JP2019119722A - Method for manufacturing compound - Google Patents

Abstract

To find a reaction condition for effectively introducing a substituent bound by a sp2 carbon atom instead of a hydrogen atom of an aromatic ring, and to effectively manufacture a compound in which the substituent bound by the sp2 carbon atom binds at a target position of the aromatic ring.SOLUTION: A compound represented by the general formula (3) is manufactured by reacting a compound represented by the general formula (1) and a compound represented by the general formula (2) in the presence of a copper catalyst of 0.3 equivalent or more of the compound represented by the general formula (2). A, Aand Arepresent C(R) or N, Rrepresents C(R)(R) or N(R), Rrepresents C(R)(R)(R) or N(R)(R), Rto Rrepresent a hydrogen atom or a substituent, and X represents a halogen atom or a leaving group.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a compound by introducing a substituent bonded to an aromatic ring via an sp2 carbon atom.

Compounds having a structure in which a substituent bonded to an sp 2 carbon atom such as an aryl group is bonded to an aromatic ring have a variety of optical functions due to the π conjugated system extending over the aromatic ring of the core and the substituent. It has an electronic function, and its application is widespread in various fields such as organic light emitting elements, organic semiconductors, and organic solar cells. Therefore, many studies have been conducted so far for the purpose of efficiently producing such compounds at low cost, and in particular, a reaction for introducing a substituent that is bonded by an sp2 carbon atom instead of a hydrogen atom of an aromatic ring. Since it is advantageous for reduction of the number of manufacturing processes and environmental load reduction, research is actively advanced.
For example, Patent Document 1 discloses C—H of the benzene ring by reacting benzene substituted with a plurality of fluorine atoms with aryl halide (aryl bromide or aryl iodide) in the presence of a copper catalyst. Described is a method of substituting a hydrogen atom (H) of a bond with an aryl group. Here, copper (I) iodide is used as a copper catalyst, and the copper (I) iodide is used in a concentration of 0.1 mmol per 1 mmol of aryl halide (0.1 per 1 equivalent of aryl halide). It is stated that the reaction was carried out in the presence of equivalent amounts).

US Patent Publication 2009/0076266

  As described above, Patent Document 1 discloses that when benzene substituted with a plurality of fluorine atoms is reacted with a halogenated aryl group to introduce an aryl group into a benzene ring, 0.1 to 1 equivalent of halogenated aryl is used. The presence of an equivalent amount of copper (I) iodide is described. However, the present inventors present 0.1 equivalent or 0.2 equivalents of copper (I) iodide to one equivalent of the halogenated aryl or the halogenated heteroaryl, and the aromatic ring is a plurality of fluorine atoms. When various substituted aromatic compounds are reacted with various aryl halides or heteroaryl heteroaryls, the reaction hardly progresses depending on the combination thereof, and compounds which can be synthesized under the conditions described in reference 1 It turned out that the structure would be limited.

  Therefore, in order to solve the problems of the prior art, the present inventors aim to find reaction conditions under which a substituent bonded with an sp2 carbon atom is efficiently introduced instead of a hydrogen atom of an aromatic ring. Repeated research. Then, investigations were advanced for the purpose of providing a method capable of efficiently producing a compound in which a substituent bonded to an sp 2 carbon atom is bonded to a target position of an aromatic ring.

  As a result of intensive studies to solve the above problems, the present inventors have found that compounds comprising a six-membered aromatic ring in which at least two fluorine atoms are bonded to each other at the meta position, a halogen atom or a When reacting a compound having a structure having a leaving group attached, in the presence of 0.3 equivalent or more of a copper catalyst with respect to 1 equivalent of the latter compound, between two fluorine atoms bonded to a six-membered aromatic ring We have found that the hydrogen atom (H) of CH is selectively and efficiently substituted by the sp2 carbon atom-derived substituent derived from the latter compound and that the desired compound is efficiently synthesized. . The present invention has been proposed based on such findings, and specifically has the following configurations.

