol, and the precipitated solid was collected by filtration. The obtained solid was purified by silica gel column chromatography to obtain 35 mg (0.0306 mmol, yield 59.7%) of compound (13-3). Compound (13-3): 1 H NMR(CDCl3) δ 1.22-1.26(42H,m), 3.96(6H,s), 7.47(4H,s), 9.03(2H,s), 9.12(2H,s).

[0336] [Synthesis of compound (13-1)] In a glass reaction vessel, 35 mg (0.0306 mmol) of compound (13-3), 15.3 mg (0.0918 mmol) of compound (13-4), and 1.7 mL of o-dichlorobenzene were placed and reacted at 100°C for 1 hour under a nitrogen atmosphere. After cooling to room temperature, the mixture was poured into 17 mL of methanol, and the precipitated solid was collected by filtration. The obtained solid was purified by silica gel column chromatography to obtain 15.0 mg (0.0143 mmol, yield 46.6%) of compound (13-1). Compound (13-1): 1 H NMR(CDCl3) δ 1.22-1.35(42H,m), 3.77(6H, s), 3.87(6H, s), 5.40(4H,s), 6.42(2H, d, J = 10Hz), 6.48 (2H, s), 7.15(2H, d, J = 10Hz), 8.98(2H,s), 9.69(2H,s).

[0337] Among the above compounds (11-1), (12-1), and (13-1), the transistor characteristics of the compound (11-1) were evaluated in the same manner as in Example 1, and it was confirmed that the compound (11-1) had characteristics equivalent to those of the compound (1-1).

[0338] [Examples 14 to 19] The compound represented by formula (2) could be synthesized from the following compound in the same manner as in Example 1. In Examples 14 to 19, the solubility of the raw materials was improved, and it was found that there were advantages in synthesis such as the ability to reduce the amount of reaction solvent. Note that the synthesis method shown below is the same as the synthesis method in Example 1 except that the starting compound is different, and only the results are shown. Furthermore, comparison of the results of Examples 14 to 19 and Examples 1, 5, and 6 reveals that the yield is superior when the number of carbon atoms in the aliphatic hydrocarbon group in the compound represented by formula (8) (or the compound represented by formula (11A)) is 2 or more.

[0339] Example 14 <Synthesis of compound (1-1)>

[0340] [ka]

[0341] Compound (1-1): Yield 470 mg (0.782 mmol, 64.1%)

[0342] Example 15 <Synthesis of compound (1-1)>

[0343] [ka]

[0344] Compound (1-1) 471 mg (0.784 mmol, yield 64.3%)

[0345] Example 16 <Synthesis of compound (1-1)>

[0346] [ka]

[0347] Compound (1-1): Yield 469 mg (0.779 mmol, 63.9%)

[0348] Example 17 <Synthesis of compound (1-1)>

[0349] [ka]

[0350] Compound (1-1): Yield 470 mg (0.781 mmol, 64.0%)

[0351] Example 18 <Synthesis of compound (1-1)>

[0352] [ka]

[0353] Compound (1-1): Yield 468 mg (0.778 mmol, 63.8%)

[0354] Example 19 <Synthesis of compound (1-1)>

[0355] [ka]

[0356] Compound (1-1): Yield 465 mg (0.775 mmol, 63.5%)

[0357] [Example 20] The compound represented by formula (2) could also be synthesized from the following compound in the same manner as in Example 8. Note that the synthesis method shown below is the same as the synthesis method in Example 8 except that the starting compound is different, and only the results are shown. Furthermore, a comparison of the results of Example 20 and Example 8 reveals that the yield is superior when the number of carbon atoms in the aliphatic hydrocarbon group in the compound represented by formula (8) (or the compound represented by formula (11A)) is 2 or more.

