Compounds and methods of making compounds

Abstract

A compound represented by formula (1A), formula (1B), formula (2-1), or formula (2-2). The description of each substituent in the formula is shown in the specification.

Description

Technical Field

[0001] This invention relates to a compound and a method for manufacturing the compound. Background Technology

[0002] In recent years, the information and communication field has seen a continuous trend towards higher signal frequencies in information and communication equipment in order to achieve high-speed / high-capacity transmission. To address this trend towards higher frequencies, the requirements for low dielectric constant and low dielectric loss tangent in insulators used in printed circuit boards or semiconductor packages are constantly increasing.

[0003] With the advent of 5G (fifth-generation mobile communication technology), the signal transmission frequency on printed circuit boards is increasing. In order to reduce transmission losses in high-frequency bands and cope with high-temperature solder or high-multilayer assembly in the board assembly process, the insulating materials of copper-clad laminates are required to have better dielectric properties and heat resistance.

[0004] As such insulating materials, hydrocarbon resins such as polyvinyl styrene resin (e.g., see Patent Document 1), polybutadiene resin, and styrene-butadiene copolymer are known (e.g., see Patent Document 2). These hydrocarbon resins are known to have low molecular chain polarity and excellent dielectric properties.

[0005] In addition, in the aforementioned Patent Document 1, as an insulating material for copper-clad laminates that reduces transmission loss in high-frequency bands while exhibiting excellent high-temperature solder resistance during substrate mounting, accompanying the advent of 5G (fifth-generation mobile communication technology), a high-Tg hydrocarbon resin comprising an aromatic monolith containing aromatic vinyl groups is disclosed.

[0006] In addition, Patent Document 2 discloses a curable resin composition for forming an insulating layer for printed circuit boards used in high-frequency bands, which has both low thermal expansion and low dielectric loss tangent, wherein any one of a polybutadiene compound, a polyfunctional styrene compound, or a bismaleimide compound is used as a curable component in the composition.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Chinese Patent No. 116284692

[0010] Patent Document 2: Chinese Patent No. 101692756 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] However, the hydrocarbon resin has disadvantages such as extremely high flexibility, poor adhesion to the substrate, poor heat resistance, low glass transition temperature, insufficient rigidity, and high coefficient of thermal expansion. In the coating process of copper clad laminates, even if resins with excellent heat resistance and mechanical properties (e.g., thermosetting polyphenyl ether, bismaleimide resin) are added to modify the material, no significant improvement can be achieved, thus limiting its application in high-frequency printed circuit boards.

[0013] Furthermore, the resin compositions disclosed in any of the aforementioned patent documents cannot uniformly and comprehensively meet the requirements of insulating materials used in electronic materials such as printed circuit boards used in high-frequency bands, including solubility in various solvents, heat resistance, low dielectric constant, low dielectric loss tangent, and adhesion to different materials. Therefore, there is a need to develop a cross-linked compound that is preferably used as an insulating material for electronic materials such as printed circuit boards used in high-frequency bands.

[0014] One embodiment of the present invention aims to provide a novel compound and a method for manufacturing the same.

[0015] Technical means to solve the problem

[0016] The means of solving the aforementioned problem include the following embodiments.

[0017] <1> A compound represented by the following formula (1A), formula (1B), formula (2-1) or formula (2-2).

[0018] [Chemistry 1]

[0019]

[0020] In equation (1A),

[0021] R 11 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group.

[0022] R 12 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0023] R 13 Each of the following is independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms, or one or more other R groups present on the same carbon atom or on adjacent carbon atoms. 13 Ring structures with 5 to 10 ring elements formed by bonding.

[0024] n12 is an integer from 2 to 4, n13 is an integer from 0 to 6, n14 is an integer from 1 to 12, and n15 is either 1 or 2.

[0025] When n15 is 1, R 10 It is a hydrogen atom.

[0026] When n15 is 2, R 10 It is a single bond, a substituted or unsubstituted methylene group, or a divalent hydrocarbon group having 2 to 20 carbon atoms.

[0027] [Chemistry 2]

[0028]

[0029] In equation (1B), R 11 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group.

[0030] R 12 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 101 It is a divalent hydrocarbon group with 3 or more carbon atoms.

[0031] [Chemistry 3]

[0032]

[0033] In equation (2-1), A 1 and A 2 Let n represent the bases represented by equations (A-1) and (A-2), respectively, where n22 is an integer from 2 to 4.

[0034] [Chemistry 4]

[0035]

[0036] In equation (A-1), R 21 R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group. 22 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The # in formula (A-1) represents the bond site with the ## in formula (A-2).

[0037] In equation (A-2), R 23 Each is an alkyl or halogen atom with 1 to 5 carbon atoms, n22 is an integer of 2 to 4, n23 is an integer of 0 to 4, n24 is 0 or 1, and ## in formula (A-2) represents the bonding site with # in formula (A-1).

[0038] Wherein, n23+n22 is the number below the maximum number of substituents of the aromatic ring contained in formula (A-2).

[0039] [Chemistry 5]

[0040]

[0041] In equation (2-2),

[0042] R 21 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group.

[0043] R 22 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0044] R 20 A polymer chain having repeating units represented by the following formula (6) or formula (7).

[0045] [Chemistry 6]

[0046]

[0047] In equations (6) and (7), Ar 1 Each can be independently represented as either substituted or unsubstituted aromatic ring groups.

[0048] In equation (6), Ar 2 Indicates substituted or unsubstituted aromatic ring groups.

[0049] In equation (7), Ar 3 Each can be independently represented as either substituted or unsubstituted aromatic ring groups.

[0050] In equation (7), R 1 Each of the following can independently represent a hydrogen atom, an alkyl or aryl group, or multiple R groups. 1 The substituted or unsubstituted ring structures formed by the combination of these bonded carbon atoms.

[0051] This indicates the bonding site with the aromatic ring in equation (2-2).

[0052] Ar represents the expression in equation (6). 1 Or the bonding site of the aromatic ring in formula (2-2),

[0053] When u and n are integers greater than or equal to 1, u and n are used as subscripts, and parentheses () or square brackets [] indicate repeated units. When u and n are greater than or equal to 2, multiple R... 1 They can be the same or different.

[0054] <2> According to the compound described in <1>, wherein the compound represented by the formula (1A) is the compound represented by the formula (1-1) or the formula (1-2) below.

[0055] [Chemistry 7]

[0056]

[0057] In equation (1-1),

[0058] R 11 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group.

[0059] R 12 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0060] R 13 Each of the following is independently an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or one or more other R groups present on or adjacent to the same carbon atom. 13 Ring structures with 5 to 10 ring elements formed by bonding.

[0061] n12 is an integer from 2 to 4, n13 is an integer from 0 to 6, and n14 is an integer from 1 to 12.

[0062] [Chemistry 8]

[0063]

[0064] In equation (1-2),

[0065] R 11 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group.

[0066] R 12 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0067] n12 is an integer from 2 to 4, n13 is an integer from 0 to 6, and n14 is an integer from 1 to 12.

[0068] R 13 Each of the following is independently an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or one or more other R groups present on the same carbon atom or adjacent carbon atoms. 13 Ring structures with 5 to 10 ring elements formed by bonding.

[0069] R 10 It is a single bond, a substituted or unsubstituted methylene group, or a divalent hydrocarbon group having 2 to 20 carbon atoms.

[0070] <3> According to the compound described in <1> or <2>, wherein R in formula (1A) or formula (1B) 11 At least one of them is an alkyl group having 1 to 5 carbons, an aryl group having 6 to 12 carbons, or an alkyl group having 1 to 5 carbons that has been substituted with an aryl group.

[0071] <4> A method for manufacturing a compound, comprising the steps indicated by (IA) below.

[0072] [Chemistry 9]

[0073]

[0074] In (IA), R 11 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group.

[0075] R 12 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0076] R 13 Each of the following is independently an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or one or more other R groups present on or adjacent to the same carbon atom. 13 Ring structures with 5 to 10 ring elements formed by bonding.

[0077] n12 is an integer from 2 to 4, n13 is an integer from 0 to 6, n14 is an integer from 1 to 12, and n15 is either 1 or 2.

[0078] When n15 is 1, R 10 For a hydrogen atom, when n15 is 2, R 10 It is a single bond, a substituted or unsubstituted methylene group, or a divalent hydrocarbon group having 2 to 20 carbon atoms.

[0079] <5> A method for manufacturing a compound, comprising the steps indicated in (II) below.

[0080] [Chemistry 10]

[0081]

[0082] In (II), in equation (2-1), A 1 and A 2 Let A-1 and A-2 represent the bases respectively.

[0083] In equation (A-1), R 21 R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group.22 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The # in formula (A-1) represents the bond site with the ## in formula (A-2).

[0084] In equation (A-2), R 23 Each is an alkyl or halogen atom with 1 to 5 carbon atoms, n22 is an integer of 2 to 4, n23 is an integer of 0 to 4, n24 is 0 or 1, and ## in formula (A-2) represents the bonding site with # in formula (A-1).

[0085] Wherein, n23+n22 is the number below the maximum number of substituents of the aromatic ring contained in formula (A-2).

[0086] <6> A method for manufacturing a compound, comprising the steps indicated in (III) below.

[0087] [Chemistry 11]

[0088]

[0089] In (III), R 21 R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group. 22 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, polym.A1 and R 20 A polymer chain having the structure represented by formula (6) or formula (7) below.

[0090] [Chemistry 12]

[0091]

[0092] In equations (6) and (7), Ar 1 Each can be independently represented as either substituted or unsubstituted aromatic ring groups.

[0093] In equation (6), Ar 2 Indicates substituted or unsubstituted aromatic ring groups.

[0094] In equation (7), Ar 3 Each can be independently represented as either substituted or unsubstituted aromatic ring groups.

