boronic acids or boronic esters, or a method for producing polycyclic aromatic compounds or polycyclic aromatic multimer compounds using the same

Abstract

The present invention relates to boronic acids or boronic esters, or a method for producing polycyclic aromatic compounds or polycyclic aromatic multimer compounds using them. A boronic acid compound effective for the production of polycyclic aromatic compounds is provided, and a method for producing polycyclic aromatic compounds using the boronic acid compound is provided. A compound represented by the following general formula (1) is subjected to acid treatment, and a polycyclic aromatic compound is produced. In the formula, A ring, B ring and C ring are each independently an aromatic ring or a heteroaromatic ring, Y 1 is -B(OH)2optionally esterified, X 1 and X 2 are -O-, >N-Ar (Ar is an aryl group or the like), -S- or -Se-.

Description

Technical Field

[0001] This invention relates to boric acid and borate esters capable of manufacturing polycyclic aromatic compounds or polycyclic aromatic polymers (hereinafter also referred to as polycyclic aromatic compounds, etc.) for use in organic electroluminescent devices, organic field-effect transistors and organic thin-film solar cells, as well as display devices and lighting devices. Background Technology

[0002] For a long time, display devices using electroluminescent light-emitting devices have been the subject of various studies due to their ability to save power and achieve thinner designs. Consequently, organic electroluminescent devices made from organic materials have been actively researched due to their ease of lightweighting and scaling. In particular, the development of organic materials with light-emitting properties such as blue (one of the three primary colors of light) and organic materials with charge transport capabilities such as holes and electrons (possibly becoming semiconductors or superconductors) has been actively pursued, regardless of whether they are high-molecular-weight or low-molecular-weight compounds.

[0003] Organic EL devices have a structure comprising a pair of electrodes consisting of an anode and a cathode, and one or more layers containing organic compounds disposed between the electrodes. These organic compound layers include light-emitting layers and charge transport / injection layers for transporting or injecting charges such as holes and electrons. Various organic materials suitable for these layers have been developed.

[0004] As materials for luminescent layers, benzo[a]fluorene compounds, for example, have been developed (International Publication No. 2004 / 061047). Furthermore, as hole transport materials, triphenylamine compounds, for example, have been developed (Japanese Patent Application Publication No. 2001-172232). Additionally, as electron transport materials, anthracene compounds, for example, have been developed (Japanese Patent Application Publication No. 2005-170911).

[0005] In addition, in recent years, materials modified from triphenylamine derivatives have been reported as materials used in organic EL elements and organic thin-film solar cells (International Publication No. 2012 / 118164). This material is characterized by improved planarity by linking the aromatic rings constituting triphenylamine to each other, using the already practical N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD) as a reference. This document evaluates the charge transport properties of, for example, NO-linked compounds (Compound 1 on page 63), but does not describe methods for manufacturing materials other than NO-linked compounds. Furthermore, the overall electronic state of the compound differs depending on the linked elements, therefore the properties obtained from materials other than NO-linked compounds are unknown. Examples of such compounds can also be found elsewhere (International Publication No. 2011 / 107186). For example, compounds with conjugated structures having high energy (T1) of triplet excitons can emit phosphorescence at shorter wavelengths, thus being advantageous as materials for blue emitting layers. Furthermore, compounds with novel conjugated structures having high T1 are also sought as electron transport and hole transport materials for sandwiching emitting layers.

[0006] The host material of organic EL devices is typically a molecule composed of multiple existing aromatic rings, such as benzene or carbazole, linked by single bonds, phosphorus atoms, and silicon atoms. This is because linking multiple conjugated aromatic rings with smaller band sizes ensures the large HOMO-LUMO band gap (band gap Eg) required by the host material. Furthermore, for the host material of organic EL devices using phosphorescent or thermally activated hysteresis fluorescent materials, a high triplet excitation energy (Eg) is essential. T It is also necessary to localize the SOMO1 and SOMO2 orbitals of the triplet excited state (T1) by attaching donor or acceptor aromatic rings or substituents to the molecule, thereby reducing the exchange interaction between the two orbitals and thus increasing the triplet excitation energy (E). T However, the redox stability of small aromatic rings in conjugated systems is insufficient, and the lifetime of components using molecules with existing aromatic rings as host materials is inadequate. On the other hand, polycyclic aromatic compounds with extended π-conjugated systems generally exhibit excellent redox stability, but their HOMO-LUMO band gap (band gap Eg) and triplet excitation energy (E) are relatively high. T The low ) value makes it unsuitable as the main material.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: International Publication No. 2004 / 061047

[0010] Patent Document 2: Japanese Patent Application Publication No. 2001-172232

[0011] Patent Document 3: Japanese Patent Application Publication No. 2005-170911

[0012] Patent Document 4: International Publication No. 2012 / 118164

[0013] Patent Document 5: International Publication No. 2011 / 107186

[0014] Patent Document 6: International Publication No. 2015 / 102118 Summary of the Invention

[0015] The problem the invention aims to solve

[0016] International Publication No. 2015 / 102118 describes a method for manufacturing the aforementioned polycyclic aromatic compounds, which involves reacting an organolithium compound generated by a halogen-lithium exchange reaction, a neighboring metallization reaction, or the like with boron tribromide to introduce boron atoms and then directly performing intramolecular cyclization in the reaction system. However, the following problems exist: (1) Due to the heat of reaction generated in the process of adding equally highly reactive boron tribromide to a highly reactive organolithium intermediate, local overheating may occur, especially when the reaction scale is increased, the yield may decrease; (2) The boron compound of the cyclization precursor is often unstable, so the intramolecular cyclization reaction as the next step needs to be carried out continuously without separation and purification, and sometimes the byproducts of this continuous reaction accumulate as impurities in the final product; (3) As a result, the selectivity of the obtained product is low, more purification steps are required for high purity, and the yield of the target product is also reduced. Furthermore, in existing methods, after lithiation and boron reagent introduction at low temperatures, a cyclization reaction often needs to be carried out directly at high temperatures. This necessitates continuous low-temperature and high-temperature reactions within the same reactor, which sometimes imposes limitations on the equipment and operation. When using compounds industrially, it is preferable to be able to stably manufacture them in large quantities. Moreover, materials used in organic EL elements typically require particularly high purity; therefore, simplifying and maximizing the efficiency of the final purification process is also crucial.

[0017] Solution for solving the problem

[0018] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that by using boric acid or borate esters, precursors of polycyclic aromatic compounds, as raw materials, Lewis acids, Brønsted acids, and especially Lewis acids such as aluminum chloride, can be reacted to produce the polycyclic aromatic compounds.

[0019] Item 1. A compound represented by the following general formula (1) (wherein, X is not included below) 1 and X 2 (all are -O-); a polymeric compound having a plurality of structures as shown in the following general formula (1) (wherein, excluding the following X) 1 and X 2 (all are -O-); a compound of the following general formula (1) for the manufacture of a polycyclic aromatic compound; or, a polymeric compound having a plurality of structures of the following general formula (1) for the manufacture of a polycyclic aromatic polymeric compound.

[0020]

[0021] (In the above formula (1),)

[0022] Rings A, B, and C are independently aromatic or heteroaromatic rings, and at least one hydrogen atom in these rings may be substituted.

[0023] Y 1 The esterified -B(OH)2 is selected as the esterified component.

[0024] X 1 and X 2 Each is independently -O-, >N-Ar, -S-, or -Se-, where the Ar in the aforementioned N-Ar is an optionally substituted aryl, optionally substituted heteroaryl, or optionally substituted alkyl group, and the Ar in the aforementioned N-Ar is optionally bonded to the aforementioned A, B, and / or C rings via a linking group or a single bond.

[0025] In the compound or structure shown in formula (1), at least one hydrogen atom may optionally be substituted with deuterium.

[0026] Item 2. The compound or polymeric compound according to Item 1, wherein rings A, B, and C are independently aromatic or heteroaromatic rings, and at least one hydrogen in these rings is optionally substituted or unsubstituted with an aryl group, a substituted or unsubstituted heteroaromatic group, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted diheteroarylamino group, a substituted or unsubstituted arylheteroarylamino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a halogen-substituted group.

[0027] Y 1 The esterified -B(OH)2 is selected as the esterified component.

[0028] X 1 and X 2Each of the above is independently -O-, >N-Ar, -S-, or -Se-, wherein the Ar of the aforementioned N-Ar is an aryl group optionally substituted with an alkyl or halogen, a heteroaryl group optionally substituted with an alkyl or halogen, or an alkyl group optionally substituted with an alkyl or halogen, the Ar of the aforementioned N-Ar is optionally bonded to the aforementioned A ring, B ring, and / or C ring via -O-, -S-, >C(R)2, or a single bond, and the R of the aforementioned >C(R)2 is independently hydrogen or an alkyl group, at least one hydrogen in which is optionally substituted with a halogen.

[0029] At least one hydrogen atom in the compound or structure shown in formula (1) may optionally be substituted with deuterium, and,

[0030] The aforementioned polymeric compounds are dimeric or trimeric compounds.

[0031] Item 3. A compound represented by the following general formula (2) (wherein, X is not included below) 1 and X 2 (in the case where all are -O-); or, a compound of the following general formula (2) for the manufacture of polycyclic aromatic compounds.

[0032]

[0033] (In the above formula (2),)

[0034] R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 and R 11 Each of the following is independently hydrogen, aryl, heteroaryl, diarylamino, diherylamino, arylherylamino, alkyl, alkoxy, aryloxy, or halogen, wherein at least one hydrogen atom is optionally substituted with an aryl, heteroaryl, alkyl, or halogen, and R 1 ~R 11 Adjacent groups may optionally bond to each other to form an aromatic or heteroaromatic ring together with ring a, ring b, or ring c, wherein at least one hydrogen atom in the formed ring may optionally be substituted with an aryl, heteroaryl, diarylamino, diarylamino, arylhelelamino, alkyl, alkoxy, aryloxy, or halogen, wherein at least one hydrogen atom may optionally be substituted with an aryl, heteroaryl, alkyl, or halogen.

[0035] Y 1 The esterified -B(OH)2 is selected as the esterified component.

[0036] X 1 and X 2Each of the above is independently -O-, >N-Ar, -S-, or -Se-, wherein the Ar of the aforementioned N-Ar is an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, or an alkyl group having 1 to 6 carbon atoms, at least one of which has hydrogen atoms optionally substituted with a halogen, the aforementioned N-Ar is optionally bonded to the aforementioned a ring, b ring, and / or c ring via -O-, -S-, >C(R)2, or a single bond, and the aforementioned >C(R)2 R is independently independently an alkyl group having 1 to 6 carbon atoms, at least one of which has hydrogen atoms optionally substituted with a halogen, and,

[0037] In the compound shown in formula (2), at least one hydrogen atom may be optionally substituted with deuterium.

[0038] Item 4. The compound according to item 3, wherein R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 and R 11 Independently, R is hydrogen, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a diarylamino group (wherein the aryl group is an aryl group having 6 to 12 carbon atoms), or a halogen, wherein at least one hydrogen atom is optionally substituted with a halogen, and R 1 ~R 11 Adjacent groups may optionally bond to each other to form an aromatic ring having 9 to 16 carbons or a heteroaromatic ring having 6 to 15 carbons together with ring a, ring b, or ring c. At least one hydrogen atom in the formed ring may optionally be substituted by an aryl group having 6 to 10 carbons or a halogen, wherein at least one hydrogen atom in the aryl group having 6 to 10 carbons may optionally be substituted by a halogen.