[0358] [ka]

[0359] Compound (8-1): Yield 36.1 mg (0.0637 mmol, 8.50% yield from compound (14-1) [Explanation of symbols]

[0360] 1 Board 2. Gate electrode 3. Gate insulating film 4A Source Electrode 4B Drain electrode 5. Organic semiconductor film (organic semiconductor layer) 6 Sealing layer 10, 20 Organic Thin Film Transistor (Organic TFT) 41 Coating Fluid 42 Substrate 43 Materials

Claims

1. A method for producing a cyclic imide compound, comprising reacting a compound represented by the following formula (1) with at least one amine compound to obtain a compound represented by the following formula (2): 【Chemistry 1】 In formula (1), A 11 ~A 18 Each independently represents -N= or -C(R 15 ) = R 15 represents a hydrogen atom or a substituent. 11 ~A 18 At least one of R represents -N=. 11 ~R 14 each independently represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or a phenyl group which may have an electron-withdrawing group. 11 and R 14 One of these represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and the other represents a phenyl group which may have an electron-withdrawing group. 12 and R 13 one of which represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and the other represents a phenyl group which may have an electron-withdrawing group. The electron-withdrawing group represents a halogen atom, an acyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a halogenated alkyl group, a halogenated alkyloxy group, an aminocarbonyl group, an alkanesulfonyl group, an arylsulfonyl group, a cyano group, a nitro group, or a formyl group. In formula (2), A 11 ~A 18 is A in formula (1). 11 ~A 18 It is the same as R. 31 and R 51 each independently represents a substituent.

2. A step Y1 of reacting the compound represented by the formula (1) with a first amine compound represented by the following formula (3) to obtain a compound represented by the following formula (4); A process Y2 of reacting the compound represented by the formula (4) with a second amine compound represented by the following formula (5) to obtain a compound represented by the following formula (6); The compound represented by formula (6) is then reacted with the protecting group P 31 to obtain a compound represented by the following formula (7); and a step Y4 of obtaining the compound represented by formula (2) from the compound represented by formula (7). 【Chemistry 2】 In formula (3), R 31 is R in formula (2). 31 It is synonymous with. 31 represents a protecting group. In formula (4), A 11 ~A 18 Each of them represents A in formula (1). 11 ~A 18 It is the same as R. 12 ~R 14 Each of them represents R in formula (1). 12 ~R 14 However, R 14 R represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. 31 is R in formula (3). 31 It is synonymous with. 31 is P in formula (3). 31 is synonymous with. In formula (5), R 51 is R in formula (2). 51 is synonymous with. In formula (6), A 11 ~A 18 Each of them represents A in formula (1). 11 ~A 18 It is the same as R. 14 R represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. 31 is R in formula (3). 31 It is synonymous with. 31 is P in formula (3). 31 It is the same as R. 51 is R in formula (5). 51 is synonymous with. In formula (7), A 11 ~A 18 Each of them represents A in formula (1). 11 ~A 18 It is the same as R. 14 R represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. 31 is R in formula (3). 31 It is the same as R. 51 is R in formula (5). 51 is synonymous with.

3. The method for producing a cyclic imide compound according to claim 1 or 2, wherein the compound represented by formula (1) is a compound represented by the following formula (8), and the compound represented by formula (2) is a compound represented by the following formula (9): 【Chemistry 3】 In formula (8), R 11 ~R 14 Each of them represents R in formula (1). 11 ~R 14 However, R 14 R represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. 81 ~R 86 each independently represents a hydrogen atom or a substituent. In formula (9), R 31 and R 51 Each of them represents R in formula (2). 31 and R 51 It is the same as R. 81 ~R 86 Each of them represents R in formula (8). 81 ~R 86 is synonymous with.

4. The method for producing a cyclic imide compound according to claim 3 , wherein the compound represented by formula (8) is a compound represented by the following formula (10): 【Chemistry 4】 In formula (10), X 101 and X 102 Each of n1 and n2 independently represents an integer of 1 to 5. 12 and R 14 R each independently represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. 81 ~R 86 Each of them represents R in formula (8). 81 ~R 86 The electron-withdrawing group represents a halogen atom, an acyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a halogenated alkyl group, a halogenated alkyloxy group, an aminocarbonyl group, an alkanesulfonyl group, an arylsulfonyl group, a cyano group, a nitro group, or a formyl group.

5. The method for producing a cyclic imide compound according to claim 4, wherein the compound represented by formula (10) is a compound represented by the following formula (10'): 【Chemistry 5】 In formula (10'), X 111 ~X 116 Each of R independently represents a halogen atom. 12 and R 14 R each independently represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. 81 ~R 86 Each of them represents R in formula (8). 81 ~R 86 is synonymous with.