[0095] In equation (7), R 1 Each can be independently a hydrogen atom, alkyl group, or aryl group, or represent multiple R groups. 1 The substituted or unsubstituted ring structures formed by the combination of these bonded carbon atoms. This indicates the bonding site with the aromatic ring in equation (2-2). Ar represents the expression in equation (6). 1 In equation (2-2), the bonding sites of the aromatic rings, u and n are integers greater than or equal to 1, and u and n are recorded as subscripts () or [] to indicate repeating units. Where u and n are 2 or greater, multiple R... 1 Same or different.

[0096] The effects of the invention

[0097] An embodiment of the present invention provides a novel compound and a method for manufacturing the same. Detailed Implementation

[0098] The compounds represented by formula (1A), formula (1B), formula (2-1) or formula (2-2) of the present invention (hereinafter, sometimes referred to as "the compounds") are novel compounds.

[0099] This compound has the specific structure shown below, and is therefore preferably used as an insulating material in electronic materials such as printed circuit boards used in high-frequency bands with excellent crosslinking properties.

[0100] The following provides a detailed description of this compound and its manufacturing method.

[0101] [Compounds represented by formula (1A) or formula (1B)]

[0102] The compounds of the present invention are represented by formula (1A) or formula (1B).

[0103] [Chemistry 13]

[0104]

[0105] In equation (1A), R 11 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group.

[0106] R 12 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0107] R 13 Each of the following is independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms, or one or more other R groups present on the same carbon atom or on adjacent carbon atoms. 13 A ring structure with 5 to 10 ring elements formed by bonding (hereinafter also referred to as "ring structure with 5 to 10 ring elements").

[0108] n12 is an integer from 2 to 4, n13 is an integer from 0 to 6, n14 is an integer from 1 to 12, and n15 is either 1 or 2.

[0109] When n15 is 1, R 10 It is a hydrogen atom.

[0110] When n15 is 2, R 10 It is a single bond, a substituted or unsubstituted methylene group, or a divalent hydrocarbon group having 2 to 20 carbon atoms.

[0111] [Chemistry 14]

[0112]

[0113] In equation (1B), R 11 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group.

[0114] R 12 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 101 It is a divalent hydrocarbon group with 3 or more carbon atoms, for example, a divalent group formed by combining a substituted or unsubstituted aromatic group and a substituted or unsubstituted methylene group.

[0115] <R 11 >

[0116] Alkyl groups having 1 to 5 carbon atoms can be straight-chain or branched, for example: methyl, ethyl, n-propyl, isopropyl, etc.

[0117] Examples of cycloalkyl groups with 5 to 10 carbon atoms include cyclopentyl, cyclohexyl, and adamantyl.

[0118] Examples of aryl groups having 6 to 12 carbon atoms include phenyl, naphthyl, and groups with alkyl groups bonded to their rings.

[0119] Examples of alkyl groups with 1 to 5 carbon atoms that are substituted with an aryl group include alkyl groups with 1 to 5 carbon atoms substituted with phenyl, naphthyl, etc. Examples of alkyl groups with 1 to 5 carbon atoms that are substituted with an aryl group include methyl, ethyl, n-propyl, isopropyl, etc., substituted with phenyl, naphthyl, etc.

[0120] As R 11 Each of the following is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms that has been substituted with an aryl group.

[0121] More preferably R 11 At least one of them is an alkyl group having 1 to 5 carbons, an aryl group having 6 to 12 carbons, or an aryl-substituted alkyl group having 1 to 5 carbons, and is preferably R. 11 At least one of them is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms, particularly preferably one of them.11 It is an alkyl group having 1 to 5 carbon atoms, and the other R 11 It is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, most preferably one of them. 11 It is an alkyl group having 1 to 3 carbon atoms, and the other R 11 It is a hydrogen atom.

[0122] <R 12 >

[0123] As R 12 Each of the following is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

[0124] <<n12, n13 and n14>>

[0125] n12 is preferably 2 or 3.

[0126] n13 is preferably an integer from 0 to 4. n14 is preferably an integer from 1 to 10, more preferably an integer from 1 to 5, and even more preferably an integer from 1 to 3, and particularly preferably 1 or 2.

[0127] <R 13 >

[0128] Alkyl groups having 1 to 5 carbon atoms can be straight-chain or branched, for example: methyl, ethyl, n-propyl, isopropyl, etc.

[0129] Examples of aryl groups with 6 to 12 carbon atoms include phenyl, naphthyl, and groups with alkyl groups bonded to their rings.

[0130] As one or more other R that exists on the same carbon atom or on adjacent carbon atoms 13 Ring structures formed by bonding have 5 to 10 ring elements, such as aromatic hydrocarbon ring structures with 6 to 10 ring elements and aromatic heterocyclic structures with 5 to 10 ring elements. The ring structure can be monocyclic or polycyclic. In the case of polycyclic structures, it can be a condensation ring of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Furthermore, the term "ring element number" refers to the number of carbon atoms or heteroatoms constituting the ring structure.

[0131] As aromatic hydrocarbon ring structures and aromatic heterocyclic structures, Ar in formulas (6) and (7) described later 1 Ar 2 and Ar 3 In this context, aromatic hydrocarbon ring structures with 5 to 10 ring elements and aromatic heterocyclic structures have the same meaning.

[0132] The ring structure having 5 to 10 ring elements is preferably a benzene structure, a naphthalene structure, a thiazole structure, an oxazole structure, or a furan structure, more preferably a benzene structure, a naphthalene structure, or a thiophene structure, and even more preferably a benzene structure.

[0133] R 13 Each is preferably an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 12 carbon atoms, or one or more other R groups present on the same carbon atom or on adjacent carbon atoms. 13 The ring structure formed by bonding has 5 to 8 ring elements, more preferably an alkyl group having 1 to 3 carbon atoms, or one or more other R groups present on the same carbon atom or adjacent carbon atoms. 13 The ring structure formed by bonding has 5 to 8 ring elements, and is preferably an alkyl group with 1 to 3 carbon atoms.

[0134] <R 10 >

[0135] In equation (1A), R is defined as follows when n15 is 2. 10 Preferably, it is a single bond, a substituted or unsubstituted methylene group, or a divalent hydrocarbon group having 2 to 10 carbon atoms; more preferably, it is an unsubstituted methylene group or a divalent hydrocarbon group having 2 to 4 carbon atoms; particularly preferably, it is a divalent hydrocarbon group having 2 to 4 carbon atoms; and most preferably, it is 2,2-propane-diyl.

[0136] <R 101 >

[0137] As a divalent hydrocarbon group with 3 or more carbon atoms, it is preferably a group represented by (-CR2-) with 3 or more carbon atoms or a divalent hydrocarbon group having therethe, more preferably a group represented by (-CR2-) with 3 or more carbon atoms or a group represented by a bond between the -CR2- and an aromatic hydrocarbon ring by one or more of the said -CR2-, and even more preferably 2,2-propanediyl or -CR2-Ar-CR2- (R is a substituent, and as a substituent, it is preferably a hydrocarbon group, more preferably an alkyl group, and even more preferably a methyl group; Ar represents an aromatic hydrocarbon group, and is preferably a phenylene group).

[0138] As R in equation (1B) 101 The divalent hydrocarbon group represented by the substituted or unsubstituted aromatic group and the substituted or unsubstituted methylene group is preferably the group shown below.

[0139] [Chemistry 15]

[0140]

[0141] R in the formula 102 Each is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. More preferably, methyl, ethyl, or propyl is the alkyl group having 1 to 5 carbon atoms, and particularly preferably methyl. In the formula... It represents the bond with the aromatic ring in equation (1B).

[0142] The compound represented by formula (1A) is preferably the compound represented by formula (1-1) or formula (1-2) below.

[0143] [Chemistry 16]

[0144]

[0145] In equation (1-1), R 11 R is independently composed of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aryl-substituted alkyl group having 1 to 5 carbon atoms. 12 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 13 Each of the following is independently an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or one or more other R groups present on or adjacent to the same carbon atom. 13 The ring structure formed by the bonding has 5 to 10 ring elements, where n12 is an integer from 2 to 4, n13 is an integer from 0 to 6, and n14 is an integer from 1 to 12.

[0146] R in equation (1-1) 11 R 12 and R 13 and R in equation (1A) from n12 to n14 11 R 12 and R 13 And n12 to n14 have the same meaning and the preferred form is also the same.

[0147] [Chemistry 17]

[0148]

[0149] In equation (1-2), R 11 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group.

[0150] R 12 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0151] R 13 Each of the following is independently an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or one or more other R groups present on the same carbon atom or adjacent carbon atoms. 13 Ring structures with 5 to 10 ring elements formed by bonding.

[0152] n12 is an integer from 2 to 4, n13 is an integer from 0 to 6, and n14 is an integer from 1 to 12.

[0153] R 10 It is a single bond, a substituted or unsubstituted methylene group, or a divalent hydrocarbon group having 2 to 20 carbon atoms.

[0154] R in equation (1-2) 10 R 11 R 12 and R 13 and R in equation (1A) from n12 to n14 10 R 11 R 12 and R 13 And n12 to n14 have the same meaning and the preferred form is also the same.

[0155] [The compound represented by formula (2-1)]

[0156] The compounds of the present invention are represented by the following formula (2-1).

[0157] [Chemistry 18]

[0158]

[0159] In equation (2-1), A 1 and A 2 Let n represent the bases represented by equations (A-1) and (A-2), respectively, where n22 is an integer from 2 to 4.

[0160] [Chemistry 19]

[0161]

[0162] In equation (A-1), R 21 R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group. 22 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The # in formula (A-1) represents the bond site with the ## in formula (A-2).

[0163] In equation (A-2), R 23 Each is an alkyl or halogen atom with 1 to 5 carbon atoms, n22 is an integer of 2 to 4, n23 is an integer of 0 to 4, n24 is 0 or 1, and ## in formula (A-2) represents the bonding site with # in formula (A-1).

[0164] Wherein, n23+n22 is the number below the maximum number of substituents of the aromatic ring contained in formula (A-2).