［上式において、Ａ^１、Ａ^２およびＡ^３は、各々独立にＣ（Ｒ^３）またはＮを表し、Ｒ^１は、Ｃ（Ｒ^４）（Ｒ^５）またはＮ（Ｒ^６）を表し、Ｒ^２は、Ｃ（Ｒ^７）（Ｒ^８）（Ｒ^９）またはＮ（Ｒ^１０）（Ｒ^１１）を表し、Ｒ^３〜Ｒ^１１は各々独立に水素原子または置換基を表し、Ｘはハロゲン原子または脱離基を表す。Ｒ^１とＲ^２は互いに結合して環状構造を形成していてもよい。また、Ａ^１、Ａ^２およびＡ^３のうちの２つ以上がＣ（Ｒ^３）を表すとき、２つ以上のＲ^３は互いに結合して環状構造を形成していてもよい。］
［２］ 前記一般式（２）で表される化合物が、置換もしくは無置換の３−ピリジルハライド、または、置換もしくは無置換の４−ピリジルハライドである、［１］に記載の方法。
［３］ 前記一般式（２）のＲ^１とＲ^２が互いに結合して、環骨格構成原子としてヘテロ原子を２つ以上含む環状構造を形成している、［１］に記載の方法。
［４］ 前記一般式（２）のＲ^１とＲ^２が互いに結合して環状構造を形成しており、前記環状構造が２つ以上のアリール基で置換されている、［１］〜［３］のいずれか１項に記載の方法。
［５］ 前記環状構造が、環骨格構成原子としてヘテロ原子を含む、［４］に記載の方法。
［６］ 前記一般式（１）のＡ^１、Ａ^２およびＡ^３のすべてが各々独立にＣ（Ｒ^３）であるか、あるいは、Ａ^１、Ａ^２およびＡ^３の２つが各々独立にＣ（Ｒ^３）であり、残りの１つがＮである、［１］に記載の方法。
［７］ 前記一般式（１）が下記のいずれかの条件を満たす、［１］に記載の方法。
＜１＞ Ａ^１およびＡ^３がＣＦであり、Ａ^２がＣＨである。
＜２＞ Ａ^２がＣＦであり、Ａ^１がＣＨであり、Ａ^３がＣ（Ｒ^３）であり、がＲ^３が置換基である。
＜３＞ Ａ^２がＣＦであり、Ａ^１およびＡ^３がＣＨである。
［８］ 前記一般式（１）のＡ^１〜Ａ^３のうちの１つまたは２つがＣＨであり、残りがＣＦであって、前記一般式（２）のＲ^１とＲ^２が互いに結合して環骨格構成原子としてヘテロ原子を含む環状構造を形成している、［１］に記載の方法。 [1] A copper catalyst containing 0.3 equivalent or more of a compound represented by the following general formula (2) and a compound represented by the following general formula (2) The method to manufacture the compound represented by General formula (3) by making it react in presence.

[Wherein, A ¹ , A ² and A ³ each independently represent C (R ³ ) or N, and R ¹ represents C (R ⁴ ) (R ⁵ ) or N (R ⁶ ), R ² represents C (R ⁷ ) (R ⁸ ) (R ⁹ ) or N (R ¹⁰ ) (R ¹¹ ), R ^{3 to} R ¹¹ each independently represent a hydrogen atom or a substituent, and X is a halogen Represents an atom or a leaving group. R ¹ and R ² may be bonded to each other to form a cyclic structure. Also, when two or more of A ¹ , A ² and A ³ represent C (R ³ ), two or more R ³ may be bonded to each other to form a cyclic structure. ]
[2] The method according to [1], wherein the compound represented by the general formula (2) is a substituted or unsubstituted 3-pyridyl halide or a substituted or unsubstituted 4-pyridyl halide.
[3] The method according to [1], wherein R ¹ and R ^{2 in} the general formula (2) are bonded to each other to form a cyclic structure containing two or more hetero atoms as ring skeleton constituent atoms.
[4] [1] to [3], wherein R ¹ and R ^{2 in} the general formula (2) are bonded to each other to form a cyclic structure, and the cyclic structure is substituted with two or more aryl groups, The method according to any one of the above.
[5] The method according to [4], wherein the cyclic structure contains a hetero atom as a ring skeleton constituent atom.
[6] All of A ¹ , A ² and A ^{3 in} the general formula (1) are each independently C (R ³ ), or ^{two of} A ¹ , A ² and A ³ are each independently C The method according to [1], wherein (R ³ ) and the remaining one is N.
[7] The method according to [1], wherein the general formula (1) satisfies any of the following conditions.
<1> A ¹ and A ³ are CF and A ² is CH.
<2> A ² is CF, A ¹ is CH, A ³ is C (R ³ ), and R ³ is a substituent.
<3> A ² is CF, and A ¹ and A ³ are CH.
[8] One or two of A ^{1 to} A ^{3 in} the general formula (1) are CH, and the remainder is CF, and R ¹ and R ^{2 in} the general formula (2) are bonded to each other The method according to [1], wherein the cyclic structure contains a hetero atom as a ring skeleton constituent atom.