6. X 111 ~X 116 The method for producing a cyclic imide compound according to claim 5 , wherein represents a chlorine atom.

7. a step Y1′ of reacting a compound represented by the following formula (X1) with a compound represented by the following formula (X2) to obtain a composition containing a compound represented by the following formula (11A) and a compound represented by the following formula (11B), and then reacting the composition with a first amine compound represented by the following formula (12) without performing column purification on the composition to obtain a compound represented by the following formula (13); A step Y2' of reacting the compound represented by the formula (13) with a second amine compound represented by the following formula (14) to obtain a compound represented by the following formula (15); The compound represented by the formula (15) may be treated with a protecting group P 31 to obtain a compound represented by the following formula (16); and a step Y4' of obtaining the compound represented by formula (9) from the compound represented by formula (16). 【Chemistry 6】 【change】 In formula (X1), X 1 ~X 4 each represents a halogen atom or —CO—O—R 101 Represents 101 represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or a phenyl group which may have an electron-withdrawing group. 1 and X 4 one represents a halogen atom, and the other represents -CO-O-R 101 Also, X 2 and X 3 one represents a halogen atom, and the other represents -CO-O-R 101 Represents 81 ~R 86 Each of them represents R in formula (8). 81 ~R 86 is synonymous with. In formula (X2), R 101 represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or a phenyl group which may have an electron-withdrawing group. In formula (11A), X 5 ~X 8 Each independently represents -CO-O-R 101 Represents 101 each independently represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or a phenyl group which may have an electron-withdrawing group. 5 Inside R 101 And, X 8 Inside R 101 one represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and the other represents a phenyl group which may have an electron-withdrawing group. 6 Inside R 101 and X 7 Inside R 101 one represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and the other represents a phenyl group which may have an electron-withdrawing group. 81 ~R 86 Each of them represents R in formula (8). 81 ~R 86 is synonymous with. R 101 The electron-withdrawing group which may be possessed by the phenyl group represented by the formula (I) represents a halogen atom, an acyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a halogenated alkyl group, a halogenated alkyloxy group, an aminocarbonyl group, an alkanesulfonyl group, an arylsulfonyl group, a cyano group, a nitro group, or a formyl group. In formula (11B), X 9 and X 10 One of the groups represents a hydrogen atom, and the other group represents -CO-O-R 101 Represents 101 is R in formula (X1). 101 It is the same as: 6 and X 7 Each of them represents X in formula (11A). 6 and X 7 It is the same as R. 81 ~R 86 Each of them represents R in formula (8). 81 ~R 86 is synonymous with. In formula (12), R 31 represents a substituent. 31 represents a protecting group. In formula (13), X 11 and X 12 On the other hand, -CO-O-R 101 and the other represents -CO-N(R 31 ) (P 31 ) represents R 101 is R in formula (X1). 101 It is the same as R. 31 and P 31 Each of them represents R in formula (12). 31 and P 31 It is the same as: 6 and X 7 Each of them represents X in formula (11A). 6 and X 7 It is the same as R. 81 ~R 86 Each of them represents R in formula (8). 81 ~R 86 is synonymous with. In formula (14), R 51 represents a substituent. In formula (15), X 11 and X 12 Each of them represents X in formula (13). 11 and X 12 It is the same as R. 51 is R in formula (14). 51 It is the same as R. 81 ~R 86 Each of them represents R in formula (8). 81 ~R 86 is synonymous with. In formula (16), X 13 and X 14 On the other hand, -CO-O-R 101 and the other represents -CO-N(R 31 ) (H). 101 is R in formula (X1). 101 It is the same as R. 51 is R in formula (14). 51 It is the same as R. 81 ~R 86 Each of them represents R in formula (8). 81 ~R 86 is synonymous with.