[0165] As the largest substitution base, for example, cases where it is 4 when n24 is 0, and 6 when n24 is 1 can be listed.

[0166] <R 21 >

[0167] R 21The alkyl group having 1 to 5 carbons, the aryl group having 6 to 12 carbons, and the alkyl group having 1 to 5 carbons substituted with aryl, and R in formula (1A) or formula (1B) are represented. 11 The terms alkyl with 1 to 5 carbon atoms, aryl with 6 to 12 carbon atoms, and alkyl with 1 to 5 carbon atoms substituted with aryl have the same meaning.

[0168] R 21 Each of the following is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group; more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms; even more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; and particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0169] <R 22 >

[0170] R 22 The alkyl group representing 1 to 5 carbon atoms and R in formula (1A) or formula (1B) 11 Alkyl groups with 1 to 5 carbon atoms have the same meaning.

[0171] R in equation (A-1) 22 Each of the following is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

[0172] <R 23 >

[0173] R 23 The alkyl group representing 1 to 5 carbon atoms and R in formula (1A) or formula (1B) 11 The alkyl groups representing 1 to 5 carbon atoms have the same meaning. As R 23 Halogen atoms in the atom can be, for example, fluorine, chlorine, iodine, bromine, etc.

[0174] R in equation (A-2) 23 Each atom is preferably an alkyl or halogen atom having 1 to 3 carbon atoms, more preferably an alkyl or fluorine atom having 1 to 3 carbon atoms, and even more preferably a fluorine atom.

[0175] <<n22, n23 and n24>>

[0176] n22 is preferably 2 or 3.

[0177] n23 is preferably an integer from 1 to 4, more preferably an integer from 2 to 4. n24 is preferably 1.

[0178] [The compound represented by formula (2-2)]

[0179] The compounds of the present invention are represented by the following formula (2-2).

[0180] [Chemistry 20]

[0181]

[0182] In equation (2-2), R 21 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group.

[0183] R 22 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0184] R 20 A polymer chain having repeating units represented by the following formula (6) or formula (7).

[0185] <<R 21 >>

[0186] R 21 R in equation (A-1) of equation (2-1) 21 For the same meaning, the preferred form is also the same.

[0187] <<R 22 >>

[0188] R 22 R in equation (A-1) of equation (2-1) 22 For the same meaning, the preferred form is also the same.

[0189] <<R 20 >>

[0190] R 20 A polymer chain having repeating units represented by the following formula (6) or formula (7).

[0191] [Chemistry 21]

[0192]

[0193] In equations (6) and (7), Ar 1 Each can be independently represented as either substituted or unsubstituted aromatic ring groups.

[0194] In equation (6), Ar 2 Indicates substituted or unsubstituted aromatic ring groups.

[0195] In equation (7), Ar 3 Each can be independently represented as either substituted or unsubstituted aromatic ring groups.

[0196] In equation (7), multiple R 1 Each can be independently a hydrogen atom, alkyl group, or aryl group, or represent two R groups.1 The substituted or unsubstituted ring structures formed by the combination of these bonded carbon atoms.

[0197] This indicates the bonding site with the aromatic ring in equation (2-2).

[0198] Ar represents the expression in equation (6). 1 Or the bonding site of the aromatic ring in formula (2-2),

[0199] When u and n are integers greater than or equal to 1, u and n are used as subscripts, and parentheses () or square brackets [] indicate repeated units. When u and n are greater than or equal to 2, multiple R... 1 They can be the same or different.

[0200] <<Ar 1 Ar 2 and Ar 3 >>

[0201] Ar 1 Ar 2 and Ar 3 The aromatic cyclic group represented is a group formed by removing two hydrogen atoms from the cyclic portion of a substituted or unsubstituted aromatic ring.

[0202] Examples of aromatic ring groups include aromatic hydrocarbon rings with 6 to 30 ring elements and aromatic heterocycles with 5 to 30 ring elements. The number of ring elements in the aromatic ring group is not particularly limited; for example, it is 5 to 30, preferably 5 to 20, and more preferably 5 to 10.

[0203] Examples of aromatic cyclic groups include: benzene rings; condensed polycyclic aromatic hydrocarbon cyclic groups such as naphthalene rings, indene rings, anthracene rings, fluorene rings, biphenylene rings, phenanthrene rings, pyrene rings, and perylene rings; cyclic aromatic hydrocarbon cyclic groups such as biphenyl rings, terphenyl rings, binaphthalene rings, and phenylnaphthalene rings; heterocyclic groups containing oxygen atoms such as furan rings, pyran rings, benzofuran rings, and benzopyran rings; heterocyclic groups containing nitrogen atoms such as pyrrole rings, pyridine rings, pyrimidine rings, indole rings, quinoline rings, and diketopyrrole rings; heterocyclic groups containing sulfur atoms such as thiophene rings and dibenzothiophene rings; heterocyclic groups containing silicon atoms such as silylfluorene rings; and heterocyclic groups containing two or more heteroatoms such as oxazole rings and thiazolyl groups.

[0204] Among these, as Ar 1 Ar 2 and Ar 3 The aromatic ring group represented is preferably an aromatic hydrocarbon ring group such as benzene ring, naphthalene ring, indene ring, anthracene ring, phenanthrene ring, fluorene ring, biphenyl ring, terphenyl ring, pyrene ring, perylene ring, dibenzothiophene ring, or silylfluorene ring.

[0205] Ar1 Ar 2 and Ar 3 Some of the hydrogen atoms in the aromatic ring group can be substituted by substituents. These hydrogen atoms are those related to Ar. 1 Ar 2 and Ar 3 The aromatic ring group other than the aromatic ring group is bonded to carbon atoms and hydrogen atoms other than hydrogen atoms.

[0206] Examples of substituents include: fluorine atom, cyano, nitro, alkyl, fluorinated alkyl, alkoxy, fluorinated alkoxy, alkylthio, or fluorinated alkylthio. "Fluorinated alkyl" refers to a group formed by substituting a fluorine atom for some or all of the hydrogen atoms in an alkyl group. The same applies to "fluorinated alkoxy" and "fluorinated alkylthio".

[0207] The number of carbon atoms in the alkyl or fluorinated alkyl group is typically 1 to 30. The term "number of carbon atoms" refers to the number of carbon atoms constituting the group. The term "alkyl" includes not only chain alkyl groups but also cycloalkyl groups.

[0208] Examples of alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, 2-methylbutyl, 1-methylbutyl, n-hexyl, isohexyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, heptyl, octyl, isooctyl, 2-ethylhexyl, 3,7-dimethyloctyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, 2-decyltetradecyl, and other chain alkyl groups; cyclopentyl, cyclohexyl, adamantyl, and other cycloalkyl groups.

[0209] The number of carbon atoms in the alkoxy or fluorinated alkoxy group is typically 1 to 30. The term "alkoxy" includes not only chain alkoxy groups but also cycloalkyloxy groups.

[0210] Examples of alkoxy groups include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentoxy, hexoxy, cyclohexyloxy, heptoxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy, trifluoromethoxy, pentafluoroethoxy, perfluorobutoxy, perfluorohexyloxy, perfluorooctyloxy, methoxymethyloxy, 2-methoxyethyloxy, etc.

[0211] The number of carbon atoms in the alkylthio group or fluorinated alkylthio group is typically 1 to 30, preferably 1 to 20. The term "alkylthio group" includes not only chain-like alkylthio groups but also cycloalkylthio groups.

[0212] Examples of alkylthio groups include: methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, tert-butylthio, pentylthio, hexylthio, cyclohexylthio, heptylthio, octylthio, 2-ethylhexylthio, nonylthio, decylthio, 3,7-dimethyloctylthio, laurylthio, trifluoromethylthio, etc.

[0213] When the aromatic ring has two or more substituents, adjacent substituents can combine with each other and together with these bonded atomic chains to form substituted or unsubstituted alicyclic structures. "Alicyclic structure" includes "aliphatic hydrocarbon ring structure" and "aliphatic heterocyclic structure". The substituents are the same as described above.

[0214] The number of ring elements in the alicyclic structure is, for example, 4 to 20, preferably 4 to 10.

[0215] Examples of alicyclic structures include aliphatic hydrocarbon ring structures with 4 to 20 ring elements and aliphatic heterocyclic structures with 4 to 20 ring elements.

[0216] Examples of aliphatic hydrocarbon ring structures include: monocyclic saturated alicyclic structures such as cyclobutane, cyclopentane, and cyclohexane; polycyclic saturated alicyclic structures such as norbornane, adamantane, tricyclic decane, and tetracyclic dodecane; monocyclic unsaturated alicyclic structures such as cyclobutene, cyclopentene, and cyclohexene; and polycyclic unsaturated alicyclic structures such as norbornene, tricyclic decene, and tetracyclic dodecene.

[0217] Examples of aliphatic heterocyclic structures include: heterocyclic structures containing oxygen atoms such as dioxane and dioxane; and heterocyclic structures containing sulfur atoms such as dithiocyclopentane and dithiane.

[0218] When the aromatic ring is an aromatic hydrocarbon ring, the substituent is preferably a fluorine atom, and more preferably a hydrogen atom in the aromatic hydrocarbon ring replaced by two or more fluorine atoms.

[0219] <<R 1 >>

[0220] As R in equation (7) 1 The number of carbon atoms in the aryl group is typically 6 to 30, preferably 6 to 20. Examples of aryl groups include phenyl and naphthyl groups.

[0221] In equation (7), as multiple R 1 The substituted or unsubstituted ring structures formed by the combination of these carbon atoms are substituted or unsubstituted. Examples include alicyclic hydrocarbon structures such as cyclopentyl, cyclohexyl, and cyclododecane; and aromatic hydrocarbon structures such as fluorene and phthalide.

[0222] Examples of substituents in the ring structure include alkyl groups and phenyl groups.