[0039] Y 1 The group obtained by esterification of -B(OH)2

[0040] X 1 and X 2 They are independently -O-, >N-Ar, or -S-, where the Ar in the aforementioned N-Ar is an aryl group having 6 to 10 carbon atoms or an alkyl group having 1 to 4 carbon atoms, and at least one of their hydrogen atoms is optionally substituted with a halogen, and,

[0041] At least one hydrogen atom in the compound shown in formula (2) may be optionally substituted with deuterium.

[0042] Item 5. A compound represented by the following formula (1-1-98); or, a compound represented by the following formula (1-1-98) for the manufacture of polycyclic aromatic compounds.

[0043]

[0044] In the formula, Bpin is a group obtained by esterifying -B(OH)2 pinacol, and tBu is tert-butyl.

[0045] Item 6. A compound of formula (1-3-139), (1-3-252), (1-3-386) or (1-3-439) for the manufacture of a polycyclic aromatic compound.

[0046]

[0047] In the formula, Bpin is a group obtained by esterifying -B(OH)2pinaol, and Me is a methyl group.

[0048] Item 7. A compound of formula (1-2-340) or formula (1-2-343) for the manufacture of polycyclic aromatic compounds.

[0049]

[0050] In the formula, Bpin is the group obtained by esterifying -B(OH)2pinaol, Me is methyl, and tBu is tert-butyl.

[0051] Item 8. A method of manufacturing, wherein an acid is applied to a compound of the following general formula (1) or a polymeric compound having a plurality of structures of the following general formula (1) to produce a polycyclic aromatic compound or a polycyclic aromatic polymeric compound.

[0052]

[0053] (In the above structural formula,

[0054] Rings A, B, and C are independently aromatic or heteroaromatic rings, and at least one hydrogen atom in these rings may be substituted.

[0055] Y 1 The esterified -B(OH)2 is selected as the esterified component.

[0056] X 1 and X 2 Each is independently -O-, >N-Ar, -S-, or -Se-, where the Ar in the aforementioned N-Ar is an optionally substituted aryl, optionally substituted heteroaryl, or optionally substituted alkyl group, and the Ar in the aforementioned N-Ar is optionally bonded to the aforementioned A, B, and / or C rings via a linking group or a single bond.

[0057] At least one hydrogen atom in the above structural formula may optionally be substituted with deuterium.

[0058] The effects of the invention

[0059] The boric acid or borate esters represented by the above general formula (1) exhibit extremely high stability, thus avoiding problems arising from high reactivity even in reactions with acids, and preventing yield reduction during scale-up. Furthermore, the highly stable boric acid or borate esters are easy to separate and purify, allowing for the production of products with high selectivity. Consequently, it is easier to obtain polycyclic aromatic compounds as materials for organic EL elements with high purity and high yield. Moreover, production can be carried out using a simple heating reaction by simply changing the temperature within the same reactor.

[0060] Furthermore, polycyclic aromatic compounds obtained from the aforementioned boric acid or borate esters, which are formed by linking aromatic rings with heteroelements such as boron, phosphorus, oxygen, nitrogen, and sulfur, possess large HOMO-LUMO band gaps (band gap Eg of thin films) and high triplet excitation energies (E0). T This is believed to be because the 6-membered ring containing heteroelements has low aromaticity, thus suppressing the reduction of the HOMO-LUMO band gap associated with the expansion of the conjugated system. The SOMO1 and SOMO2 of the triplet excited state (T1) are localized due to electronic perturbations by the heteroelement. Furthermore, the localization of SOMO1 and SOMO2 in the triplet excited state (T1) of this polycyclic aromatic compound reduces the exchange interaction between the two orbitals, resulting in a small energy difference between the triplet excited state (T1) and the singlet excited state (S1), exhibiting thermally activated hysteretic fluorescence. Therefore, it is also useful as a fluorescent material for organic EL elements. Additionally, it possesses a high triplet excitation energy (E0). T These materials are also useful as electron transport layers and hole transport layers for phosphorescent organic EL elements and organic EL elements utilizing thermally activated hysteresis fluorescence. Furthermore, the energies of HOMO and LUMO can be arbitrarily varied by introducing substituents, thus allowing for optimization of ionization potential and electron affinity based on surrounding materials. Attached Figure Description

[0061] Figure 1 This is a cross-sectional schematic diagram of the organic EL element according to this embodiment.

[0062] Explanation of reference numerals in the attached figures

[0063] 100 Organic electroluminescent devices

[0064] 101 substrate

[0065] 102 Anode

[0066] 103 Hole Injection Layer

[0067] 104 Hole Transport Layer

[0068] 105 Emissive Layer

[0069] 106 Electron Transport Layer

[0070] 107 Electron Injection Layer

[0071] 108 cathode Detailed Implementation

[0072] 1. Summary of the Invention

[0073] If the present invention is described in a general sense, one aspect of the invention relates to compounds represented by the following general formula (1) and polymeric compounds having a plurality of structures represented by the following general formula (1). It should be noted that, regarding polymeric compounds, the compound structure varies depending on the number and morphology of polymerization. Therefore, the following polymeric compound is an example where the central polymeric compound is a compound formed by bonding two structures represented by formula (1) with single bonds, and the right-hand polymeric compound is a compound formed by bonding two structures represented by formula (1) with a common ring A. Furthermore, the symbols in the formulas are the same as defined in item 1 above.

[0074]

[0075] For these compounds, due to Y 1 The substituted -B(OH)₂ is optionally esterified and is therefore also referred to as boric acid or borate ester in this specification. The uses of these compounds are not particularly limited, excluding X. 1 and X 2 The case where all are -O-.

[0076] Furthermore, other aspects of the present invention relate to compounds of the following general formula (1) for the manufacture of polycyclic aromatic compounds, or polymeric compounds having a plurality of structures of the following general formula (1) for the manufacture of polycyclic aromatic polymeric compounds. These compounds for the manufacture of polycyclic aromatic compounds and polycyclic aromatic polymeric compounds can be X 1 and X 2 All are -O-. These compounds are also due to Y 1 The esterified -B(OH)2 is referred to as boric acid or borate ester in this specification. It should be noted that, for polymeric compounds, the compound structure varies depending on the amount and form of polymerization; therefore, the following structure is an example. Furthermore, the symbols in the formula are the same as defined in item 1 above.

[0077]

[0078] The following is a summary of the process for manufacturing polycyclic aromatic compounds using the compound represented by the general formula (1) for manufacturing polycyclic aromatic compounds. Furthermore, the symbols in the formula are the same as those defined in item 7 above.

[0079]

[0080] Furthermore, the following is a summary of the process for manufacturing polycyclic aromatic polymers using polymers having structures shown in multiple general formulas (1) for manufacturing polycyclic aromatic polymers. It should be noted that the structure of a polymer, or polycyclic aromatic polymer, varies depending on the amount and form of polymerization; therefore, the following structure is an example. Additionally, the symbols in the formula are the same as those defined in item 7 above.

[0081]

[0082] 2. The boric acid and borate esters of the present invention

[0083] The invention described herein is a compound represented by the following general formula (1), or a polymeric compound having a plurality of structures represented by the following general formula (1). Preferably, the invention described herein is a compound represented by the following general formula (2), or a polymeric compound having a plurality of structures represented by the following general formula (2). It should be noted that Y in the following formula (1)... 1 X 1 and X 2 As defined in item 1 above, Y in the following equation (2) 1 X 1 X 2 and R 1 ~R 11 Same as the definition in item 3 above.

[0084]

[0085] In general formula (1), rings A, B, and C are independently aromatic or heteroaromatic rings, and at least one hydrogen atom in these rings may optionally be substituted with a substituent. The substituent is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaromatic group, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted diheteroaromatic amino group, a substituted or unsubstituted arylheteroaromatic amino group (an amino group having both an aryl and a heteroaromatic group), a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a halogen. Examples of substituents for these groups when they have substituents include aryl, heteroaromatic, alkyl, or halogen groups.

[0086] Furthermore, rings A, B, and C are preferably 5-membered or 6-membered rings fused together with other rings, independently of each other. The structure of general formula (2) is an example where rings A, B, and C are benzene rings (6-membered rings). Wherein, as described later, R... 1 ~R 11 The adjacent groups can be optionally bonded to each other to form an aromatic ring or heteroaromatic ring together with the a ring, b ring or c ring. Therefore, the benzene ring can also be a structure fused with other rings.

[0087] In general formula (1), ring A (or ring B, ring C) corresponds to ring a and its substituent R in general formula (2). 1 ~R 3 (or b ring and its substituent R) 4 ~R 7 c-ring and its substituent R 8 ~R 11 In this sense, the rings of general formula (2) are represented by lowercase a to c.

[0088] In general formula (2), the substituents R of rings a, b, and c are... 1 ~R 11 Adjacent groups may optionally bond to each other to form an aromatic or heteroaromatic ring together with ring a, ring b, or ring c. At least one hydrogen atom in the formed ring may optionally be substituted by an aryl, heteroaryl, diarylamino, diarylamino, arylhelelamino, alkyl, alkoxy, aryloxy, or halogen. Therefore, the ring structure of the compound represented by general formula (2) varies depending on the bonding morphology of the substituents in rings a, b, and c, as shown in formulas (2-1) and (2-2) below. In each formula, rings A', B', and C' correspond to rings A, B, and C in general formula (1), respectively. It should be noted that Y in the following formulas... 1 X 1 X 2 and R 1 ~R 11 Same as the definition in item 3 above.

[0089]

[0090] If the A' ring, B' ring, and C' ring in equations (2-1) and (2-2) above are explained by general formula (2), then they represent the substituent R. 1 ~R 11 The adjacent groups in the ring are bonded to each other to form aromatic or heteroaromatic rings with rings a, b, and c, respectively (or fused rings formed by other ring structures fused to rings a, b, or c). It should be noted that although not shown in the formula, there are compounds in which rings a, b, and c are all transformed into rings A', B', and C', respectively. Furthermore, as can be seen from formulas (2-1) and (2-2) above, for example, R of ring b... 8 R with c ring 7 R of ring b 11 R with ring a 1 R of c ring 4 R with ring a 3 These are not considered "adjacent groups to each other" because they are not bonded. That is, "adjacent groups" refers to groups that are adjacent to each other on the same ring.

[0091] The compounds shown in formulas (2-1) and (2-2) above correspond to, for example, the compounds shown in formulas (1-3-323) to (1-3-391) listed as specific compounds below. That is, for example, a compound having an A' ring (or B' ring or C' ring) formed by fused benzene ring, indole ring, pyrrole ring, benzofuran ring or benzothiophene ring to a benzene ring as a ring (or b ring or c ring), wherein the fused ring A' (or fused ring B' or fused ring C') formed is a naphthyl ring, carbazole ring, indole ring, dibenzofuran ring or dibenzothiophene ring, etc.

[0092] Y in general formula (1) 1 The esterified -B(OH)2 is optional. Preferred Y 1 The group obtained by esterification of -B(OH)2. This description applies to Y in general formula (2). 1 The same applies to them.

[0093] The group (-B(OR)2) obtained by esterifying -B(OH)2 is not particularly limited, and can be listed as a group obtained by reacting a hydroxyl group, such as an alkyl group or an aryl group, with boric acid. R in -B(OR)2 can be any alkyl group having 1 to 4 carbon atoms (branched alkyl group having 3 to 4 carbon atoms), which can optionally be bonded to each other to form a ring, and the formed ring can contain an aromatic ring such as benzene. Specifically, groups with the following structures can be listed.