  According to the method of the present invention, a hydrogen atom of an aromatic ring can be replaced with a substituent bonded with an sp2 carbon atom efficiently, and a substituent bonded with an sp2 carbon atom is bonded to a target position of an aromatic ring The compound can be efficiently produced.

Hereinafter, the present invention will be described in detail. The description of the configuration requirements described below may be made based on typical embodiments and specific examples, but the present invention is not limited to such embodiments. In addition, the numerical range represented using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. Also, the isotope species of the hydrogen atom present in the molecule of the compound used in the present invention is not particularly limited. For example, all hydrogen atoms in the molecule may be ¹ H, or some or all of the hydrogen atoms may be ² H (Deuterium D) may be used.

<Method for producing a compound>
In the method of producing the compound of the present invention, the compound represented by the following general formula (1) and the compound represented by the following general formula (2) are each prepared by using 0. It is a method of producing the compound represented by General formula (3) by making it react in presence of 3 equivalent or more of copper catalysts.

The "equivalent weight" in the present invention is a value when the compound represented by the general formula (2) is made 1 equivalent. Thus, for example, when the compound represented by the general formula (2) is A equivalent (A is a positive number), a copper catalyst of 0.3 times or more the equivalent of A is present, and the general formula is The compound represented by (1) is reacted with the compound represented by the general formula (2).
In the conventional method of introducing an aryl group into an aromatic ring, the reaction was carried out in the presence of 0.1 equivalent of a copper catalyst per 1 equivalent of aryl halide, whereas in the present invention, 1 equivalent of a general catalyst was used. The reaction is carried out in the presence of 0.3 equivalent or more of a copper catalyst relative to the compound represented by the formula (2). Thereby, in the compound represented by the general formula (1), the hydrogen atom (H) of CH between two fluorine atoms bonded to the aromatic ring is a compound represented by the general formula (2) It is possible to obtain the desired compound represented by the general formula (3) which is selectively and efficiently substituted by the derived substituent attached to the sp2 carbon atom.
Although the reaction mechanism is not clear, the copper catalyst, which is present in a much larger amount than the conventional amount used, effectively acts to C—C between two fluorine atoms bonded to the aromatic ring. As a result of selectively activating the H bond, the C—H bond is cleaved, and the atomic group after X of the compound represented by the general formula (2) is eliminated at the carbon atom (C) It is presumed that (the substituent derived from the compound represented by the general formula (2)) is bonded to the sp2 carbon atom to synthesize the compound represented by the general formula (3).
When A ² in the general formula (1) is CH or when at least one of A ¹ and A ³ is CH, the remaining A ^{1 to} A ³ is selected depending on the selection of the remaining A ^{1 to} A ³ groups. Instead of the hydrogen atom (H), a substituent derived from the compound represented by the general formula (2) can also be introduced.
In the following, each compound, copper catalyst and reaction conditions used in the present invention will be described in detail.