[0223] As R 1 The alkyl group referred to is not particularly limited and can be straight-chain, branched-chain, or cyclic. Examples of alkyl groups with 1 to 30 carbon atoms include alkyl groups.

[0224] Examples of alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, 2-methylbutyl, 1-methylbutyl, n-hexyl, isohexyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, heptyl, octyl, isooctyl, 2-ethylhexyl, 3,7-dimethyloctyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, 2-decyltetradecyl, and other chain alkyl groups; cyclopentyl, cyclohexyl, adamantyl, and other cycloalkyl groups.

[0225] As R 1 Preferably aryl or multiple R 1 The substituted or unsubstituted ring structure formed by the interaction of the carbon atoms bonded together, more preferably multiple R... 1 The unsubstituted ring structure formed by the combination of the carbon atoms and the bonds thereto is preferably an alkyl-substituted alicyclic structure.

[0226] <>

[0227] The values ​​of u and n are preferably 1 to 3, and more preferably 1.

[0228] As a repeating unit represented by formula (6) or formula (7), the repeating units represented by formulas (A-7) to (A-10) below can be listed as examples. As specific examples of repeating units represented by formula (7), the repeating units represented by formulas (A-7) to (A-10) below can be listed, but the present invention is not limited to these.

[0229] [Chemistry 22]

[0230]

[0231] Furthermore, in equation (2-2), in R 20 In the case of a polymer chain having repeating units as represented by equation (6), equation (2-2) can be represented by the following equation (2-2-1).

[0232] In equation (2-2-1), R 21 R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group. 22Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, Ar 1 and Ar 2 Each of the substituted or unsubstituted aromatic cyclic groups represents an independent substituted or unsubstituted aromatic cyclic group, where n is an integer greater than or equal to 1.

[0233] R in equation (2-2-1) 21 and R 22 R in equation (2-2) respectively 21 and R 22 For the same meaning, the preferred form is also the same.

[0234] Additionally, Ar in equation (2-2-1) 1 Ar 2 and n are respectively related to Ar in equation (6) 1 Ar 2 Both 'n' and 'n' have the same meaning and the preferred form is also the same.

[0235] [Chemistry 23]

[0236]

[0237] The lower limit of the number average molecular weight (Mn) of the compound represented by formula (2-2) in terms of polystyrene is preferably 1500, more preferably 2000, and even more preferably 2500, and the upper limit of the number average molecular weight (Mn) is preferably 10000, more preferably 8500, and even more preferably 7000.

[0238] The lower limit of the weight average molecular weight (Mw) of the compound represented by formula (2-2) based on polystyrene is preferably 1,000, more preferably 2,000, and even more preferably 3,000, and the upper limit of the weight average molecular weight (Mw) is preferably 15,000, more preferably 13,000, and even more preferably 10,000.

[0239] If Mn and Mw are within the aforementioned range, the solubility in solvents, compatibility with other compounds, and crosslinking density can be easily controlled, thus making it suitable for a variety of applications and therefore preferred.

[0240] Mn and Mw are values ​​determined by gel permeation chromatography (GPC) under the conditions described in the examples described later.

[0241] The following compounds can be listed as examples of the compounds described herein, but the invention is not limited to these compounds.

[0242] [Chemistry 24]

[0243]

[0244] [Chemistry 25]

[0245]

[0246] [Chemistry 26]

[0247]

[0248] In the illustrated compounds, Z is a base represented by the following formula (Z1) or formula (Z2).

[0249] [Chemistry 27]

[0250]

[0251] In the formulas (Z1) and (Z2) These represent the bonding sites of carbon atoms bonded to Z in compounds (1a) to (17a), (1b) to (4b), and (1c) to (8c), respectively.

[0252] [Method for manufacturing this compound]

[0253] The following describes the method for manufacturing the compound represented by formula (1A), formula (1B), formula (2-1) or formula (2-2) (hereinafter referred to as "the method for manufacturing this compound").

[0254] <Method for manufacturing the compound represented by formula (1A) or formula (1B)>

[0255] The method for manufacturing the compound represented by formula (1A) of the present invention includes the steps represented by (IA) below (hereinafter, sometimes referred to as "process (IA)").

[0256] Furthermore, the method for manufacturing the compound represented by formula (1B) of the present invention preferably includes the steps represented by (IB) (hereinafter, sometimes referred to as "process (IB)").

[0257] [Chemistry 28]

[0258]

[0259] In the process (IA), R 11 R is independently composed of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aryl-substituted alkyl group having 1 to 5 carbon atoms. 12 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 13 Each of the following is independently an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or one or more other R groups present on the same carbon atom or adjacent carbon atoms.13 The ring structure formed by bonding has 5 to 10 ring elements, where n12 is an integer from 2 to 4, n13 is an integer from 0 to 6, n14 is an integer from 1 to 12, and n15 is 1 or 2.

[0260] When n15 is 1, R 10 For a hydrogen atom, when n15 is 2, R 10 It is a single bond, a substituted or unsubstituted methylene group, or a divalent hydrocarbon group having 2 to 20 carbon atoms.

[0261] In the process (IA), R 11 R 12 and R 13 respectively with R in the above formula (1A) 11 R 12 and R 13 For the same meaning, the preferred form is also the same.

[0262] In addition, n12, n13, n14 and n15 in (IA) have the same meaning as n12, n13, n14 and n15 in the above formula (1A), and the preferred forms are also the same.

[0263] [Chemistry 29]

[0264]

[0265] In the process (IB), R 101 R is a divalent hydrocarbon group with 3 or more carbon atoms. 11 R is independently composed of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aryl-substituted alkyl group having 1 to 5 carbon atoms. 12 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0266] In the process (IB), R 101 R 11 and R 12 Respectively with R in equation (1B) 101 R 11 and R 12 For the same meaning, the preferred form is also the same.

[0267] In manufacturing methods that include the steps represented by process (IA) or process (IB), the reaction yield can be increased by adding a neutral inorganic salt to the reaction. By adding a neutral inorganic salt to the reaction, byproducts such as metal salts generated during the reaction combine with the neutral inorganic salt, thereby further promoting the reaction.

[0268] There are no particular limitations on the neutral inorganic salts mentioned above, and examples include: lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, and cesium chloride. Among these, from the viewpoint of better binding with metal salts produced as byproducts in the reaction, cesium fluoride and lithium chloride are preferred as neutral inorganic salts.

[0269] The amount of neutral inorganic salt added, in the steps represented by process (IA) or process (IB), is typically 1.0 molar to 100 molar equivalents, preferably 1.5 molar to 20 molar equivalents, and more preferably 2.0 molar to 10 molar equivalents, relative to the trifluoromethanesulfonic acid residues in the intermediate compound.

[0270] <<Manufacturing Conditions>>

[0271] The reaction temperature in the method for producing this compound is, for example, about 50°C to 160°C, preferably 60°C to 140°C. The reaction time is, for example, about 0.1 hours to 200 hours, preferably 1 hour to 30 hours.

[0272] There are no particular limitations on the environment for the manufacturing method of this compound, but an inert gas environment such as a nitrogen environment or an environment such as a vacuum environment that can suppress catalyst deactivation is preferred.

[0273] The preparation of this compound is generally carried out in a solvent. Examples of solvents include hydrocarbon solvents, ether solvents, and amide solvents. The solvent used in the steps represented by process (IA) or process (IB) is preferably the solvent used in the preparation of the compound including the steps represented by (II) described below or the preparation of the compound including the steps represented by (III).

[0274] <Method for manufacturing the compound represented by formula (2-1)>

[0275] The method for manufacturing the compound represented by formula (2-1) includes the steps represented by (II) below (hereinafter sometimes also referred to as "process (II)").

[0276] [Chemistry 30]

[0277]

[0278] In process (II), in equation (2-1), A 1 and A 2 Let n represent the bases represented by equations (A-1) and (A-2) respectively, and let n22 represent integers from 2 to 4.

[0279] In equation (A-1), R 21R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group. 22 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The # in formula (A-1) represents the bond site with the ## in formula (A-2).

[0280] In equation (A-2), R 23 Each is an alkyl or halogen atom with 1 to 5 carbon atoms, n22 is an integer of 2 to 4, n23 is an integer of 0 to 4, n24 is 0 or 1, and ## in formula (A-2) represents the bonding site with # in formula (A-1).

[0281] Wherein, n23+n22 is the number below the maximum number of substituents of the aromatic ring contained in formula (A-2).

[0282] In (II) the R in formula (A-1) or formula (A-2) 21 R 22 and R 23 R in equation (A-1) or equation (A-2) of equation (2-1) respectively 21 R 22 and R 23 For the same meaning, the preferred form is also the same.

[0283] In addition, n22, n23 and n24 in formula (2-1) or formula (A-2) in (II) have the same meaning as n22, n23 and n24 in formula (2-1) or formula (A-2), and the preferred forms are also the same.

[0284] The compound represented by formula (2-1) can be manufactured, for example, by reacting the compound represented by formula (3) described below with the compound represented by formula (Y) using the process represented by process (II).

[0285] [Chemistry 31]

[0286]

[0287] In formula (Y), R 21 R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group. 22 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0288] R in equation (Y) 21 and R 22 Respectively with R in equation (2-1) or equation (A-2) 21 and R 22For the same meaning, the preferred form is also the same.

[0289] <Method for manufacturing the compound represented by formula (2-2)>

[0290] The method for manufacturing the compound represented by formula (2-2) includes the steps represented by (III) below (hereinafter sometimes referred to as "process (III)").

[0291] [Chemistry 32]

[0292]

[0293] In (III), R 21 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group.

[0294] R 22 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0295] polym.A1 and R 20 A polymer chain having repeating units represented by the following formula (6) or formula (7).

[0296] [Chemistry 33]

[0297]

[0298] In equations (6) and (7), Ar 1 Each can be independently represented as either substituted or unsubstituted aromatic ring groups.

[0299] Ar in equation (6) 2 Indicates substituted or unsubstituted aromatic ring groups.