[0094]

[0095] X in general formula (1) 1 and X 2 The R in ">C(R)2" is independently -O-, >N-Ar, -S-, or -Se-, where the Ar in the aforementioned N-Ar is an optionally substituted aryl, optionally substituted heteroaryl, or optionally substituted alkyl group, and the Ar in the aforementioned N-Ar is optionally bonded to the aforementioned A, B, and / or C rings via a linking group or a single bond, preferably -O-, -S-, or >C(R)2. It should be noted that the R in the aforementioned ">C(R)2" is independently hydrogen or alkyl, and at least one hydrogen in the alkyl group is optionally substituted with a halogen. This specification refers to X in general formula (2). 1 and X 2 The same.

[0096] Here, the limitation in general formula (1) that “the Ar of N-Ar is bonded to the aforementioned ring A, ring B and / or ring C by a linking group or a single bond” corresponds to the limitation in general formula (2) that “the Ar of N-Ar is bonded to the aforementioned ring a, ring b and / or ring c by -O-, -S-, >C(R)2 or a single bond”.

[0097] This limitation can be represented by the following formula (2-3-1), having X 1 X 2 Compounds with ring structures incorporated into fused rings B' and C' are represented. That is, for example, compounds having a benzene ring as ring b (or ring c) in general formula (2) to incorporate X. 1 (or X) 2 Compounds that form a B' ring (or C' ring) by fusing with other rings. The formed fused ring B' (or fused ring C') is, for example, a phenoxazine ring, a phenothiazine ring, or an acridine ring.

[0098] Alternatively, the above limitation can also be expressed as shown in equations (2-3-2) and (2-3-3), having X. 1 and / or X 2 Compounds with ring structures incorporated into the fused ring A' are represented. That is, for example, compounds having a benzene ring as the a ring in general formula (2) to incorporate X. 1 (and / or X) 2 Compounds that form an A' ring by fusing with other rings. The formed fused ring A' can be, for example, a phenoxazine ring, a phenothiazine ring, or an acridine ring.

[0099] It should be noted that Y in the following formula 1 X 1 X 2 and R 1 ~R 11 Same as the definition in item 3 above.

[0100]

[0101] Regarding the "aromatic ring" in general formula (1), which serves as ring A, ring B, and ring C, examples include aromatic rings with 6 to 30 carbon atoms, preferably aromatic rings with 6 to 16 carbon atoms, more preferably aromatic rings with 6 to 12 carbon atoms, and particularly preferably aromatic rings with 6 to 10 carbon atoms. It should be noted that this "aromatic ring" corresponds to "R" defined in general formula (2). 1 ~R 11 "An aromatic ring is formed by adjacent groups bonding together with the a ring, b ring or c ring". In addition, the a ring (or the b ring or c ring) is already composed of a benzene ring with 6 carbons, so the total number of carbons of the fused ring formed by fusing it with the 5-membered ring is 9, which is the lower limit of the number of carbons.

[0102] As specific "aromatic rings," examples include benzene rings belonging to monocyclic systems; biphenyl rings belonging to bicyclic systems; naphthalene rings belonging to fused bicyclic systems; terphenyl rings (m-terphenyl, o-terphenyl, p-terphenyl) belonging to tricyclic systems; acenaphthene rings, fluorene rings, phenanthene rings, and phenanthrene rings belonging to fused tricyclic systems; benzo[a]phenanthrene rings, pyrene rings, and fused tetraphenyl rings belonging to fused tetracyclic systems; and perylene rings and fused pentaphenyl rings belonging to fused pentacyclic systems.

[0103] Regarding the "heteroaromatic ring" in general formula (1), which serves as ring A, ring B, and ring C, examples include heteroaromatic rings with 2 to 30 carbon atoms, preferably heteroaromatic rings with 2 to 25 carbon atoms, more preferably heteroaromatic rings with 2 to 20 carbon atoms, even more preferably heteroaromatic rings with 2 to 15 carbon atoms, and particularly preferably heteroaromatic rings with 2 to 10 carbon atoms. Furthermore, as a "heteroaromatic ring," examples include heterocycles that, in addition to carbon atoms, contain 1 to 5 heteroatoms selected from oxygen, sulfur, and nitrogen. It should be noted that this "heteroaromatic ring" corresponds to "R" defined in general formula (2). 1 ~R 11 "The adjacent groups in the ring are bonded to each other to form a heteroaromatic ring together with the a ring, b ring or c ring. In addition, the a ring (or the b ring, c ring) is already composed of a benzene ring with 6 carbons, so the total number of carbons of the fused ring formed by fusing it with the 5-membered ring is 6, which is the lower limit of the number of carbons."

[0104] Specific examples of "heteroaromatic rings" include pyrrole rings, oxazole rings, isoxazole rings, thiazole rings, isothiazole rings, imidazole rings, oxadiazole rings, thiadiazole rings, triazole rings, tetraazole rings, pyrazole rings, pyridine rings, pyrimidine rings, pyrazine rings, pyrazine rings, triazine rings, indole rings, isoyindole rings, 1H-indazole rings, benzimidazole rings, benzoxazole rings, benzothiazole rings, and 1H-benzotriazole rings. Quinoline ring, isoquinoline ring, cyclophosphine ring, quinazolinoline ring, quinoxaline ring, phthalazine ring, naphthidine ring, purine ring, pteridine ring, carbazole ring, acridine ring, phenoxthia ring, phenoxazine ring, phenthiazine ring, phenazine ring, indoleazine ring, furan ring, benzofuran ring, isobenzofuran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, furazine ring, oxadiazole ring, thiathrone ring, etc.

[0105] At least one hydrogen atom in the aforementioned "aromatic ring" or "heteroaromatic ring" may be optionally replaced by a first substituent, a substituted or unsubstituted "aryl", a substituted or unsubstituted "heteroaromatic", a substituted or unsubstituted "diarylamino", a substituted or unsubstituted "diheteroaromatic", a substituted or unsubstituted "arylheteroaromatic", a substituted or unsubstituted "alkyl", a substituted or unsubstituted "alkoxy", a substituted or unsubstituted "aryloxy", or a halogen-substituted. Examples of monovalent groups of the aforementioned "aromatic ring" or "heteroaromatic ring" may be listed regarding the aryl, "heteroaromatic", "diarylamino", "heteroaromatic", "aryl and heteroaromatic of "arylheteroaromatic", or "aryloxy" groups that are the first substituents.

[0106] Furthermore, the "alkyl" group used as the first substituent can be either straight-chain or branched, for example, straight-chain alkyl groups with 1 to 24 carbon atoms or branched alkyl groups with 3 to 24 carbon atoms. Alkyl groups with 1 to 18 carbon atoms (branched alkyl groups with 3 to 18 carbon atoms) are preferred, alkyl groups with 1 to 12 carbon atoms (branched alkyl groups with 3 to 12 carbon atoms) are more preferred, alkyl groups with 1 to 6 carbon atoms (branched alkyl groups with 3 to 6 carbon atoms) are even more preferred, and alkyl groups with 1 to 4 carbon atoms (branched alkyl groups with 3 to 4 carbon atoms) are particularly preferred.

[0107] Specific alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl, etc.

[0108] Furthermore, regarding the "alkoxy group" as the first substituent, examples include straight-chain alkoxy groups with 1 to 24 carbon atoms or branched alkoxy groups with 3 to 24 carbon atoms. Preferably, alkoxy groups with 1 to 18 carbon atoms (branched alkoxy groups with 3 to 18 carbon atoms), more preferably, alkoxy groups with 1 to 12 carbon atoms (branched alkoxy groups with 3 to 12 carbon atoms), even more preferably, alkoxy groups with 1 to 6 carbon atoms (branched alkoxy groups with 3 to 6 carbon atoms), and particularly preferably, alkoxy groups with 1 to 4 carbon atoms (branched alkoxy groups with 3 to 4 carbon atoms).

[0109] Specific alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, hexoxy, heptoxy, octoxy, etc.

[0110] In addition, regarding "halogens" as the first substituent, examples include fluorine, chlorine, bromine, or iodine.

[0111] Regarding the first substituent, substituted or unsubstituted "aryl", substituted or unsubstituted "heteroaryl", substituted or unsubstituted "diarylamino", substituted or unsubstituted "diheteroarylamino", substituted or unsubstituted "arylheteroarylamino", substituted or unsubstituted "alkyl", substituted or unsubstituted "alkoxy", or substituted or unsubstituted "aryloxy", as described above for substitution or unsubstituent, at least one hydrogen atom in any of them may optionally be substituted by a second substituent. Examples of the second substituent include, for example, aryl, heteroaryl, alkyl, or halogen, specific examples of which can be found in the description of the monovalent group of the "aromatic ring" or "heteroaryl ring" above, or the "alkyl" or "halogen" as the first substituent. Furthermore, groups in which at least one hydrogen atom in the aryl or heteroaryl as the second substituent is substituted with an aryl group such as phenyl (specific examples as described above) or an alkyl group such as methyl (specific examples as described above) are also included within the aryl or heteroaryl as the second substituent. As an example, when the second substituent is carbazolyl, carbazolyl groups formed by replacing at least one hydrogen at the 9th position with aryl groups such as phenyl or alkyl groups such as methyl are also included among heteroaryl groups as the second substituent.

[0112] R as general formula (2) 1 ~R 11 The aryl, heteroaryl, aryl of diarylamino, heteroaryl of diarylamino, aryl and heteroaryl of arylheylamino, aryl or halogen of aryloxy groups can be listed as monovalent groups of the "aromatic ring" or "heteroaryl ring" described in general formula (1). Additionally, as R 1 ~R 11 The alkyl, alkoxy, or halogen groups can be referred to in the description of "alkyl," "alkoxy," or "halogen" as the first substituent in the above general formula (1). Similarly, the aryl, heteroaryl, alkyl, or halogen groups that are substituents on these groups are also referred to. Furthermore, regarding R... 1 ~R 11 In cases where adjacent groups are bonded to each other to form an aromatic or heteroaromatic ring together with ring a, ring b, or ring c, the heteroaromatic, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, alkoxy, aryloxy, or halogen as substituents on these rings, and the aryl, heteroaromatic, alkyl, or halogen as further substituents, are also included.

[0113] X of general formula (1) 1 and X 2In the N-Ar group, Ar is an aryl, heteroaryl, or alkyl group optionally substituted with the second substituent mentioned above, and at least one hydrogen atom in the aryl, heteroaryl, or alkyl group is optionally substituted with, for example, an alkyl group or a halogen. Examples of such aryl, heteroaryl, alkyl, and halogen groups are listed above. Particularly preferred are aryl groups with 6 to 10 carbon atoms (e.g., phenyl, naphthyl, etc.), heteroaryl groups with 2 to 15 carbon atoms (e.g., carbazolyl, etc.), and alkyl groups with 1 to 4 carbon atoms (e.g., methyl, ethyl, etc.). This description applies to X in general formula (2). 1 and X 2 The same applies to them.

[0114] In general formula (1), the Rs in ">C(R)2", which serve as linking groups, are independently hydrogen or alkyl groups, at least one of which may be substituted with a halogen. Examples of such alkyl or halogen groups include those mentioned above. As an alkyl group, alkyl groups having 1 to 4 carbon atoms (e.g., methyl, ethyl, etc.) are particularly preferred. The same description applies to ">C(R)2", which serves as linking groups in general formula (2).