8. 2. A method for producing a cyclic imide compound according to claim 1, comprising the steps of: reacting a compound represented by the following formula (X1) with a compound represented by the following formula (X2) to obtain a composition containing a compound represented by the following formula (11A) and a compound represented by the following formula (11B), and then reacting the composition with an amine compound represented by the following formula (14) without performing column purification on the composition to obtain a compound represented by the following formula (9'). 【Chemistry 7】 【change】 In formula (X1), X 1 ~X 4 each independently represents a halogen atom or -CO-O-R 101 Represents 101 represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or a phenyl group which may have an electron-withdrawing group. 1 and X 4 one represents a halogen atom, and the other represents -CO-O-R 101 Also, X 2 and X 3 one represents a halogen atom, and the other represents -CO-O-R 101 Represents 81 ~R 86 each independently represents a hydrogen atom or a substituent. In formula (X2), R 101 represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or a phenyl group which may have an electron-withdrawing group. In formula (11A), X 5 ~X 8 Each independently represents -CO-O-R 101 Represents 101 each independently represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or a phenyl group which may have an electron-withdrawing group. 5 R in 101 And, X 8 R in 101 one represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and the other represents a phenyl group which may have an electron-withdrawing group. 6 R in 101 and X 7 R in 101 one represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and the other represents a phenyl group which may have an electron-withdrawing group. 81 ~R 86 Each of them represents R in formula (X1). 81 ~R 86 is synonymous with. R 101 The electron-withdrawing group which may be possessed by the phenyl group represented by the formula (I) represents a halogen atom, an acyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a halogenated alkyl group, a halogenated alkyloxy group, an aminocarbonyl group, an alkanesulfonyl group, an arylsulfonyl group, a cyano group, a nitro group, or a formyl group. In formula (11B), X 9 and X 10 One of the groups represents a hydrogen atom, and the other group represents -CO-O-R 101 Represents 101 is R in formula (X1). 101 It is the same as: 6 and X 7 Each of them represents X in formula (11A). 6 and X 7 It is the same as R. 81 ~R 86 Each of them represents R in formula (X1). 81 ~R 86 is synonymous with. In formula (14), R 51 represents a substituent. In formula (9'), R 51 represents a substituent.

9. The method for producing a cyclic imide compound according to claim 7 or 8, further comprising a step Y0' of purifying the compound represented by formula (X2) before reacting the compound represented by formula (X1) with the compound represented by formula (X2).

10. A composition used for synthesizing a compound represented by the following formula (9): The composition contains at least a compound represented by the following formula (8): The composition, wherein the total content of the compound represented by the following formula (17) and the compound represented by the following formula (18) is 3.0 mass % or less based on the total solid content of the composition. 【Chemistry 8】 In formula (9), R 31 and R 51 Each independently represents a substituent. 81 ~R 86 each independently represents a hydrogen atom or a substituent. In formula (8), R 11 ~R 14 each independently represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or a phenyl group which may have an electron-withdrawing group. 11 and R 14 One of these represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and the other represents a phenyl group which may have an electron-withdrawing group. 12 and R 13 One of R represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and the other represents a phenyl group which may have an electron-withdrawing group. 81 ~R 86 are R represented by the formula (9), 81 ~R 86 R in formula (8) 11 ~R 14 The electron-withdrawing group which may be possessed by the phenyl group represented by the formula (I) represents a halogen atom, an acyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a halogenated alkyl group, a halogenated alkyloxy group, an aminocarbonyl group, an alkanesulfonyl group, an arylsulfonyl group, a cyano group, a nitro group, or a formyl group. In formula (17), R 12 ~R 14 each independently represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or a phenyl group which may have an electron-withdrawing group. 12 and R 13 One of R represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and the other represents a phenyl group which may have an electron-withdrawing group. 81 ~R 86 are R represented by the formula (9), 81 ~R 86 R in formula (17) 12 ~R 14 The electron-withdrawing group which may be possessed by the phenyl group represented by the formula (I) represents a halogen atom, an acyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a halogenated alkyl group, a halogenated alkyloxy group, an aminocarbonyl group, an alkanesulfonyl group, an arylsulfonyl group, a cyano group, a nitro group, or a formyl group. In formula (18), R 11 ~R 13 each independently represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or a phenyl group which may have an electron-withdrawing group. 12 and R 13 One of R represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and the other represents a phenyl group which may have an electron-withdrawing group. 81 ~R 86 are R represented by the formula (9), 81 ~R 86 R in formula (18) is the same as 11 ~R 13 The electron-withdrawing group which may be possessed by the phenyl group represented by the formula (I) represents a halogen atom, an acyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a halogenated alkyl group, a halogenated alkyloxy group, an aminocarbonyl group, an alkanesulfonyl group, an arylsulfonyl group, a cyano group, a nitro group, or a formyl group.