[0300] In equation (7), Ar 3 Each can be independently represented as either substituted or unsubstituted aromatic ring groups.

[0301] In equation (7), R 1 Each can be independently a hydrogen atom, alkyl group, or aryl group, or represent multiple R groups. 1 The substituted or unsubstituted ring structures formed by the combination of these bonded carbon atoms. This indicates the bonding site with the aromatic ring in equation (2-2). Ar represents the expression in equation (6). 1 Or the bonding site of the aromatic ring in formula (2-2),

[0302] When u and n are integers greater than or equal to 1, u and n are used as subscripts, and parentheses () or square brackets [] indicate repeated units. When u and n are greater than or equal to 2, multiple R... 1 They can be the same or different.

[0303] The compound represented by formula (2-2) can be manufactured, for example, by reacting polym.A1 with the compound represented by formula (Y) using the process represented by process (III).

[0304] [Chemistry 34]

[0305]

[0306] In formula (Y), R 21 R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group. 22 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0307] R in equation (Y) 21 and R 22 respectively with R in equation (2-2) 21 and R 22 For the same meaning, the preferred form is also the same.

[0308] In (III), R 21 and R 22 respectively with R in equation (2-2) 21 and R 22 For the same meaning, the preferred form is also the same.

[0309] Furthermore, in (III), Ar of equations (6) and (7) 1 Ar 2 Ar 3 R 1 , u and n are respectively related to Ar in equations (6) and (7) of the above equation (2-2). 1 Ar 2 Ar 3 R 1 、u and n have the same meaning and the preferred form is also the same.

[0310] <<Process of synthesizing polym.A1>>

[0311] The method for manufacturing the compound represented by formula (2-2) may also include the process of synthesizing polym.A1.

[0312] The preferred process for synthesizing polym.A1 is to react the compound represented by formula (3) with the compound represented by formula (4) or formula (5) in the presence of a palladium complex and a phosphine compound.

[0313] The following describes the compounds used in the synthesis of polym.A1.

[0314] [Chemistry 35]

[0315]

[0316] In equation (3), Ar 1 For substituted or unsubstituted aromatic rings, s is an integer greater than or equal to 1, where, in Ar 1 In the case of substituents, (Ar) 1 The maximum number of substituents is -s) hydrogen atoms substituted by substituents.

[0317] The value of s is preferably an integer from 1 to 6, more preferably an integer from 1 to 4, and even more preferably 1 or 2.

[0318] As the aromatic ring of formula (3), it is related to Ar in formulas (6) and (7). 1 Ar 2 and Ar 3 The aromatic rings in the text have the same meaning.

[0319] The aromatic ring in formula (3) is preferably a benzene ring, a biphenyl ring, a thiophene ring, a thiazole ring, an oxazole ring, a furan ring, a diketopyrrolopyrrole ring, or a ring formed by two or more of these rings bonded together by a single bond.

[0320] When the aromatic ring in formula (3) is an aromatic hydrocarbon ring, it is preferably substituted with a substituent other than a hydrogen atom to form an aromatic hydrocarbon ring, more preferably a benzene ring, and s is preferably 2.

[0321] Examples of substituents include: fluorine atom, cyano, nitro, alkyl, fluorinated alkyl, alkoxy, fluorinated alkoxy, alkylthio or fluorinated alkylthio.

[0322] When the aromatic ring in formula (3) is an aromatic hydrocarbon ring, the fluorine atom is preferred as a substituent.

[0323] In Ar 1 When the aromatic ring represented is an aromatic hydrocarbon ring, the compounds represented by formula (3) can be, for example, those represented by formulas (B1-1) to (B1-10). In addition, R in the formula represents cyano, nitro, alkyl, fluorinated alkyl, alkoxy, fluorinated alkoxy, alkylthio or fluorinated alkoxy.

[0324] [Chemistry 36]

[0325]

[0326] In equation (3) Ar 1 When the aromatic ring represented is an aromatic heterocycle, it is preferably a sulfur-containing heterocycle, and more preferably a thiophene ring.

[0327] Ar as in equation (3) 1 When the aromatic ring is an aromatic heterocycle, the substituents can be, for example, hydrogen atoms, fluorine atoms, cyano groups, nitro groups, alkyl groups, fluorinated alkyl groups, alkoxy groups, fluorinated alkoxy groups, alkylthio groups, or fluorinated alkoxy groups. Among these, in the case of an aromatic heterocycle, alkyl or alkoxy groups are preferred as unsubstituted or as substituents. When s is 2 or more, the alkyl and alkoxy groups may be the same or different, and are preferably a ring structure with 5 to 10 ring elements formed by bonding to one or more other alkyl or alkoxy groups present on the same carbon atom of the aromatic heterocycle or on an adjacent carbon atom in the ring structure.

[0328] In equation (3), Ar 1 Compounds that are thiophene rings include, for example, compounds represented by the following formulas (B2-9), (B2-10), (B2-15), (B2-16), (B2-19), and (B2-20).

[0329] In addition, R in the following formula represents a hydrogen atom, a fluorine atom, a cyano group, a nitro group, an alkyl group, a fluorinated alkyl group, an alkoxy group, a fluorinated alkoxy group, an alkylthio group, or a fluorinated alkylthio group.

[0330] [Chemistry 37]

[0331]

[0332] [Chemistry 38]

[0333]

[0334] [Chemistry 39]

[0335]

[0336] In formulas (4) and (5), X is a chlorine atom or a trifluoromethanesulfonic acid group (hereinafter sometimes referred to as "trifluoromethanesulfonic acid ester group" or "OTf"), and in formula (4), Ar 2 The structure can be substituted or unsubstituted aromatic rings. t is an integer greater than or equal to 1. When t is greater than or equal to 2, multiple Xs can be identical or different from each other.

[0337] Ar in equation (5) 3 and R 1respectively with Ar in the above formula (7) 3 and R 1 For the same meaning, the preferred form is also the same.

[0338] The value of t is preferably an integer from 1 to 6, and more preferably 1 or 2.

[0339] The value of u is preferably an integer from 1 to 3, and more preferably 1.

[0340] In formula (4), X is preferably a chlorine atom. In formula (5), X is preferably a trifluoromethanesulfonic acid group.

[0341] Compounds represented by formula (5) may include, for example, trifluoromethanesulfonate diesters derived from bisphenols. Examples of bisphenols include: bisphenol F, bisphenol A, bisphenol E, 4,4'-(1,3-dimethylbutylene)diphenol (BisP-MIBK), bisphenol AP, bisphenol BP, 9,9-bis(4-hydroxyphenyl)fluorene, bisphenol Z, 4,4'-cyclohexylene dodecyl bisphenol, bisphenol TMC, etc.

[0342] Compounds represented by formula (5) can be listed, for example, those represented by formulas (C2-1) to (C2-16).

[0343] [Chemistry 40]

[0344]

[0345] (Palladium complex)

[0346] There are no particular limitations on the palladium complex if it is a palladium complex that is used as a catalyst in cross-coupling reactions, such as palladium(0) complexes, palladium(II) complexes, etc.

[0347] Specifically, examples include palladium [tetra(triphenylphosphine)], dichlorobis(triphenylphosphine)palladium, palladium acetate, tris(dibenzylacetone)palladium, and bis(dibenzylacetone)palladium. Among these, from the viewpoint of ease of reaction operation or improvement of reaction rate, tris(dibenzylacetone)palladium (Pd2(dba)3) or dichlorobis(triphenylphosphine)palladium is preferred as a palladium complex.

[0348] The amount of palladium complex added is not particularly limited if it is the effective amount of catalyst, and can be adjusted appropriately. The amount of palladium complex added is usually 0.0001 mol to 0.5 mol relative to 1 mol of the compound represented by formula (3), preferably 0.0003 mol to 0.2 mol.

[0349] (phosphine compounds)

[0350] Phosphine compounds are preferably compounds represented by the following formula (1) (hereinafter also referred to as "P(2-OMePh)3") and compounds represented by the following formula (2) (hereinafter also referred to as "XPhos").

[0351] [Chemistry 41]

[0352]

[0353] In formula (1), Me represents methyl. In formula (2), Cy represents cyclohexyl, and i-Pr represents isopropyl.

[0354] By using P(2-OMePh)3 and XPhos as phosphine compounds as palladium complexes, the compound represented by formula (3) reacts with the compound represented by formula (4) or formula (5) to generate polym.A1.

[0355] In the synthesis of polym.Al, the reactivity tends to decrease and the formation of polym.Al tends to decrease when either P(2-OMePh)3 or XPhos is present in the reaction system. It is speculated that the reactivity is increased by the presence of P(2-OMePh)3 and XPhos in the reaction system, where P(2-OMePh)3 and XPhos act as ligands of the palladium complex and are coordinated to the palladium atom.

[0356] In the process of synthesizing polym.A1, the amount of P(2-OMePh)3 and XPhos added, relative to 1 mole of palladium atoms, is usually 0.5 moles to 4 moles, preferably 1 mole to 3 moles, and more preferably 1 mole to 2 moles.

[0357] <<Manufacturing Conditions>>

[0358] The reaction temperature in the method for producing this compound is, for example, about 50°C to 160°C, preferably 60°C to 120°C. The reaction time is, for example, about 0.1 hours to 200 hours, preferably 1 hour to 30 hours.

[0359] There are no particular limitations on the environment for the manufacturing method of this compound, but an inert gas environment such as a nitrogen environment or an environment such as a vacuum environment that can suppress catalyst deactivation is preferred.

[0360] The preparation of this compound is usually carried out in a solvent. Examples of solvents include hydrocarbon solvents, ether solvents, and amide solvents.

[0361] Examples of hydrocarbon solvents include n-pentane, n-hexane, toluene, and xylene.

[0362] Examples of ether-based solvents include: diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisopentyl ether, dihexyl ether, diheptyl ether, cyclopentylmethyl ether, dimethoxyethane, tetrahydrofuran, tetrahydropyran, dioxane, diphenyl ether, and anisole.