[0115] Furthermore, the present invention is a polymeric compound having multiple unit structures shown in general formula (1), and preferably a polymeric compound having multiple unit structures shown in general formula (2). The polymeric compound is preferably a 2 to 6-mer, more preferably a 2 to 3-mer, and particularly preferably a 2-mer. The polymeric compound can be any compound having multiple of the above-mentioned unit structures. For example, it can be a compound in which multiple of the above-mentioned unit structures are bonded together by single bonds, alkylene groups with 1 to 3 carbon atoms, phenylene groups, naphthylene groups, etc. (for example, compounds corresponding to formulas (1-1-223) and (1-1-226) described later). In addition, it can be a compound in which any ring (A ring, B ring or C ring, a ring, b ring or c ring) contained in the above-mentioned unit structures is shared in multiple unit structures. In addition, it can be a compound in which any ring (A ring, B ring or C ring, a ring, b ring or c ring) contained in the above-mentioned unit structures are bonded together in a fused manner.

[0116] Examples of such polymeric compounds include those shown in formulas (2-4), (2-4-1), (2-4-2), (2-5-1) to (2-5-4), or (2-6). Specifically, these are compounds corresponding to those shown in formulas (1-1-224), (1-1-225), (1-1-227), and (1-1-228) described later. The polymeric compound shown in formula (2-4) described below, if explained by general formula (2), is a polymeric compound having multiple unit structures shown in general formula (2) in a compound, with a benzene ring as the a ring being shared. More specifically, the polymeric compound shown in formula (2-4-1) below, if described by general formula (2), is a polymeric compound having two unit structures shown in general formula (2) in a compound, with a benzene ring as the common a ring. The polymeric compound shown in formula (2-4-2) below, if described by general formula (2), is a polymeric compound having three unit structures shown in general formula (2) in a compound, with a benzene ring as the common a ring. In addition, the polymeric compounds shown in formulas (2-5-1) to (2-5-4) below, if described by general formula (2), are polymeric compounds having multiple unit structures shown in general formula (2) in a compound, with a benzene ring as the common b ring (or c ring). Furthermore, if the polymeric compounds shown in formulas (2-6) below are described using general formula (2), then they are polymeric compounds having multiple unit structures shown in general formula (2) in a compound, for example, in which a benzene ring of a certain unit structure as a b ring (or a ring, c ring) is fused with a benzene ring of a certain unit structure as a b ring (or a ring, c ring). It should be noted that Y in the following formulas 1 X 1 X 2 and R 1 ~R 11 Same as the definition in item 3 above.

[0117]

[0118] The polymeric compound can also be a polymeric compound formed by combining the polymeric form represented by formula (2-4), formula (2-4-1) or formula (2-4-2) with the polymeric form represented by any one of formulas (2-5-1) to (2-5-4) or formula (2-6), or a polymeric compound formed by combining the polymeric form represented by any one of formulas (2-5-1) to (2-5-4) with the polymeric form represented by formula (2-6), or a polymeric compound formed by combining the polymeric form represented by formula (2-4), formula (2-4-1) or formula (2-4-2) with the polymeric form represented by any one of formulas (2-5-1) to (2-5-4) with the polymeric form represented by formula (2-6).

[0119] In addition, the hydrogen in the chemical structure of the compound represented by general formula (1) or (2), or the polymeric compound having a plurality of structures represented by general formula (1) or (2), may be all or part of deuterium.

[0120] More specific examples of the boric acids and borate esters of the present invention can be listed below. In each formula, Bpin is a group obtained by esterifying -B(OH)₂pinacol, and Me is a methyl group. t Bu is schottinki. i Pr is isopropyl.

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182] In the above examples, the preferred compounds are those represented by any one of formulas (1-1-1) to (1-1-209), any one of formulas (1-2-1) to (1-2-306), and any one of formulas (1-3-1) to (1-3-466).

[0183] 3. Method for manufacturing boric acid or borate esters of general formula (1)

[0184] The compounds (boronic acid or borate ester) represented by general formula (1) or (2) can be basically prepared as follows: by using a bonding group (X 1 and X 2 The intermediate is prepared by bonding ring A (ring a) with ring B (ring b) and ring C (ring c) (reaction 1), and then Y is introduced. 1The group allows for the initial production of boronic esters, which can then be hydrolyzed to produce boronic acid. In the first reaction, for example, if it is an etherification reaction, conventional reactions such as nucleophilic substitution or Ullmann reactions can be used; if it is an amination reaction, conventional reactions such as the Buchwald-Hartwig reaction can be used. It should be noted that the symbols in the structural formulas of the schemes shown below are the same as those defined above.

[0185] The second reaction is as shown in scheme (1) or (2) below, which involves introducing the intermediate obtained by the first reaction as Y. 1 The reaction of borate esters like Bpin.

[0186] Option (1)

[0187]

[0188] Option (2)

[0189]

[0190] In schemes (1) and (2) above, firstly, hydrogen atoms are lithiated by ortho-metallization using n-butyllithium, sec-butyllithium, or tert-butyllithium. Here, a method using n-butyllithium, sec-butyllithium, or tert-butyllithium alone is shown, but to improve reactivity, N,N,N',N'-tetramethylethylenediamine or the like can also be added. Then, a borate esterification agent such as 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxapentylborane is added to the obtained lithiated body, thereby enabling the production of pinacol esters of boric acid. Here, a method using 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxapentylborane is shown; in addition, trimethoxyborane, triisopropoxyborane, etc., can also be used. Alternatively, 4,4,5,5-tetramethyl-1,3,2-dioxapentylborane and the like can also be used by applying the method described in International Publication No. 2013 / 016185.

[0191] In addition, as shown in scheme (3) or (4) below, borate esters produced by the method of scheme (1) or (2) above can be hydrolyzed to produce boric acid.

[0192] Option (3)

[0193]

[0194] Option (4)

[0195]

[0196] Furthermore, by acting an appropriate alcohol on the borate ester or boric acid obtained through the above schemes (1) to (4), different borate esters can be produced by transesterification or re-esterification.

[0197] It should be noted that the above schemes (1) and (2) show the manufacturing method of the borate ester shown in general formula (1) or (2). Regarding the polymeric compound having multiple structures shown in general formula (1) or (2), it can be manufactured by using an intermediate having multiple A rings (a ring), B rings (b ring), and C rings (c ring). The details are explained in the following schemes (5) to (7). In this case, by setting the amount of reagents such as butyllithium used to 2 times, 3 times, etc., the target compound such as dimer compound and trimer compound can be obtained.

[0198] Option (5)

[0199]

[0200] Option (6)

[0201]

[0202] Option (7)

[0203]

[0204] The above schemes (5) to (7) show a method for manufacturing a polymeric compound of borate ester. The borate body can be manufactured by hydrolysis according to the above scheme (4). In addition, different ester bodies can also be manufactured by transesterification and re-esterification using alcohol.

[0205] By appropriately selecting the above-mentioned synthetic method and the raw materials used, it is possible to synthesize boronic acid or boronic esters with substituents at the desired positions.

[0206] In the above schemes (1) to (7), lithium is introduced to the desired position through ortho-metallization. Lithium can also be introduced to the desired position by introducing halogens such as bromine atoms to the desired lithium position and performing halogen-metal exchange as in schemes (8) or (9) below. Then, borate esters can be manufactured from the obtained lithium compound.

[0207] Option (8)

[0208]

[0209] Option (9)

[0210]

[0211] In schemes (8) and (9) above, firstly, a halogen-lithium exchange reaction is carried out using n-butyllithium, sec-butyllithium, or tert-butyllithium, thereby lithiating the halogen atom. Here, a method using n-butyllithium, sec-butyllithium, or tert-butyllithium alone is shown, but to improve reactivity, N,N,N',N'-tetramethylethylenediamine or the like can also be added. Then, a borate esterification agent such as 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxapentylborane is added to the obtained lithiated body, thereby enabling the production of pinacol esters of boric acid. Here, a method using 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxapentylborane is shown, and trimethoxyborane, triisopropoxyborane, etc., can also be used. Alternatively, 4,4,5,5-tetramethyl-1,3,2-dioxapentylborane and the like can also be used by applying the method described in International Publication No. 2013 / 016185.

[0212] It should be noted that schemes (8) and (9) above illustrate methods for manufacturing borate esters represented by general formula (1) or (2). Boric acid can be produced by hydrolyzing the borate esters thus obtained (see schemes (3) or (4) above). In addition, different borate esters can be produced by reacting appropriate alcohols with these borate esters and boric acid via transesterification or re-esterification. Furthermore, polymeric compounds having multiple structures represented by general formula (1) or (2) can also be produced by using intermediates having multiple A rings (a ring), B rings (b ring), and C rings (c ring) (see schemes (5) to (7) above).

[0213] Alternatively, as shown in schemes (10) or (11) below, borate esters can also be synthesized by coupling the bromide with bis(pinacol)diborane or 4,4,5,5-tetramethyl-1,3,2-dioxapentoborane using a palladium catalyst and a base.

[0214] Option (10)

[0215]

[0216] Option (11)

[0217]

[0218] It should be noted that the above schemes (10) and (11) illustrate a method for manufacturing borate esters of general formula (1) or (2). Boric acid can be manufactured by hydrolyzing the borate esters thus obtained (see above schemes (3) or (4)). In addition, by reacting these borate esters and boric acid with a suitable alcohol, different borate esters can be manufactured via transesterification or re-esterification. Furthermore, polymeric compounds having multiple structures shown in general formula (1) or (2) can also be manufactured by using intermediates having multiple A rings (a ring), B rings (b ring), and C rings (c ring) (see above schemes (5) to (7)).

[0219] Examples of metallizing reagents used in the halogen-metal exchange reaction described above include alkyl lithiums such as methyl lithium, n-butyl lithium, sec-butyl lithium, and tert-butyl lithium, isopropyl magnesium chloride, isopropyl magnesium bromide, phenyl magnesium chloride, phenyl magnesium bromide, and lithium chloride complexes of isopropyl magnesium chloride known as TurboGrignard reagents.

[0220] In addition to the reagents mentioned above, other organic base compounds that can be listed as metallizing agents used in the ortho-metal exchange reaction in the scheme described above include lithium diisopropylamide, lithium tetramethylpiperidinium, lithium hexamethyldisilamide, potassium hexamethyldisilamide, lithium chloride tetramethylpiperidinium magnesium-lithium chloride complex, and lithium tri-n-butylmagnesium oxide.

[0221] Furthermore, when alkyllithium is used as the metallizing agent, N,N,N',N'-tetramethylethylenediamine, 1,4-diazabicyclo[2.2.2]octane, and N,N-dimethylpropylene urea can be listed as additives to promote the reaction.

[0222] In addition, the boric acid or borate ester of the present invention also includes boric acid or borate ester in which at least some of the hydrogen atoms are replaced by deuterium, or boric acid or borate ester in which halogens such as fluorine and / or chlorine are replaced, and such compounds can be synthesized in the same manner as described above using raw materials in which deuteration, fluorination or chlorination has occurred at the desired positions.

[0223] 4. A method for manufacturing polycyclic aromatic compounds from boric acid and other substances of general formula (1)

[0224] Next, methods for manufacturing polycyclic aromatic compounds and polycyclic aromatic polymers using boric acid or borate esters as shown in general formula (1) will be described. It should be noted that the symbols in the structural formulas shown below are the same as those defined above.