[Each compound represented by formulas (1) to (3)]
First, each compound represented by General Formula (1)-(3) is demonstrated.
In formulas (1) and (3), each of A ¹ , A ² and A ³ independently represents C (R ³ ) or N, and R ³ represents a hydrogen atom or a substituent. Between the general formula (1) and the general formula (3), A ¹ , A ² and A ³ are preferably identical to each other except in a specific case. In a specific case, at least one of A ¹ , A ² and A ^{3 in} the general formula (1) is CH and the hydrogen atom (H) thereof is obtained by the reaction with a compound represented by the general formula (2) There refers to a case where substituted with a substituent derived from a compound represented by the general formula (2), has become a ^1, a ² or a ³ in the general formula (3).

In each of the general formulas (1) and (3), all of A ¹ , A ² and A ³ may be C (R ³ ) or all may be N, A ¹ , A ² and A one of ³ or two a C (R ³⁾ may be a remainder N. Among them, preferred is that all of A ¹ , A ² and A ³ are C (R ³ ), or ^{two of} A ¹ , A ² and A ³ are C (R ³ ) Is one where N is N. Here, when two or more of A ¹ , A ² and A ³ represent C (R ³ ), the two or more R ³ may be identical to or different from each other.
R ³ is not particularly limited as long as it is a hydrogen atom or a substituent, and preferred as R ^{3 in the} general formula (1) are a hydrogen atom, deuterium, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, It is an aryl group such as a phenyl group or a naphthyl group, an alkyl group such as a methyl group, an alkoxy group such as a methoxy group, more preferably a fluorine atom, a bromine atom, a cyano group or a phenyl group, and a fluorine atom More preferable. With regard to those preferred as R ^{3 in the} general formula (3), preferred examples of R ^{3 in} the general formula (1) can be referred to, and in addition, in the general formula (2) introduced in the above specific case The substituent derived from the compound represented is mentioned. Of the specific examples of R ³ , those which can be further substituted by a substituent may be substituted.

Also, when two or more of A ¹ , A ² and A ³ represent C (R ³ ), two or more R ³ may be bonded to each other to form a cyclic structure. With regard to the preferred range and specific examples of the cyclic structure formed by bonding two or more R ³ to each other, the preferred range and specific examples of the cyclic structure formed by combining R ¹ and R ² can be referred to .

In the general formulas (2) and (3), R ¹ represents C (R ⁴ ) (R ⁵ ) or N (R ⁶ ), and R ² represents C (R ⁷ ) (R ⁸ ) (R ⁹ ) Or N (R ¹⁰ ) (R ¹¹ ), and R ^{4 to} R ¹¹ each independently represent a hydrogen atom or a substituent. Preferably, R ¹ and R ² are the same between the general formula (2) and the general formula (3).

When R ¹ is C (R ⁴ ) (R ⁵ ) in each of the general formulas (2) and (3), R ² is C (R ⁷ ) (R ⁸ ) (R ⁹ ) and N (R) ¹⁰ ) Any of (R ¹¹ ) may be used. When R ¹ is C (R ⁴ ) (R ⁵ ) and R ² is C (R ⁷ ) (R ⁸ ) (R ⁹ ), R ⁴ , R ⁵ and R ^{7 to} R ⁹ are identical to each other And may be different. The number of substituents among R ⁴ , R ⁵ and R ^{7 to} R ⁹ is not particularly limited, and all may be substituents or all may be hydrogen atoms, and some may be substituents The rest may be a hydrogen atom. When R ¹ is C (R ⁴ ) (R ⁵ ) and R ² is N (R ¹⁰ ) (R ¹¹ ), R ⁴ , R ⁵ , R ¹⁰ and R ¹¹ are identical to each other and are different It may be The number of substituents among R ⁴ , R ⁵ , R ¹⁰ and R ¹¹ is not particularly limited, and all may be substituents or all may be hydrogen atoms, and some may be substituents The rest may be a hydrogen atom.