[0363] Examples of amide-based solvents include: N-methylpyrrolidone, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, etc.

[0364] Toluene, tetrahydrofuran, or cyclopentylmethyl ether are preferred solvents. In these cases, the solubility of the obtained compound can be improved.

[0365] The preferred method for producing this compound is a reaction in the presence of the palladium complex and a basic compound. When the reaction is carried out in the presence of the palladium complex and a basic compound, the strong acid (HX) produced as a byproduct of the reaction can be neutralized, and undesirable reactions caused by the strong acid, such as catalyst decomposition, can be suppressed.

[0366] Examples of alkaline compounds include inorganic salts such as sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, potassium phosphate, sodium phosphate, cesium phosphate, potassium hydrogen phosphate, sodium hydrogen phosphate, and potassium tert-butoxide. Among these, carbonates are preferred, and cesium carbonate is more preferred. Compared to metal carbonates such as sodium carbonate or potassium carbonate, cesium carbonate has higher solubility in organic solvents and can further suppress undesirable reactions caused by strong acids produced as byproducts of the reaction.

[0367] The amount of alkaline compound added is typically 0.5 to 100 moles relative to 1 mole of the compound represented by formula (3), preferably 0.9 to 20 moles, and more preferably 1 to 10 moles.

[0368] When an inorganic salt, which is a basic compound, is added, it is usually added to the reaction system in the form of an aqueous solution to improve the solubility of the inorganic salt. In the steps indicated by (IA), (IB), (II), and (III), the reaction can also be carried out in a two-phase solvent, namely an aqueous phase and an organic phase. In the above cases, a phase transfer catalyst such as a quaternary ammonium salt may be further added if necessary.

[0369] In the method for producing this compound, it is preferable to further add an organic acid to the reaction. The inclusion of an organic acid can further promote the catalytic reaction. Examples of organic acids include carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, trimethylacetic acid, and benzoic acid, as well as sulfonic acids. From the viewpoint of solubility in organic solvents or ease of purification, carboxylic acids are preferred, and trimethylacetic acid is more preferred.

[0370] There is no particular limitation on the amount of organic acid added, and it can be adjusted appropriately. In the method for manufacturing this compound, when the reaction is carried out in the presence of a basic compound, the amount of organic acid added relative to 1 mole of the basic compound is preferably 0.01 mole to 90 moles, more preferably 0.1 mole to 70 moles.

[0371] Examples of compounds represented by formula (Y) as used in (II) and (III) include 4-chlorostyrene, 3-chlorostyrene, 2-chlorostyrene, 2-methyl-4-chlorostyrene, 3-methyl-chlorostyrene, and 2,6-dimethyl-4-chlorostyrene. Among these, 4-chlorostyrene, 3-chlorostyrene, or 2-chlorostyrene are preferred as compounds represented by formula (Y).

[0372] [Other processes]

[0373] The manufacturing method of this compound may also include steps other than those indicated by (IA), (IB), (II) and (III) (hereinafter also referred to as "other steps").

[0374] Other steps include, for example, a step of cleaning the compound obtained through the reaction step (cleaning step), and a step of purifying the compound obtained through the steps represented by (IA), (IB), (II), and (III) (purification step). There are no particular limitations on the specific methods of the cleaning or purification steps, and they can be carried out according to known methods.

[0375] Example

[0376] The present invention will now be specifically described based on embodiments, but the present invention is not limited to these embodiments. The methods for determining various physical properties are shown below.

[0377] [Nuclear Magnetic Resonance (NMR) Spectroscopy]

[0378] Regarding the NMR spectra of the compounds from Synthetic Examples 1 and 2, as well as Examples 1 to 6, the compounds were dissolved in deuterated chloroform as a deuterated solvent, and the NMR spectra were determined using a nuclear magnetic resonance spectrometer (Bruker's "AVANCE III-400").

[0379] [Molecular weight determination]

[0380] Regarding the compounds obtained in Synthetic Examples 1 to 3 and Examples 1, 2, 5, and 6, according to 1 The molecular structure with the target molecular weight was confirmed by the integral value of H-NMR. The molecular weight (number average molecular weight and weight average molecular weight) of the polymers obtained in Examples 3 and 4 were determined by using a GPC system (Tosoh Corporation's "HLC-8420GPC") with tetrahydrofuran as the eluent.

[0381] <Synthesis of Starting Materials>

[0382] The compounds represented by formulas (C-1) to (C-3) below (hereinafter also referred to as "compounds (C-1) to (C-3)") are synthesized according to the following method as starting materials used in the synthesis of compounds (A-3) to (A-6) described later.

[0383] [Chemistry 42]

[0384]

[0385] [Synthesis example 1]

[0386] <<Synthesis of Compound (C-1)>>

[0387] 57.9 mmol of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane was added to a 500 mL four-necked flask equipped with a magnetic rotor. The flask was then purged with nitrogen to create a nitrogen atmosphere. 100 mL of dichloromethane and 579 mmol of pyridine were added, and the mixture was cooled to 0°C in an ice bath. 177 mol of trifluoromethanesulfonic anhydride was then added dropwise. The flask was then brought back to room temperature, and the reaction was carried out with stirring for 4 hours. The flask was cooled to 0°C again, and the aqueous layer was acidified by adding 10% hydrochloric acid. The aqueous layer was then separated. The organic layer was washed twice with 10% hydrochloric acid and three times with pure water, followed by concentration using an evaporator. The resulting pale yellow oily liquid was purified by column chromatography (silica gel, toluene) to obtain BOC-TMC-OTf (C-1) as a highly viscous oily liquid.

[0388] The following shows the synthetic process of compound (C-1).

[0389] [Chemistry 43]

[0390]

[0391] The following shows the NMR results for compound (C-1).

[0392] 1 H-NMR (400 MHz, CDCl3): δ=0.32 (s, 3H), 0.86 (t, J=13 Hz, 1H), 1.00 (s,6H), 1.14 (t, J=13 Hz, 1H), 1.40 (d, J=13 Hz, 1H), 1.91 (d, J=14 Hz, 1H),1.97 (br, 1H), 2.31 (s, 3H), 2.34 (s, 3H), 2.42 (d, J=14 Hz, 1H), 2.63 (d, J=14 Hz, 1H), 7.03-7.27 (m, 6H).

[0393] [Synthesis example 2]

[0394] <<Synthesis of Compound (C-2)>>

[0395] 59.1 mmol of 9,9-bis(3-methyl-4-hydroxyphenyl)fluorene was added to a 500 mL four-necked flask equipped with a magnetic rotor. The internal environment was then purged with nitrogen to create a nitrogen atmosphere. 114 mL of dichloromethane and 590 mmol of pyridine were added, and the mixture was cooled to 0°C in an ice bath. 177 mol of trifluoromethanesulfonic anhydride was then added dropwise. The flask was then brought back to room temperature, and the reaction was carried out with stirring for 4 hours. The flask was cooled to 0°C again, and the aqueous layer was acidified by adding 10% hydrochloric acid. The aqueous layer was then separated. The organic layer was washed twice with 10% hydrochloric acid and three times with pure water, followed by concentration using an evaporator. The resulting pale yellow oily liquid was purified by column chromatography (silica gel, toluene) to obtain BOC-FL-OTf (C-2) as a highly viscous oily liquid.

[0396] The following shows the synthetic process of compound (C-2).

[0397] [Chemistry 44]

[0398]

[0399] The following shows the NMR results for compound (C-2).

[0400] 1H-NMR (400 MHz, CDCl3): δ=2.25 (s, 6H), 7.04-7.11 (m, 6H), 7.28-7.42(m, 6H), 7.77-7.79 (br, 2H).

[0401] [Synthesis example 3]

[0402] <<Synthesis of Compound (C-3)>>

[0403] 29.54 mmol of 4,4',4'',4'''-[isopropylidene bis(cyclohexane-4-yl-1-ylidene)]tetra(2-methylphenol) was added to a 500 mL four-necked flask equipped with a magnetic rotor. The flask was then placed in a nitrogen atmosphere by purging the interior with nitrogen. 100 mL of dichloromethane and 591 mmol of pyridine were added, and the mixture was cooled to 0°C in an ice bath. 177 mol of trifluoromethanesulfonic anhydride was then added dropwise. The flask was then brought back to room temperature, and the reaction was carried out with stirring for 3 hours. The flask was then cooled to 0°C again, and a 10% hydrochloric acid solution was added to acidify the aqueous layer. The aqueous layer was then separated. The organic layer was washed twice with a 10% hydrochloric acid solution and three times with pure water, followed by concentration using an evaporator. The obtained pale yellow oily liquid was purified by column chromatography (silica gel, toluene) to obtain TOC-4HBPA-OTf (C-3) in powder form.

[0404] The following shows the synthetic process of compound (C-3).

[0405] [Chemistry 45]

[0406]

[0407] The following shows the NMR results for compound (C-3).

[0408] 1 H-NMR (400 MHz, CDCl3): δ=0.54 (s, 6H), 1.10-1.19 (m, 4H), 1.35-1.38(m, 2H), 1.62-1.65 (m, 4H), 1.82-1.88 (m, 4H), 2.30 (s, 6H), 2.36 (s, 6H), 2.64-2.67 (m, 4H), 6.98-7.26 (m, 12H).

[0409] <Compound Synthesis>

[0410] The following compounds (A-1) to (A-7) are synthesized according to the following methods as compounds represented by formula (1), formula (2-1) or formula (2-2).