[0225] In schemes (12) or (13) below, polycyclic aromatic compounds can be produced by reacting boric acid or borate esters represented by general formula (1) with a Lewis acid such as aluminum chloride.

[0226] Option (12)

[0227]

[0228] Option (13)

[0229]

[0230] Alternatively, Brønsted acids such as p-toluenesulfonic acid can be used. Especially when using Lewis acids in the reaction, bases such as diisopropylethylamine can be added to improve selectivity and yield.

[0231] Alternatively, polycyclic aromatic polymers can also be manufactured using polymers having structures shown in multiple general formulas (1) or (2) by means of the methods described in schemes (14) to (16) below. In this case, by setting the amount of reagents such as aluminum chloride used to 2 times, 3 times, etc., corresponding to the structure of the polymer, target compounds such as dimer compounds and trimer compounds can be obtained.

[0232] Option (14)

[0233]

[0234] Option (15)

[0235]

[0236] Option (16)

[0237]

[0238] Examples of Lewis acids used in schemes (12) to (16) include AlCl3, AlBr3, AlF3, BF3·OEt2, BCl3, BBr3, GaCl3, GaBr3, InCl3, InBr3, In(OTf)3, SnCl4, SnBr4, AgOTf, ScCl3, Sc(OTf)3, ZnCl2, ZnBr2, Zn(OTf)2, MgCl2, MgBr2, Mg(OTf)2, LiOTf, NaOTf, KOTf, Me3SiOTf, Cu(OTf)2, CuCl2, YCl3, Y(OTf)3, TiCl4, TiBr4, ZrCl4, ZrBr4, FeCl3, FeBr3, CoCl3, and CoBr3. Furthermore, substances formed by loading these Lewis acids onto solids can also be used.

[0239] Examples of Brønsted acids used in schemes (12) to (16) above include p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, fluorosulfonic acid, carboxylic acid, trifluoroacetic acid, (trifluoromethanesulfonyl)imide, tris(trifluoromethanesulfonyl)methane, hydrogen chloride, hydrogen bromide, and hydrogen fluoride. Additionally, examples of solid Brønsted acids include Amberlist (trade name: Dow Chemical), Nafion (trade name: DuPont), zeolite, and Taycacure (trade name: Tayca Corporation).

[0240] As amines that can be added in the above schemes (12) to (16), diisopropylethylamine, triethylamine, tributylamine, 1,4-diazabicyclo[2.2.2]octane, N,N-dimethyl-p-toluidine, N,N-dimethylaniline, pyridine, 2,6-dimethylpyridine, 2,6-ditert-butylamine, etc.

[0241] In addition, the solvents used in the above schemes (12) to (16) include o-dichlorobenzene, chlorobenzene, toluene, benzene, dichloromethane, chloroform, dichloroethylene, trifluorotoluene, decahydronaphthalene, cyclohexane, hexane, heptane, 1,2,4-trimethylbenzene, xylene, diphenyl ether, anisole, cyclopentylmethyl ether, tetrahydrofuran, dioxane, methyl-tert-butyl ether, etc.

[0242] 5. Organic devices

[0243] The polycyclic aromatic compounds and polycyclic aromatic polymers produced in this invention can be used as materials for organic devices. Examples of organic devices include organic electroluminescent devices, organic field-effect transistors, and organic thin-film solar cells.

[0244] 5-1. Organic electroluminescent devices

[0245] The polycyclic aromatic compounds and polycyclic aromatic polymers manufactured in this invention can be used as materials constituting the various layers of an organic electroluminescent device. Hereinafter, the organic EL element of this embodiment will be described in detail based on the accompanying drawings. Figure 1 This is a cross-sectional schematic diagram of the organic EL element according to this embodiment.

[0246] Figure 1 The organic electroluminescent device 100 shown includes a substrate 101, an anode 102 disposed on the substrate 101, a hole injection layer 103 disposed on the anode 102, a hole transport layer 104 disposed on the hole injection layer 103, a light-emitting layer 105 disposed on the hole transport layer 104, an electron transport layer 106 disposed on the light-emitting layer 105, an electron injection layer 107 disposed on the electron transport layer 106, and a cathode 108 disposed on the electron injection layer 107.

[0247] It should be noted that the organic electroluminescent device 100 can also be manufactured in a reverse order, for example, having a substrate 101, a cathode 108 disposed on the substrate 101, an electron injection layer 107 disposed on the cathode 108, an electron transport layer 106 disposed on the electron injection layer 107, a light-emitting layer 105 disposed on the electron transport layer 106, a hole transport layer 104 disposed on the light-emitting layer 105, a hole injection layer 103 disposed on the hole transport layer 104, and an anode 102 disposed on the hole injection layer 103.

[0248] Not all of the above layers are indispensable. The smallest constituent unit is set as a structure formed by an anode 102, a light-emitting layer 105, and a cathode 108. The hole injection layer 103, hole transport layer 104, electron transport layer 106, and electron injection layer 107 are optional layers. In addition, each of the above layers can be formed by a single layer or by multiple layers.

[0249] The layers constituting an organic electroluminescent device can be formed as follows: The materials used to form each layer are deposited into thin films using methods such as vapor deposition, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular stacking, printing, spin coating, casting, or coating. There is no particular limitation on the film thickness of each layer formed in this way; it can be appropriately set according to the properties of the material, typically in the range of 2 nm to 5000 nm. The film thickness can usually be measured using a crystal oscillating film thickness measuring device. When using vapor deposition for thin film formation, the deposition conditions vary depending on the type of material, the target crystal structure of the film, and the association structure. The preferred deposition conditions are typically a boat heating temperature of +50 to +400°C and a vacuum degree of 10... -6 ~10 -3 The Pa, evaporation rate (0.01–50 nm / s), substrate temperature (-150–+300 °C), and film thickness (2 nm–5 μm) are appropriately set within the range.

[0250] When a DC voltage is applied to the organic electroluminescent device thus obtained, the anode is set to + and the cathode to - polarity. When the applied voltage is approximately 2–40V, light emission can be observed from the transparent or semi-transparent electrode side (anode or cathode, or both). Furthermore, this organic electroluminescent device also emits light when a pulsed current or alternating current is applied. It should be noted that the waveform of the applied alternating current can be arbitrary.

[0251] 5-2. Organic field-effect transistor

[0252] The polycyclic aromatic compounds and polycyclic aromatic polymers manufactured in this invention can be used as materials for constructing organic field-effect transistors (FETs). An organic field-effect transistor is a transistor that controls current using an electric field generated by a voltage input. In addition to source and drain electrodes, it also has a gate electrode. Applying a voltage to the gate electrode generates an electric field that can arbitrarily block the flow of electrons (or holes) between the source and drain electrodes, thereby controlling the current. FETs are easier to miniaturize than simple transistors (bipolar transistors) and are commonly used as components in integrated circuits, etc.

[0253] Regarding the structure of organic field-effect transistors, generally, the source and drain electrodes are simply disposed in contact with an organic semiconductor active layer formed using polycyclic aromatic compounds and polycyclic aromatic polymers manufactured in this invention, and the gate electrode is disposed sandwiched between an insulating layer (dielectric layer) in contact with the organic semiconductor active layer. Examples of such device structures include the following.

[0254] (1) Substrate / Gate electrode / Insulator layer / Source electrode / Drain electrode / Organic semiconductor active layer

[0255] (2) Substrate / Gate electrode / Insulator layer / Organic semiconductor active layer / Source electrode / Drain electrode

[0256] (3) Substrate / Organic semiconductor active layer / Source electrode / Drain electrode / Insulator layer / Gate electrode

[0257] (4) Substrate / Source electrode, Drain electrode / Organic semiconductor active layer / Insulator layer / Gate electrode

[0258] Organic field-effect transistors constructed in this way can be used as pixel driving switching elements in active matrix driven liquid crystal displays and organic electroluminescent displays.

[0259] 5-3. Organic thin-film solar cells

[0260] The polycyclic aromatic compounds and polycyclic aromatic polymers manufactured in this invention can be used as materials for constructing organic thin-film solar cells. Organic thin-film solar cells have a structure in which an anode (such as ITO), a hole transport layer, a photoelectric conversion layer, an electron transport layer, and a cathode are stacked on a transparent substrate such as glass. The photoelectric conversion layer has a p-type semiconductor layer on the anode side and an n-type semiconductor layer on the cathode side. The polycyclic aromatic compounds and polycyclic aromatic polymers manufactured in this invention can be used as materials for the hole transport layer, p-type semiconductor layer, n-type semiconductor layer, and electron transport layer according to their physical properties. The polycyclic aromatic compounds and polycyclic aromatic polymers manufactured in this invention can function as hole transport materials and electron transport materials in organic thin-film solar cells. In addition to the above, organic thin-film solar cells can also appropriately include hole blocking layers, electron blocking layers, electron injection layers, hole injection layers, smoothing layers, etc. In organic thin-film solar cells, known materials used in organic thin-film solar cells can be appropriately selected and combined.

[0261] Example

[0262] The present invention will be described in more detail below with reference to examples, but the invention is not limited thereto. First, examples of the synthesis of boric acid or borate esters will be described below.

[0263] Synthetic Example (1): Synthesis of Compound (1-1-98)

[0264]

[0265] A flask containing intermediate 1 (15 g) and toluene (300 ml) was heated to 70 °C under a nitrogen atmosphere to completely dissolve intermediate 1. The flask was cooled to -20 °C, and tetramethylethylenediamine (20.8 g) and a 1.00 M solution of sec-butyllithium in cyclohexane and n-hexane (89 ml) were added. The mixture was heated to 0 °C and stirred for 3 hours, then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxapentylborane (33.3 g) was added, and the mixture was refluxed for 1 hour. Water and toluene were added, and the mixture was separated. The solvent in the organic layer was removed by vacuum distillation. The resulting solid was washed with Solmix A-11 (trade name: Japan Alcohol Trading Co., Ltd.), dissolved in toluene, and allowed to stand at 0 °C for 1 hour. The precipitate was separated by filtration, and the filtrate was passed through a silica gel column (eluent: toluene / heptane = 1 / 5 mixed solvent (volume ratio)). After removing the solvent by distillation, the compound was reprecipitated with a mixture of ethyl acetate and Solmix A-11 to give the compound (9.5 g) of formula (1-1-98) as a white solid.

[0266]

[0267] The structure of the obtained compound was confirmed by NMR determination.

[0268] 1 H-NMR (400MHz, CDCl3): δ=7.18~7.16(m, 8H), 7.05~7.02(m, 4H), 6.95~6.92(m, 12H), 6.86~6.84(m, 2H), 6.44(s, 2H), 1.27(s, 36H), 0.54(s, 12H).

[0269] Synthesis Example (2): Synthesis of compound (1-3-139)

[0270]

[0271] A flask containing 1-bromo-2,6-difluorobenzene (85.4 g), phenol (100 g), potassium carbonate (244.7 g), and N-methyl-2-pyrrolidone (NMP, 300 ml) was heated to 180 °C under a nitrogen atmosphere and stirred for 22 hours. After the reaction was complete, the potassium carbonate was separated by filtration at 150 °C, and the solvent in the filtrate was removed by vacuum distillation. The resulting solid was dissolved in toluene and passed through a short silica gel column (eluent: toluene). After removing the solvent by vacuum distillation, the resulting solid was washed with heptane to give intermediate 2 (126.6 g) as a white solid.