11. A compound represented by the following formula (4): 【Chemistry 9】 In formula (4), A 11 ~A 18 Each independently represents -N= or -C(R 15 ) = R 15 represents a hydrogen atom or a substituent. 11 ~A 18 At least one of R represents -N=. 12 ~R 13 each independently represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or a phenyl group which may have an electron-withdrawing group. 12 and R 13 One of R represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and the other represents a phenyl group which may have an electron-withdrawing group. 14 R represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. 31 represents a substituent. 31 represents a benzyl group, a naphthylmethyl group, a 2-methoxybenzyl group, a p-methoxybenzyl group, a 2,4-dimethoxybenzyl group, a 3,4,5-trimethoxybenzyl group, a 3,4-dimethoxybenzyl group, a 2-thienylmethyl group, a 2-furylmethyl group, a nitrobenzenesulfonyl group, a dinitrobenzenesulfonyl group, a tert-butoxycarbonyl group, an allyloxycarbonyl group, a benzyloxycarbonyl group, a methoxycarbonyl group, a 2,2,2-trichloroethoxycarbonyl group, a 9-fluorenylmethoxycarbonyl group, a trimethylsilylethoxycarbonyl group, or a (2-trimethylsilyl)ethanesulfonyl group. The electron-withdrawing group represents a halogen atom, an acyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a halogenated alkyl group, a halogenated alkyloxy group, an aminocarbonyl group, an alkanesulfonyl group, an arylsulfonyl group, a cyano group, a nitro group, or a formyl group.

12. A compound represented by the following formula (6): 【Chemistry 10】 In formula (6), A 11 ~A 18 Each independently represents -N= or -C(R 15 ) = R 15 represents a hydrogen atom or a substituent. 11 ~A 18 At least one of R represents -N=. 14 R represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. 31 and R 51 Each independently represents a substituent. 31 represents a benzyl group, a naphthylmethyl group, a 2-methoxybenzyl group, a p-methoxybenzyl group, a 2,4-dimethoxybenzyl group, a 3,4,5-trimethoxybenzyl group, a 3,4-dimethoxybenzyl group, a 2-thienylmethyl group, a 2-furylmethyl group, a nitrobenzenesulfonyl group, a dinitrobenzenesulfonyl group, a tert-butoxycarbonyl group, an allyloxycarbonyl group, a benzyloxycarbonyl group, a methoxycarbonyl group, a 2,2,2-trichloroethoxycarbonyl group, a 9-fluorenylmethoxycarbonyl group, a trimethylsilylethoxycarbonyl group, or a (2-trimethylsilyl)ethanesulfonyl group.

13. A compound represented by the following formula (7): 【Chemistry 11】 In formula (7), A 11 ~A 18 Each independently represents -N= or -C(R 15 ) = R 15 represents a hydrogen atom or a substituent. 11 ~A 18 At least one of R represents -N=. 14 R represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. 31 and R 51 each independently represents a substituent.

14. A compound represented by the following formula (11A″): 【Chemistry 12】 In formula (11A''), X 5 ~X 8 Each independently represents -CO-O-R 101 Represents 101 each independently represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or a phenyl group which may have an electron-withdrawing group. However, X 5 R in 101 And, X 8 R in 101 one represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and the other represents a phenyl group which may have an electron-withdrawing group. 6 R in 101 and X 7 R in 101 one represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and the other represents a phenyl group which may have an electron-withdrawing group. 101 When the alkyl group of R has one carbon atom, 101 The phenyl group represents a phenyl group that is unsubstituted or substituted with one or two electron-withdrawing groups. R 83 ~R 86 each independently represents a hydrogen atom or a substituent. The electron-withdrawing group represents a halogen atom, an acyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a halogenated alkyl group, a halogenated alkyloxy group, an aminocarbonyl group, an alkanesulfonyl group, an arylsulfonyl group, a cyano group, a nitro group, or a formyl group.

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