[0411] [Chemistry 46]

[0412]

[0413] [Example 1]

[0414] <<Synthesis of Compound (A-1)>>

[0415] After heating and drying the pressure-resistant reaction vessel equipped with a magnetic rotor, the internal environment was purged with nitrogen to create a nitrogen atmosphere. 300 μmol of tris(dibenzylacetone)dipalladium(O)-chloroform adduct, 1.2 mmol of tris(2-methoxyphenyl)phosphine, 1.2 mmol of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (hereinafter also referred to as "XPhos"), 300 μmol of Adekastab (hereinafter also referred to as "LA-7RD"), 60 mmol of cesium carbonate, and 30 mmol of trimethylacetic acid were added. The reaction vessel was purged with a vacuum pump, and then purged with nitrogen to create a nitrogen atmosphere. 30 mL of tetrahydrofuran, 30 mmol of 4-chlorostyrene, and 90 mmol of 1,2,3,5-tetrafluorobenzene were then added. The reaction vessel was sealed with a stopper, and the reaction mixture was heated to 100°C in an oil bath and reacted with stirring for 8 hours. After the reaction was complete, the oil bath was removed and allowed to cool to room temperature. Then, toluene was added for dilution, and the mixture was washed three times with water. The washed organic layer was concentrated using an evaporator to obtain compound (A-1).

[0416] The following shows the synthetic process of compound (A-1).

[0417] [Chemistry 47]

[0418]

[0419] The following shows the NMR results for compound (A-1).

[0420] 1 H-NMR (400 MHz, CDCl3): δ=5.33 (d, J=10.9 Hz, 2H), 5.83 (d, J=18 Hz, 2H), 6.76 (dd, J=18 Hz and 11 Hz, 2H), 7.43 (d, J=8 Hz, 4H), 7.52 (d, J=8 Hz,4H).

[0421] [Example 2]

[0422] <<Synthesis of Compound (A-2)>>

[0423] After heating and drying the pressure-resistant reaction vessel equipped with a magnetic rotor, a nitrogen environment was established by purging the interior with nitrogen. 150 μmol of tris(dibenzylacetone)dipalladium(O)-chloroform adduct, 600 μmol of tris(2-methoxyphenyl)phosphine, 600 μmol of XPos, 500 μmol of LA-7RD, 60 mmol of cesium carbonate, and 15 mmol of trimethylacetic acid were added. The reaction vessel was evacuated using a vacuum pump and then purged with nitrogen to create a nitrogen environment. 30 mL of tetrahydrofuran, 49.5 mmol of 4-chlorostyrene, and 15 mmol of 1,2,3,5-tetrafluorobenzene were then added. The reaction vessel was sealed by stoppering, and the reaction mixture was heated to 100°C in an oil bath while stirring for 8 hours. After the reaction was complete, the oil bath was removed and the mixture was allowed to cool to room temperature. Then, toluene was added for dilution, and the mixture was washed three times with water. The cleaned organic layer is concentrated by evaporation to obtain compound (A-2).

[0424] The following shows the synthetic process of compound (A-2).

[0425] [Chemistry 48]

[0426]

[0427] The following shows the NMR results for compound (A-2).

[0428] 1 H-NMR (400 MHz, CDCl3): δ=5.31 (d, J=11 Hz, 3H), 5.82 (d, J=18 Hz, 3H), 6.76 (dd, J=18 Hz and 11 Hz, 3H), 7.39-7.62 (m, 12H).

[0429] [Example 3]

[0430] <<Synthesis of Compound (A-3)>>

[0431] After heating and drying the pressure-resistant polymerization container equipped with a magnetic rotor, the internal environment was purged with nitrogen to create a nitrogen atmosphere. 24.0 mmol of BOC-TMC-OTf(C-1), 90 mmol of cesium carbonate, 30.0 mmol of trimethylacetic acid, 0.13 mmol of LA-7RD, 0.300 mmol of tris(dibenzylacetone)dipalladium(O)-chloroform adduct, 1.20 mmol of tris(2-methoxyphenyl)phosphine, and 1.20 mmol of XPhos were added. The reaction vessel was purged with a vacuum pump, then purged with nitrogen to create a nitrogen atmosphere. 60 mL of tetrahydrofuran and 30.0 mmol of 1,2,3,5-tetrafluorobenzene were added. The reaction vessel was then sealed with a stopper, and the reaction mixture was heated to 100°C in an oil bath and reacted with stirring for 6 hours. Next, 12.6 mmol of 4-chlorostyrene was added, and the reaction was carried out at 100 °C with stirring for 3 hours. After the reaction was completed, the oil bath was removed and the mixture was allowed to cool to room temperature. Then, toluene was added, and the mixture was washed three times with water. The washed organic layer was filtered through filter paper and concentrated using an evaporator. The concentrated solution was then injected into methanol, causing the solid to recrystallize, thus obtaining compound (A-3) as a pale yellow solid. The polystyrene-converted number-average molecular weight of compound (A-3) was 3,150, the polystyrene-converted weight-average molecular weight was 5,210, and the molecular weight distribution was 1.6.

[0432] The following shows the synthetic process of compound (A-3).

[0433] [Chemistry 49]

[0434]

[0435] The following shows the NMR results for compound (A-3).

[0436] 1H-NMR (400 MHz, CDCl3): δ=0.36 (br, 3H), 0.89 (t, J=12 Hz, 1H), 0.99 (br, 6H), 1.18-1.29 (m, 1H), 1.39 (d, J=10 Hz, 1H), 1.95-2.04 (m, 2H), 2.15-2.19 (m, 6H), 2.51 (d, J=7 Hz, 1H), 2.74 (d, J=12 Hz, 1H), 5.30 (d, J=11 Hz), 5.80 (d, J=18 Hz), 6.74 (dd, J=18 and 11 Hz), 7.07-7.30 (m, 6H), 7.40-7.48 (m).

[0437] [Example 4]

[0438] <<Synthesis of Compound (A-4)>>

[0439] After heating and drying the pressure-resistant polymerization container equipped with a magnetic rotor, the internal environment was purged with nitrogen to create a nitrogen atmosphere. 4.8 mmol of BOC-FL-OTf(C-2), 18 mmol of cesium carbonate, 6.0 mmol of trimethylacetic acid, 0.030 mmol of LA-7RD, 0.060 mmol of tris(dibenzylacetone)dipalladium(O)-chloroform adduct, 0.24 mmol of tris(2-methoxyphenyl)phosphine, and 0.24 mmol of XPhos were added. The reaction vessel was purged with a vacuum pump, then purged with nitrogen to create a nitrogen atmosphere. 12 mL of tetrahydrofuran and 6.0 mmol of 3,4-ethylenedioxythiophene were added. The reaction vessel was then sealed with a stopper, and the reaction mixture was heated to 100°C in an oil bath and reacted with stirring for 6 hours. Next, 2.52 mmol of 4-chlorostyrene was added, and the mixture was reacted at 100°C with stirring for 3 hours. After the reaction was complete, the oil bath was removed and the mixture was allowed to cool to room temperature. Then, toluene was added, and the mixture was washed three times with water. The washed organic layer was filtered through filter paper and concentrated using an evaporator. The concentrated solution was then injected into methanol, causing the solid to precipitate again, thus yielding compound (A-4) as a pale yellow solid. The polystyrene-converted number-average molecular weight of compound (A-4) was 4,200, the polystyrene-converted weight-average molecular weight was 7,000, and the molecular weight distribution was 1.7.

[0440] The following shows the synthetic process of compound (A-4).

[0441] [Transformation 50]

[0442]

[0443] The following shows the NMR results for compound (A-4).

[0444] 1 H-NMR (400 MHz, CDCl3): δ=2.25 (s, 6H), 4.16-4.29 (m, 4H), 5.21 (d, J=11 Hz), 5.73 (d, J=18 Hz), 6.65-6.74 (m), 7.06 (br, 4H), 7.21-7.43 (m, 8H),7.66-7.76 (m, 2H).

[0445] [Example 5]

[0446] <<Synthesis of Compound (A-5)>>

[0447] After heating and drying the pressure-resistant polymerization container equipped with a magnetic rotor, the internal environment was purged with nitrogen to create a nitrogen atmosphere. 7.41 mmol of BOC-TMC-OTf(C-1) obtained in Synthesis Example 1, 0.741 mmol of bis(triphenylphosphine)palladium(II) dichloride, 75.5 mmol of lithium chloride, and 0.371 mmol of LA-7RD were added. The reaction container was purged with a vacuum pump and then purged with nitrogen to create a nitrogen atmosphere. 40 mL of N,N-dimethylformamide and 17.8 mmol of tributyl(vinyl)tin were added. The reaction container was then sealed with a stopper, and the reaction mixture was heated to 125°C in an oil bath while stirring for 3 hours. After the reaction was complete, the oil bath was removed and the mixture was allowed to cool to room temperature. Toluene was then added, and the mixture was washed three times with water. The cleaned organic layer was concentrated by evaporator, and the obtained pale yellow oily liquid was purified by column chromatography (silica gel, toluene) and then concentrated to obtain compound (A-5) as a white powder.

[0448] The following shows the synthetic process of compound (A-5).

[0449] [Chemistry 51]

[0450]

[0451] The following shows the NMR results for compound (A-5).

[0452] 1¹H-NMR (400 MHz, CDCl₃): δ = 0.38 (s, 3H), 0.87 (d, J = 13 Hz, 1H), 0.96–1.01 (bs, 6H), 1.12 (dd, J = 14 Hz and 12 Hz, 1H), 1.37 (d, J = 13 Hz, 1H), 1.90 (d, J = 14 Hz, 1H), 2.01 (m, 1H), 2.28 (s, 3H), 2.30 (s, 3H), 2.48 (d, J = 11 Hz, 1H), 2.71 (d, J = 14 Hz, 1H), 5.20 (td, J = 10 and 2 Hz, 2H), 5.53 (dd, J = 17 and 2 Hz, 1H), 5.59 (dd, J=17 and 2 Hz, 1H), 6.86 (td, J=18 and 11 Hz, 2H), 6.99-7.38 (m, 6H).