[0272]

[0273] A 1.29 M tetrahydrofuran solution (351 mL) of the isopropyl magnesium chloride-lithium chloride complex was added to a flask containing intermediate 2 (103 g) and tetrahydrofuran (500 mL) under a nitrogen atmosphere at room temperature. After stirring for 1 hour, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxapentylborane (65.7 g) was added, and the mixture was stirred at room temperature for 2 hours. 3% dilute hydrochloric acid (1 L) and toluene (500 mL) were added, and the mixture was separated to extract the organic layer. After removing the solvent by vacuum distillation, the resulting solid was dissolved in toluene and passed through a silica gel column (eluent: toluene). The solvent was removed by distillation, yielding the compound (109 g) of formula (1-3-139) as a white solid.

[0274]

[0275] The structure of the obtained compound was confirmed by NMR determination.

[0276] 1H-NMR (400MHz, CDCl3): δ=7.31~7.25(m, 6H), 7.05~6.98(m, 5H), 6.71(d, 2H), 1.08(s, 12H).

[0277] Synthesis Example (3): Synthesis of compound (1-3-252)

[0278]

[0279] A flask containing intermediate 3 (40 g) synthesized by the method described in International Publication No. 2015 / 102118 and tetrahydrofuran (200 ml) was cooled to -20 °C under a nitrogen atmosphere. A 1.6 M solution of n-butyllithium in n-hexane (60 ml) was added, and the mixture was stirred at 0 °C for 2 hours. After cooling again to -20 °C, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxapentylborane (22.2 g) was added, and the mixture was stirred at room temperature for 1 hour while cooling to room temperature. Toluene and dilute hydrochloric acid were added, and the mixture was separated. The solvent of the organic layer was removed by vacuum distillation. The resulting solid was reprecipitated with a mixed solvent of toluene and heptane to give the compound (33.3 g) of formula (1-3-252) as a white solid.

[0280]

[0281] The structure of the obtained compound was confirmed by NMR determination.

[0282] 1 H-NMR (400MHz, CDCl3): δ=8.13 (d, 2H), 7.69 (d, 2H), 7.57 (d, 2H), 7.40~7.39 (m, 4H), 7.36~7.33 (m, 4H) 7.29~7.26 (m, 2H) 7.09~7.07 (m, 6H) 1.11 (s, 12H).

[0283] Synthesis Example (4): Synthesis of Compound (1-3-386)

[0284]

[0285] A flask containing methyl 4-methoxysalicylate (50.0 g) and pyridine (dehydrated) (350 ml) was cooled in an ice bath under a nitrogen atmosphere. Then, trifluoromethanesulfonic anhydride (154.9 g) was added dropwise to the solution. After the addition was complete, the ice bath was removed, and the mixture was stirred at room temperature for 2 hours. Water was added to stop the reaction. Toluene was added, and the mixture was separated from the liquid. The solution was purified by silica gel short-pass column chromatography (elution: toluene) to obtain methyl 4-methoxy-2-((trifluoromethyl)sulfonyl)oxy)benzoate (86.0 g).

[0286]

[0287] Pd(PPh3)4 (2.5 g) was added to a suspension of methyl 4-methoxy-2-((trifluoromethyl)sulfonyl)oxy)benzoate (23.0 g), (4-(diphenylamino)phenyl)boronic acid (25.4 g), tripotassium phosphate (31.1 g), toluene (184 ml), ethanol (27.6 ml), and water (27.6 ml) under a nitrogen atmosphere and stirred at reflux for 3 hours. The reaction mixture was cooled to room temperature, water and toluene were added, and the mixture was separated. The solvent in the organic layer was removed by vacuum distillation. The obtained solid was purified by silica gel column chromatography (elution: heptane / toluene mixed solvent). Methyl 4'-(diphenylamino)-5-methoxy-[1,1'-biphenyl]-2-carboxylic acid (29.7 g) was obtained. At this point, referring to the method described on page 94 of "Guide to Organic Chemistry Experiments (1) - Substance Processing and Separation and Purification Methods" published by Chemical Dojin Co., Ltd., the ratio of toluene in the eluent is slowly increased to dissolve the target substance.

[0288]

[0289] A THF solution (111.4 ml) containing methyl 4'-(diphenylamino)-5-methoxy-[1,1'-biphenyl]-2-carboxylic acid (11.4 g) was cooled in a water bath under a nitrogen atmosphere. A 1.0 M, 295 ml solution of magnesium methyl bromide in THF was added dropwise to this solution. After the addition was complete, the water bath was removed, the temperature was raised to reflux, and the mixture was stirred for 4 hours. Then, the mixture was cooled in an ice bath, and an aqueous solution of ammonium chloride was added to stop the reaction. Ethyl acetate was added, and the mixture was separated. The solvent was removed by vacuum distillation. The resulting solid was purified by silica gel column chromatography (eluent: toluene) to give 2-(5'-(diphenylamino)-5-methoxy-[1,1'-biphenyl]-2-yl)propane-2-ol (8.3 g).

[0290]

[0291] Under a nitrogen atmosphere, a flask containing 2-(5'-(diphenylamino)-5-methoxy-[1,1'-biphenyl]-2-yl)propane-2-ol (27.0 g), TAYCACURE-15 (trade name: Tayca Corporation) (13.5 g), and toluene (162 ml) was stirred at reflux for 2 hours. The reaction mixture was cooled to room temperature and passed through a short silica gel column (eluent: toluene) to remove TAYCACURE-15. The solvent was then removed by vacuum distillation to obtain 6-methoxy-9,9'-dimethyl-N,N-diphenyl-9H-fluorene-2-amine (25.8 g).

[0292]

[0293] Under a nitrogen atmosphere, a flask containing 25.0 g of 6-methoxy-9,9'-dimethyl-N,N-diphenyl-9H-fluorene-2-amine, 36.9 g of pyridine hydrochloride, and 22.5 mL of NMP was stirred at reflux for 6 hours. The reaction mixture was cooled to room temperature, and water and ethyl acetate were added, followed by separation. After removing the solvent by vacuum distillation, the mixture was purified by silica gel column chromatography (eluent: toluene) to give 22.0 g of 7-(diphenylamino)-9,9'-dimethyl-9H-fluorene-3-ol.

[0294]

[0295] A flask containing 14.1 g of 7-(diphenylamino)-9,9'-dimethyl-9H-fluorene-3-ol, 3.6 g of 2-bromo-1,3-difluorobenzene, 12.9 g of potassium carbonate, and 30 ml of NMP was heated and stirred at reflux for 5 hours under a nitrogen atmosphere. After the reaction was stopped, the reaction solution was cooled to room temperature, water was added, and the precipitate was collected by filtration. The precipitate was washed with water, then with methanol, and purified by silica gel column chromatography (elution: heptane / toluene mixed solvent) to obtain 12.6 g of 6,6'-((2-bromo-1,3-phenylene)bis(oxy))bis(9,9-dimethyl-N,N-diphenyl-9H-fluorene-2-amine). At this point, the ratio of toluene in the eluent was slowly increased to dissolve the target analyte.

[0296]

[0297] A flask containing intermediate 4 (25 g) and tetrahydrofuran (250 ml) was heated to 70 °C under a nitrogen atmosphere to completely dissolve intermediate 4. The flask was then immersed in an ice bath and cooled to 5 °C. A 1.28 M solution of the tetrahydrofuran complex of isopropyl magnesium chloride and lithium chloride (65 ml) was added. After heating to room temperature and stirring for 3 hours, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxapentylborane (15.4 g) was added, and the mixture was stirred at room temperature for 1 hour. 3% dilute hydrochloric acid (100 ml) and toluene (100 ml) were added, and the mixture was separated. The solvent in the organic layer was removed by vacuum distillation. The resulting solid was redissolved in toluene and passed through a silica gel column (eluent: toluene). After removing the solvent by distillation, the crude purified product was reprecipitated using tetrahydrofuran and Solmix A-11 to give the compound (19.6 g) of formula (1-3-386) as a white solid.

[0298]

[0299] The structure of the obtained compound was confirmed by NMR determination.

[0300] 1 H-NMR (400MHz, CDCl3): δ=7.49 (d, 2H), 7.30~7.22 (m, 13H), 7.17 (d, 2H), 7.13~7.11 (m, 8H), 7.03~6.99 (m, 6H), 6.93 (dd, 2H), 6.67 (d, 2H), 1.39 (s, 12H), 1.14 (s, 12H).

[0301] Synthesis Example (5): Synthesis of compound (1-3-439)

[0302]

[0303] A flask containing 1-bromo-2,6-difluorobenzene (62.5 g), 3-chlorophenol (100 g), potassium carbonate (179.2 g), and NMP (300 ml) was heated to 180 °C under a nitrogen atmosphere and stirred for 15 hours. After the reaction was complete, the potassium carbonate was separated by filtration, and the solvent in the filtrate was removed by vacuum distillation. Toluene and water were added to the obtained solid, and the organic layer was extracted. The organic layer was dried with anhydrous sodium sulfate and then passed through a silica gel short-pass column (eluent: toluene). After removing the solvent by vacuum distillation, the obtained solid was washed with heptane to give intermediate 5 (105.3 g) as a light pink solid.

[0304]

[0305] A 1.29 M tetrahydrofuran solution (68 mL) of the isopropyl magnesium chloride-lithium chloride complex was added to a flask containing intermediate 5 (30 g) and tetrahydrofuran (500 mL) under a nitrogen atmosphere at room temperature. After stirring for 2 hours, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxapentylborane (24.5 g) was added, and the mixture was stirred at room temperature for 2 hours. After the reaction was complete, 3% dilute hydrochloric acid (200 mL) and toluene (200 mL) were added to the reaction mixture, and the organic layer was extracted by separation. After removing the solvent by vacuum distillation, the resulting solid was dissolved in toluene and passed through a silica gel column (eluent: toluene). The solvent was removed by distillation, thus giving the compound (29.6 g) of formula (1-3-439) as a white solid.

[0306]

[0307] The structure of the obtained compound was confirmed by LC-MS determination. It should be noted that methanol was used as the solvent in the determination; therefore, the results yielded the mass of the adduct formed by the addition of methanol to the borate ester compound.

[0308] MS(ACPI)m / z=488(M+MeOH)

[0309] Synthesis Example (6): Synthesis of Compound (1-2-340)

[0310]

[0311] A flask containing 100 g of 7-(diphenylamino)-9,9'-dimethyl-9H-fluorene-3-ol, 58.3 g of 1-bromo-2-chloro-3-fluorobenzene, 91.5 g of potassium carbonate, and 500 ml of NMP was heated and stirred at reflux for 4 hours under a nitrogen atmosphere. After the reaction was stopped, the reaction solution was cooled to room temperature, water was added, and the precipitate was collected by filtration. The precipitate was washed with water, then with methanol, and purified by silica gel column chromatography (eluent: toluene) to give the intermediate compound 150 g of 6-(3-bromo-2-chlorophenoxy)-9,9-dimethyl-N,N-diphenyl-9H-fluorene-2-amine.

[0312]

[0313] A flask containing 40 g of 6-(3-bromo-2-chlorophenoxy)-9,9-dimethyl-N,N-diphenyl-9H-fluorene-2-amine, 12.5 g of diphenylamine, 1.5 g of bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloride as a palladium catalyst, 17.0 g of sodium tert-butoxide, and 200 ml of xylene was heated under a nitrogen atmosphere and stirred at 85 °C for 2 hours. After cooling the reaction solution to room temperature, water and toluene were added and the mixture was separated. The solvent in the organic layer was removed by vacuum distillation. The resulting solid was washed several times with Solmix A-11 (trade name: Japan Alcohol Trading Co., Ltd.) and then purified by silica gel column chromatography (eluent: toluene / heptane = 1 / 2 (volume ratio)) to give the compound represented by intermediate 6 (35.6 g).

[0314]

[0315] A flask containing intermediate 6 (18.9 g) and toluene (150 ml) was heated to 70 °C under a nitrogen atmosphere until completely dissolved. After cooling the flask to 0 °C, a 2.6 M solution of n-butyllithium in n-hexane (14.4 ml) was added. The mixture was heated to 65 °C and stirred for 3 hours. Then, the flask was cooled to -10 °C, and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxapentylborane (13.4 g) was added, and the mixture was stirred at room temperature for 2 hours. Water and toluene were added, and the mixture was separated. The organic layer was passed through a short NH2 silica gel column (eluent: toluene). After removing the solvent by vacuum distillation, the compound of formula (1-2-340) (22.0 g) was obtained.

[0316]

[0317] The structure of the obtained compound was confirmed by NMR determination.

[0318] 1 H-NMR (400MHz, CDCl3): δ=7.49 (d, 1H), 7.30~7.08 (m, 19H), 7.04~6.99 (m, 6H), 6.94 (dd, 1H), 6.77 (d, 1H), 6.73 (d, 1H), 1.39 (s, 6H), 0.93 (s, 12H).

[0319] Synthesis Example (7): Synthesis of Compound (1-2-343)

[0320]

[0321] A flask containing 6-(3-bromo-2-chlorophenoxy)-9,9-dimethyl-N,N-diphenyl-9H-fluorene-2-amine (60 g), bis(4-tert-butylphenyl)amine (29.8 g), bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloride (2.2 g) as a palladium catalyst, sodium tert-butoxide (25.4 g), and xylene (300 ml) was heated under a nitrogen atmosphere and stirred at 85 °C for 2 hours. After cooling the reaction solution to room temperature, water and toluene were added and the mixture was separated. The solvent in the organic layer was removed by vacuum distillation. The obtained solid was washed several times with Solmix A-11 (trade name: Japan Alcohol Trading Co., Ltd.) and then purified by silica gel column chromatography (elution: toluene) to give intermediate 7 (66.2 g).

[0322]

[0323] A flask containing intermediate 7 (2.5 g) and xylene (20 ml) was heated to 70 °C under a nitrogen atmosphere to completely dissolve the compound. After cooling the flask to 0 °C, a 2.6 M solution of n-butyllithium in n-hexane (3.1 ml) was added. The mixture was heated to 65 °C and stirred for 3 hours. Then, the flask was cooled to -10 °C, and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxapentylborane (3.0 g) was added. The mixture was stirred at room temperature for 2 hours. Water and toluene were added, and the mixture was separated, allowing the organic layer to pass through a short-pass column of NH2 silica gel (eluent: toluene). After removing the solvent by vacuum distillation, the compound of formula (1-2-343) (2.7 g) was obtained.

[0324]

[0325] The structure of the obtained compound was confirmed by NMR determination.

[0326] 1 H-NMR (400MHz, CDCl3): δ=7.49 (d, 1H), 7.29~7.10 (m, 15H), 7.01 (d, 8H), 6.93 (dd, 1H), 6.75 (d, 1H), 6.69 (d, 1H), 1.39 (s, 6H), 1.28 (s, 18H), 0.96 (s, 12H).

[0327] By appropriately modifying the compounds of the raw materials, other boric acids or borate esters of the present invention can be synthesized by the method according to the above-described synthesis examples.

[0328] Next, examples of polycyclic aromatic compounds made from boric acid or borate esters will be given.

[0329] [Example 1]

[0330] <Synthesis of polycyclic aromatic compound A using compound (1-1-98)>

[0331] A flask containing compound (1-1-98) (8.7 g), aluminum chloride (12.5 g), N,N-diisopropylethylamine (DIPEA) (6.0 g), and chlorobenzene (44 ml) was stirred at 120 °C for 1 hour under a nitrogen atmosphere. The reaction mixture, cooled to room temperature, was injected into ice water (200 ml), toluene was added, and the organic layer was extracted. The solvent in the organic layer was removed by vacuum distillation, and the resulting solid was dissolved in chloroform and passed through a short silica gel column (eluent: toluene). The crude purified product obtained by removing the solvent by vacuum distillation was reprecipitated with cyclopentylmethyl ether and Solmix A-11 to give polycyclic aromatic compound A (6.2 g, 70% yield) as a yellow solid.

[0332]

[0333] The structure of the obtained compound was confirmed by NMR determination.

[0334] 1 H-NMR (400MHz, CDCl3): δ = 8.95 (d, 2H), 7.45 (dd, 6H), 7.13 (d, 4H), 7.08-7.04 (m , 4H), 6.95-6.88(m, 6H), 6.75(d, 2H), 5.56(s, 2H), 1.46(s, 18H), 1.33(s, 18H).

[0335] [Example 2]

[0336] <Synthesis of polycyclic aromatic compound B using compound (1-3-139)>

[0337] A flask containing compound (1-3-139) (22.8 g), aluminum chloride (23.5 g), and chlorobenzene (230 ml) was stirred at 130 °C for 2 hours under a nitrogen atmosphere. The reaction mixture, cooled to room temperature, was injected into ice water (1 L) at 0 °C, toluene (500 ml) was added, and the organic layer was extracted. The solid obtained by removing the solvent from the organic layer by vacuum distillation was washed with Solmix A-11 (500 ml) to give polycyclic aromatic compound B (14.2 g, 60% yield) as a pale yellow solid.

[0338]

[0339] The structure of the obtained compound was confirmed by NMR determination.

[0340] 1 H-NMR (400MHz, CDCl3): δ=8.69 (dd, 2H), 7.79 (t, 1H), 7.70 (ddd, 2H), 7.54 (dt, 2H), 7.38 (ddd, 2H), 7.22 (d, 2H).

[0341] [Example 3]

[0342] <Synthesis of polycyclic aromatic compound C using compound (1-3-252)>

[0343] A flask containing compound (1-3-252) (124 g), aluminum chloride (131.3 g), and toluene (620 ml) was stirred at 90 °C for 1 hour under a nitrogen atmosphere. The reaction mixture, cooled to room temperature, was injected into an aqueous sodium acetate solution at 5 °C, and the organic layer was extracted. The crude product obtained by removing the solvent by vacuum distillation was reprecipitated with o-dichlorobenzene and ethyl acetate to give polycyclic aromatic compound C (91 g, yield 63%) as a yellow solid.

[0344]

[0345] The structure of the obtained compound was confirmed by NMR determination.

[0346] 1 H-NMR (400MHz, CDCl3): δ = 8.73 (d, 2H), 8.17 (d, 2H), 8.01 (d, 2H), 7.74 (m, 4 H), 7.60(d, 2H), 7.58(s, 2H), 7.53(d, 2H), 7.40-7.48(m, 4H), 7.32(t, 2H).

[0347] [Example 4]

[0348] <Synthesis of polycyclic aromatic compound D using compound (1-3-386)>

[0349] A flask containing compound (1-3-386) (32 g), aluminum chloride (44.7 g), N,N-dimethyl-p-toluidine (4.53 g), and toluene (170 ml) was stirred at 85 °C for 10 hours under a nitrogen atmosphere. The reaction mixture, cooled to room temperature, was injected into a 0.2 M aqueous solution of tetrasodium ethylenediaminetetraacetate (200 ml) at 0 °C. Toluene was added, and the organic layer was extracted. The solid obtained by removing the solvent from the organic layer by vacuum distillation was dissolved in chloroform and passed through a silica gel column (eluent: chloroform / heptane = 1 / 10 mixed solvent (volume ratio)). The crude purified product obtained by removing the solvent by vacuum distillation was washed with a mixed solvent of toluene and acetone and recrystallized using cyclopentylmethyl ether to give polycyclic aromatic compound D (24.9 g, yield 77%) as a yellow solid.

[0350]

[0351] The structure of the obtained polycyclic aromatic compound D was confirmed by NMR determination.

[0352] 1H-NMR (400MHz, CDCl3): δ=8.64 (s, 2H), 7.75 (m, 3H), 7.69 (d, 2H), 7.30 (t, 8H), 7.25 (s, 2H), 7.20 (m, 10H), 7.08 (m, 6H), 1.58 (s, 12H).

[0353] [Example 5]

[0354] <Synthesis of polycyclic aromatic compound E using compound (1-3-439)>

[0355] A flask containing compound (1-3-439) (29.5 g), aluminum chloride (25.8 g), and chlorobenzene (290 ml) was stirred at 110 °C for 2 hours under a nitrogen atmosphere. After the reaction was complete, the reaction mixture, cooled to room temperature, was injected into ice water (1 L) at 0 °C, toluene (500 ml) was added, and the organic layer was extracted. The solid obtained by removing the solvent from the organic layer by vacuum distillation was washed with Solmix A-11 (500 ml) to give polycyclic aromatic compound E (12.3 g, yield 41%) as a pale yellow solid.

[0356]

[0357] The structure of the obtained compound was confirmed by NMR determination.

[0358] 1 H-NMR (400MHz, CDCl3): δ=8.51 (dd, 2H), 7.81 (t, 1H), 7.56 (d, 2H), 7.36 (dd, 2H), 7.38 (m, 2H).

[0359] [Example 6]

[0360] <Synthesis of polycyclic aromatic compound F using compound (1-2-340)>

[0361] Aluminum chloride (19.2 g) and N,N-diisopropylethylamine (DIPEA) (3.7 g) were added to a flask containing compound (1-2-340) (21.5 g) and toluene (215 ml), and the mixture was refluxed for 3 hours. The reaction mixture, cooled to room temperature, was then injected into ice water (250 ml), toluene was added, and the organic layer was extracted. The solid obtained by removing the solvent from the organic layer by vacuum distillation was purified by short-column chromatography with NH2 silica gel (eluent: toluene / heptane = 1 / 4 (volume ratio)), followed by several reprecipitations with methanol. The crude product was purified by short-column chromatography with silica gel (eluent: toluene / heptane = 1 / 2 (volume ratio)) to give polycyclic aromatic compound F (15.5 g, yield 71%) as a yellow solid.

[0362]

[0363] The structure of the obtained compound was confirmed by NMR determination.

[0364] 1 H-NMR (400MHz, CDCl3): δ = 8.94 (dd, 1H), 8.70 (s, 1H), 7.74~7.69 (m, 4H), 7.62 (t, 1H), 7.53~7.47 (m, 2H), 7.38 (d d, 2H), 7.33~7.28 (m, 5H), 7.24 (d, 1H), 7.18 (dd, 4H), 7.09~7.05 (m, 4H), 6.80 (d, 1H), 6.30 (d, 1H), 1.58 (s, 6H).