[0453] [Example 6]

[0454] <<Synthesis of Compound (A-6)>>

[0455] After heating and drying the pressure-resistant polymerization container equipped with a magnetic rotor, the internal environment was purged with nitrogen to create a nitrogen atmosphere. 7.41 mmol of BOC-FL-OTf(C-2) obtained in Synthesis Example 2, 0.741 mmol of bis(triphenylphosphine)palladium(II) dichloride, 75.5 mmol of lithium chloride, and 0.371 mmol of LA-7RD were added. The reaction vessel was purged with a vacuum pump and then purged with nitrogen to create a nitrogen atmosphere. 40 mL of N,N-dimethylformamide and 17.8 mmol of tributyl(vinyl)tin were added. The reaction vessel was then sealed with a stopper, and the reaction mixture was heated to 125°C in an oil bath while stirring for 3 hours. After the reaction was complete, the oil bath was removed and the mixture was allowed to cool to room temperature. Toluene was then added, and the mixture was washed three times with water. The cleaned organic layer was concentrated by evaporator, and the obtained pale yellow oily liquid was purified by column chromatography (silica gel, toluene) and then concentrated to obtain compound (A-6) as a white powder.

[0456] The following shows the synthetic process of compound (A-6).

[0457] [Chemistry 52]

[0458]

[0459] The following shows the NMR results for compound (A-6).

[0460] 1 ¹H-NMR (400 MHz, CDCl₃): δ = 2.11 (s, 3H), 5.20 (td, J = 10 and 2 Hz, 2H), 5.53 (dd, J = 17 and 2 Hz, 1H), 5.59 (dd, J = 17 and 2 Hz, 1H), 7.00–7.55 (m, 12H), 7.90 (d, J = 2 Hz, 2H).

[0461] [Example 7]

[0462] <<Synthesis of Compound (A-7)>>

[0463] After heating and drying the pressure-resistant polymerization container equipped with a magnetic rotor, the internal environment was purged with nitrogen to create a nitrogen atmosphere. 3.00 mmol of TOC-4HBPA-OTf(C-3) obtained in Synthesis Example 3, 0.600 mmol of bis(triphenylphosphine)palladium(II) dichloride, 61.1 mmol of lithium chloride, and 0.300 mmol of LA-7RD were added. The reaction vessel was purged with a vacuum pump and then purged with nitrogen to create a nitrogen atmosphere. 63 mL of N,N-dimethylformamide and 14.4 mmol of tributyl(vinyl)tin were added. The reaction vessel was then sealed with a stopper, and the reaction mixture was heated to 125°C in an oil bath and reacted with stirring for 3 hours. After the reaction was complete, the oil bath was removed and the mixture was allowed to cool to room temperature. Toluene was then added, and the mixture was washed three times with water. The cleaned organic layer was concentrated by evaporator, and the resulting pale yellow oily liquid was purified by column chromatography (silica gel, toluene) and then concentrated to obtain compound (A-7) as a white powder.

[0464] The following shows the synthetic process of compound (A-7).

[0465] [Chemistry 53]

[0466]

[0467] The following shows the NMR results for compound (A-7).

[0468] 1H-NMR (400 MHz, CDCl3): δ=0.52 (s, 6H), 1.19 (q, J=13 Hz, 4H), 1.61 (d, J=12 Hz, 4H), 1.83 (t, J=11 Hz, 4H), 2.27 (s, 6H), 2.32 (s, 6H), 2.71 (d, J=13 Hz, 4H), 5.21 (ddd, J=18, 11 and 1 Hz, 4H), 5.21 (ddd, J=18, 11 and 1 Hz, 4H), 5.54 (dd, J=18 and 2 Hz, 2H), 5.62 (dd, J=18 and 2 Hz, 2H), 6.81-6.91 (m, 4H), 6.94-6.99 (m, 4H), 7.09 (s, 2H), 7.17 (d, J=8 Hz, 2H), 7.31 (d, J=8 Hz, 2H), 7.42 (d, J=8 Hz, 2H).

Claims

1. A compound represented by the following formula (1A), formula (1B), formula (2-1) or formula (2-2); [Chemistry 1] In equation (1A), R 11 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group. R 12 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 13 Each of the following is independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms, or one or more other R groups present on the same carbon atom or on adjacent carbon atoms. 13 Ring structures with 5 to 10 ring elements formed by bonding. n12 is an integer from 2 to 4, n13 is an integer from 0 to 6, n14 is an integer from 1 to 12, and n15 is either 1 or 2. When n15 is 1, R 10 It is a hydrogen atom. When n15 is 2, R 10 It is a single bond, a substituted or unsubstituted methylene group, or a divalent hydrocarbon group having 2 to 20 carbon atoms; [Chemistry 2] In equation (1B), R 11 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group. R 12 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 101 It is a divalent hydrocarbon group with 3 or more carbon atoms; [Chemistry 3] In equation (2-1), A 1 and A 2 Let n represent the bases represented by equations (A-1) and (A-2) respectively, where n22 is an integer from 2 to 4; [Chemistry 4] In equation (A-1), R 21 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group, R 22 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The # in formula (A-1) represents the bond site with the ## in formula (A-2). In equation (A-2), R 23 Each is an alkyl or halogen atom with 1 to 5 carbon atoms, n22 is an integer of 2 to 4, n23 is an integer of 0 to 4, n24 is 0 or 1, and ## in formula (A-2) represents the bonding site with # in formula (A-1); in, n23+n22 is the number below the maximum number of substituents in the aromatic ring contained in formula (A-2); [Chemistry 5] In equation (2-2), R 21 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group. R 22 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 20 A polymer chain having repeating units represented by the following formula (6) or the following formula (7); [Chemistry 6] In equations (6) and (7), Ar 1 Each can be independently represented as either substituted or unsubstituted aromatic ring groups. In equation (6), Ar 2 Indicates substituted or unsubstituted aromatic ring groups. In equation (7), Ar 3 Each can be independently represented as either substituted or unsubstituted aromatic ring groups. In equation (7), R 1 Each can be independently a hydrogen atom, alkyl group, or aryl group, or represent multiple R groups. 1 The substituted or unsubstituted ring structures formed by the combination of these bonded carbon atoms. This indicates the bonding site with the aromatic ring in equation (2-2). Ar represents the expression in equation (6). 1 Or the bonding site of the aromatic ring in formula (2-2), u and n are integers greater than or equal to 1, and u and n are recorded as subscripts using parentheses () or square brackets [] to indicate repeated units; where u and n are greater than or equal to 2, multiple R 1 They can be the same or different.

2. The compound according to claim 1, wherein, The compound represented by formula (1A) is a compound represented by formula (1-1) or formula (1-2) below; [Chemistry 7] In equation (1-1), R 11 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group. R 12 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 13 Each of the following is independently an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or one or more other R groups present on the same carbon atom or adjacent carbon atoms. 13 Ring structures with 5 to 10 ring elements formed by bonding. n12 is an integer from 2 to 4, n13 is an integer from 0 to 6, and n14 is an integer from 1 to 12; [Chemistry 8] In equation (1-2), R 11 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group. R 12 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. n12 is an integer from 2 to 4, n13 is an integer from 0 to 6, and n14 is an integer from 1 to 12. R 13 Each of the following is independently an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or one or more other R groups present on or adjacent to the same carbon atom. 13 Ring structures with 5 to 10 ring elements formed by bonding. R 10 It is a single bond, a substituted or unsubstituted methylene group, or a divalent hydrocarbon group having 2 to 20 carbon atoms.

3. The compound according to claim 1, wherein, R in equation (1A) or equation (1B) 11 At least one of them is an alkyl group having 1 to 5 carbons, an aryl group having 6 to 12 carbons, or an alkyl group having 1 to 5 carbons that has been substituted with an aryl group.

4. A method for manufacturing a compound, comprising the steps indicated by (IA) below; [Chemistry 9] In (IA), R 11 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group. R 12 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 13 Each of the following is independently an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or one or more other R groups present on or adjacent to the same carbon atom. 13 Ring structures with 5 to 10 ring elements formed by bonding. n12 is an integer from 2 to 4, n13 is an integer from 0 to 6, n14 is an integer from 1 to 12, and n15 is either 1 or 2. When n15 is 1, R 10 For a hydrogen atom, when n15 is 2, R 10 It is a single bond, a substituted or unsubstituted methylene group, or a divalent hydrocarbon group having 2 to 20 carbon atoms.

5. A method for manufacturing a compound, comprising the steps indicated in (II) below; [Chemistry 10] In (II), in equation (2-1), A 1 and A 2 Let n represent the bases represented by equations (A-1) and (A-2) respectively, and let n22 represent integers from 2 to 4. In equation (A-1), R 21 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group, R 22 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The # in formula (A-1) represents the bond site with the ## in formula (A-2). In equation (A-2), R 23 Each is an alkyl or halogen atom with 1 to 5 carbon atoms, n23 is an integer from 0 to 4, n24 is 0 or 1, and ## in formula (A-2) represents the bonding site with # in formula (A-1); in, n23+n22 is the number below the maximum number of substituents in the aromatic ring contained in formula (A-2).

6. A method for manufacturing a compound, comprising the steps indicated in (III) below; [Chemistry 11] In (III), R 21 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group, R 22 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, polym.A1 and R 20 A polymer chain having the structure represented by the following formula (6) or the following formula (7); [Chemistry 12] In equations (6) and (7), Ar 1 Each can be independently represented as either substituted or unsubstituted aromatic ring groups. In equation (6), Ar 2 Indicates substituted or unsubstituted aromatic ring groups. In equation (7), Ar 3 Each can be independently represented as either substituted or unsubstituted aromatic ring groups. In equation (7), R 1 Each can be independently a hydrogen atom, alkyl group, or aryl group, or represent multiple R groups. 1 The substituted or unsubstituted ring structures formed by the combination of these bonded carbon atoms. This indicates the bonding site with the aromatic ring in equation (2-2). Ar represents the expression in equation (6). 1 Or the bonding sites of the aromatic rings in equation (2-2), where u and n are integers greater than or equal to 1; u and n are recorded as subscripts () or [] to indicate repeating units; where, When u and n are 2 or more, multiple R 1 Same or different.

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