[0365] [Comparative Example 1]

[0366] <Synthesis of polycyclic aromatic compound D using the precursor bromide and boron tribromide>

[0367] Under a nitrogen atmosphere, a flask containing intermediate 4 (11.0 g) of the bromide precursor and xylene (60.5 ml) was cooled to -40 °C, and 5.1 ml of a 2.6 M n-butyllithium hexane solution was added dropwise. After the addition was complete, the mixture was stirred at this temperature for 0.5 hours, then heated to 60 °C and stirred for 3 hours. The reaction mixture was then subjected to reduced pressure, distilled to remove low-boiling components, and cooled to -40 °C. Boron tribromide (4.3 g) was added. The mixture was heated to room temperature and stirred for 0.5 hours, then cooled to 0 °C, and N,N-diisopropylethylamine (3.8 g) was added. The mixture was heated and stirred at 125 °C for 8 hours. The reaction mixture was cooled to room temperature, and an aqueous sodium acetate solution was added to stop the reaction. Toluene was then added, and the mixture was separated. The organic layer was purified by short silica gel column chromatography, followed by silica gel column chromatography (eluent: heptane / toluene = 4 / 1 mixed solvent (volume ratio)), and further purified by activated carbon column chromatography (eluent: toluene) to obtain polycyclic aromatic compound D (1.2 g, yield 12%).

[0368]

[0369] [Comparative Example 2]

[0370] <Synthesis of polycyclic aromatic compound F using precursor chloride and boron tribromide>

[0371] A flask containing intermediate 6 (5.0 g) as a precursor chloride and xylene (100 ml) was cooled to -40 °C under a nitrogen atmosphere, and 9.3 ml of 2.6 M sec-butyllithium hexane solution was added dropwise. After the addition was complete, the mixture was stirred at this temperature for 0.5 hours, then heated to 60 °C and stirred for 3 hours. The reaction mixture was then subjected to reduced pressure, distilled to remove low-boiling components, and cooled to -40 °C. Boron tribromide (7.1 g) was added. The mixture was heated to room temperature and stirred for 0.5 hours, then cooled to 0 °C, and N,N-diisopropylethylamine (2.6 g) was added. The mixture was heated and stirred at 125 °C for 8 hours. The reaction mixture was cooled to room temperature, and an aqueous sodium acetate solution was added to stop the reaction. Toluene was then added, and the mixture was separated. The organic layer was purified by short-pass silica gel column chromatography, followed by silica gel column chromatography (eluent: heptane / toluene = 4 / 1 mixed solvent (volume ratio)), and further purified by activated carbon column chromatography (eluent: toluene) to obtain polycyclic aromatic compound F (0.8 g, yield 16%).

[0372]

[0373] The results of Examples 1 to 6 and Comparative Examples 1 to 2 are shown together in Table 1.

[0374] Table 1

[0375]

[0376] Industrial availability

[0377] The boric acid or borate ester of the present invention exhibits extremely high stability, thus avoiding problems arising from high reactivity even in reactions with acids, and preventing yield reduction during scaling up. Furthermore, the highly stable boric acid or borate ester is easily separated and purified, enabling the product to be obtained with high selectivity. Consequently, it is easier to obtain polycyclic aromatic compounds as materials for organic EL elements with high purity and high yield.

Claims

1. A compound represented by the following general formula (1), or a plurality of polymeric compounds having the structure represented by the following general formula (1), In the above formula (1), Rings A, B, and C are independently aromatic rings having 6 to 16 carbon atoms, wherein at least one hydrogen atom in these rings is optionally substituted with a diarylamino group, an alkyl group having 1 to 6 carbon atoms, or a halogen, wherein the aryl group in the diarylamino group is an aryl group having 6 to 16 carbon atoms. Y 1 It is boric acid-B(OH)2 or borate ester. X 1 and X 2 They are independently -O-, >N-Ar, or -S-, where, X 1 and X 2 Both are not -O-. Here, the Ar in the >N-Ar group is an aryl group with 6 to 16 carbon atoms, and at least one hydrogen atom in the aryl group is optionally substituted with an alkyl group or a halogen with 1 to 6 carbon atoms. At least one hydrogen atom in the compound or structure shown in formula (1) may optionally be replaced by deuterium.

2. The compound or polymer compound according to claim 1, wherein, Rings A, B, and C are independently aromatic rings having 6 to 16 carbon atoms, wherein at least one hydrogen atom in these rings is optionally substituted with a diarylamino group, an alkyl group having 1 to 6 carbon atoms, or a halogen, wherein the aryl group in the diarylamino group is an aryl group having 6 to 12 carbon atoms. Y 1 It is a borate ester. X 1 and X 2 Independently, they are -O-, >N-Ar, or -S-, where X 1 and X 2 Both are not -O-. Here, the Ar in >N-Ar is an aryl group with 6 to 10 carbon atoms, and at least one hydrogen atom in the aryl group is optionally replaced by an alkyl group with 1 to 6 carbon atoms or a halogen. At least one hydrogen atom in the compound or structure shown in formula (1) may optionally be substituted with deuterium, and, The polymeric compound is a dimer or a trimer.

3. A compound represented by the following general formula (2), or a polymeric compound having a plurality of structures represented by the following general formula (2), In the above formula (2), R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 and R 11 Each of the following is independently hydrogen, a diarylamino group, an alkyl group having 1 to 6 carbon atoms, or a halogen, wherein, In diarylamino compounds, the aryl group is an aryl group with 6 to 16 carbon atoms. Y 1 It is boric acid-B(OH)2 or borate ester. X 1 and X 2 Independently, they are -O-, >N-Ar, or -S-, where X 1 and X 2 Both are not -O-, where the Ar of >N-Ar is an aryl group with 6 to 12 carbon atoms, and at least one hydrogen atom in the aryl group is optionally substituted with a halogen, and, At least one hydrogen atom in the compound or structure shown in formula (2) may optionally be substituted with deuterium, and, The polymeric compound is a dimer or a trimer.

4. The compound or polymer compound according to claim 3, wherein, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 and R 11 Each of them can be hydrogen, diarylamino, or halogen, wherein the aryl group in the diarylamino group is an aryl group with 6 to 12 carbon atoms. Y 1 It is a borate ester. X 1 and X 2 Independently, they are -O-, >N-Ar, or -S-, where X 1 and X 2 Both are not -O-, where the Ar of >N-Ar is an aryl group with 6 to 10 carbon atoms, and at least one hydrogen atom in the aryl group is optionally substituted with a halogen, and, At least one hydrogen atom in the compound or structure shown in formula (2) may optionally be substituted with deuterium, and, The polymeric compound is a dimer or a trimer.

5. A compound represented by the following formula (1-1-98), In the formula, Bpin is a group obtained by esterifying -B(OH)2pinaol, and tBu is tert-butyl.

6. Compounds represented by formula (1-2-340) or formula (1-2-343) below, In the formula, Bpin is the group obtained by esterifying -B(OH)2pinaol, Me is methyl, and tBu is tert-butyl.

7. A manufacturing method, wherein, By reacting an acid with a compound of the following general formula (1) or a polymeric compound having a plurality of structures shown in the following general formula (1), a polycyclic aromatic compound of the following general formula (3) or a polycyclic aromatic polymeric compound having a plurality of structures shown in the following general formula (3) is produced. In equations (1) and (3), Rings A, B, and C are independently aromatic rings having 6 to 16 carbon atoms, wherein at least one hydrogen atom in these rings is optionally substituted with a diarylamino group, an alkyl group having 1 to 6 carbon atoms, or a halogen, wherein the aryl group in the diarylamino group is an aryl group having 6 to 16 carbon atoms. Y 1 It is boric acid-B(OH)2 or borate ester. X 1 and X 2 Each is independently -O-, >N-Ar, or -S-, where the Ar in >N-Ar is an aryl group having 6 to 16 carbon atoms, and at least one hydrogen atom in the aryl group is optionally substituted with an alkyl group having 1 to 6 carbon atoms or a halogen. At least one hydrogen atom in the compound or structure shown in formula (1) and the compound or structure shown in formula (3) may be optionally substituted with deuterium.

8. The manufacturing method according to claim 7, wherein, In equations (1) and (3), Rings A, B, and C are independently aromatic rings having 6 to 16 carbon atoms, wherein at least one hydrogen atom in these rings is optionally substituted with a diarylamino group, an alkyl group having 1 to 6 carbon atoms, or a halogen, wherein the aryl group in the diarylamino group is an aryl group having 6 to 12 carbon atoms. Y 1 It is a borate ester. X 1 and X 2 They are independently -O-, >N-Ar, or -S-, where the Ar in >N-Ar is an aryl group having 6 to 10 carbon atoms, and at least one hydrogen atom in the aryl group is optionally substituted with an alkyl group having 1 to 6 carbon atoms or a halogen. In the compound or structure shown in formula (1) and the compound or structure shown in formula (3), at least one hydrogen atom is optionally substituted with deuterium, and, The polymeric compounds and polycyclic aromatic polymeric compounds are dimeric or trimeric compounds.

9. A manufacturing method, wherein, By reacting an acid with a compound of the following general formula (2) or a polymeric compound having a plurality of structures shown in the following general formula (2), a polycyclic aromatic compound of the following general formula (4) or a polycyclic aromatic polymeric compound having a plurality of structures shown in the following general formula (4) is produced. In equations (2) and (4), R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 and R 11 Each of the following is independently hydrogen, a diarylamino group, an alkyl group having 1 to 6 carbon atoms, or a halogen, wherein the aryl group in the diarylamino group is an aryl group having 6 to 16 carbon atoms. Y 1 It is boric acid-B(OH)2 or borate ester. X 1 and X 2 They are independently -O-, >N-Ar, or -S-, where the Ar in >N-Ar is an aryl group having 6 to 12 carbon atoms, and at least one hydrogen atom in the aryl group is optionally substituted with a halogen. In the compound or structure shown in formula (2) and the compound or structure shown in formula (4), at least one hydrogen atom is optionally substituted with deuterium, and, The polymeric compounds and polycyclic aromatic polymeric compounds are dimeric or trimeric compounds.

10. The manufacturing method according to claim 9, wherein, In equations (2) and (4), R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 and R 11 Each of them can be hydrogen, diarylamino, or halogen, wherein the aryl group in the diarylamino group is an aryl group with 6 to 12 carbon atoms. Y 1 It is a borate ester. X 1 and X 2 They are independently -O-, >N-Ar, or -S-, where the Ar in >N-Ar is an aryl group having 6 to 10 carbon atoms, and at least one hydrogen atom in the aryl group is optionally substituted with a halogen. In the compound or structure shown in formula (2) and the compound or structure shown in formula (4), at least one hydrogen atom is optionally substituted with deuterium, and, The polymeric compounds and polycyclic aromatic polymeric compounds are dimeric or trimeric compounds.

11. A method for producing a polycyclic aromatic compound by reacting an acid with any of the compounds represented by the following formulas. In the formula, Bpin is the group obtained by esterifying -B(OH)2pinaol, Me is methyl, and tBu is tert-butyl.

12. Use of the compound or polymer of any one of claims 1 to 4, or the compound of claim 5 or 6, for the manufacture of a polycyclic aromatic compound or a polycyclic aromatic polymer, wherein the polycyclic aromatic compound or polycyclic aromatic polymer is selected from the polycyclic aromatic compound of general formula (3) of claim 7 or a polycyclic aromatic polymer having a plurality of structures shown in general formula (3) or the polycyclic aromatic compound of general formula (4) of claim 9 or a polycyclic aromatic polymer having a plurality of structures shown in general formula (4). in, In equations (1) and (2), X is included. 1 and X 2 The case where both are -O-.

Images