In each of the general formulas (2) and (3), when R ¹ is N (R ⁶ ), R ² is C (R ⁷ ) (R ⁸ ) (R ⁹ ) and N (R ¹⁰ ) (R ¹¹ ) may be used. When R ¹ is N (R ⁶ ) and R ² is C (R ⁷ ) (R ⁸ ) (R ⁹ ), R ^{6 to} R ⁹ may be identical to or different from each other. The number of substituents among R ^{6 to} R ⁹ is not particularly limited, and all may be substituents or all may be hydrogen atoms, a part is a substituent and the rest is a hydrogen atom. It may be. When R ¹ is N (R ⁶ ) and R ² is N (R ¹⁰ ) (R ¹¹ ), R ⁶ , R ¹⁰ and R ¹¹ may be identical to or different from each other. The number of substituents among R ⁶ , R ¹⁰ and R ¹¹ is not particularly limited, and all may be substituents or all may be hydrogen atoms, and some are substituents and the remainder is It may be a hydrogen atom.

R ^{4 to} R ¹¹ are not particularly limited as long as they are hydrogen atoms or substituents. Preferred examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, and 2 to 10 carbon atoms. The alkenyl group, a C2-C10 alkynyl group, a C1-C10 haloalkyl group, a C7-C40 aralkyl group etc. can be mentioned. Among these specific examples, those which can be further substituted by a substituent may be substituted.

Further, R ¹ and R ² may be bonded to each other to form a cyclic structure. The cyclic structure may be an aromatic ring or an unsaturated alicyclic ring, and may contain a hetero atom as a ring skeleton constituent atom, and the cyclic structure is a condensed ring of two or more rings. It is also good. The hetero atom as referred to herein is preferably selected from the group consisting of nitrogen atom, oxygen atom and sulfur atom. Examples of the cyclic structure formed include benzene ring, naphthalene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, pyrrol ring, imidazole ring, imidazole ring, pyrazole ring, triazole ring, imidazoline ring, oxazole ring, isoxazole And rings, thiazole ring, isothiazole ring, benzoxazole ring, benzimidazole ring, cyclohexadiene ring, cyclohexene ring, cyclopentaene ring, cycloheptatriene ring, cycloheptadiene ring, cycloheptaene ring and the like. These cyclic structures may be substituted by a substituent. Preferred range and specific examples of the substituents may be reference to the preferred examples of the substituents R ¹¹ to R ¹⁵ described below can be taken.

In the general formula (2), X represents a halogen atom or a leaving group. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be mentioned, and a bromine atom and an iodine atom are preferable. It not particularly limited as leaving groups, but a trifluoromethanesulfonyloxy group (OTf group: _OSO 2 CF _3), and the like.

The above general formula (1) preferably satisfies any one of the following conditions.
<1> A ¹ and A ³ are CF and A ² is CH.
<2> A ² is CF, A ¹ is CH, A ³ is C (R ³ ), and R ³ is a substituent.
<3> A ² is CF, and A ¹ and A ³ are CH.
When General Formula (1) satisfies the condition <1>, as General Formula (1), as a hydrogen atom (H) of CH between two fluorine atoms bonded to an aromatic ring, and A ² The hydrogen atom (H) of CH may be substituted with a substituent derived from the compound represented by the general formula (2). As a result, it is possible to obtain a compound represented by the general formula (3) in which the substituents are introduced at two places.
When General Formula (1) satisfies the condition of <2>, as General Formula (1), a hydrogen atom (H) of CH between two fluorine atoms bonded to an aromatic ring, and A ¹ The hydrogen atom (H) of CH may be substituted with a substituent derived from the compound represented by the general formula (2). As a result, it is possible to obtain a compound represented by the general formula (3) in which the substituents are introduced at two places.
At this time, a compound in which a substituent is introduced only at one site may occur as a by-product, but by controlling the reaction conditions, a compound in which a substituent is introduced at two sites can be obtained in higher yield. be able to.
Further, when General Formula (1) satisfies the condition of <3>, in General Formula (1), a hydrogen atom (H) of CH between two fluorine atoms bonded to an aromatic ring, and A The hydrogen atom (H) of each CH as ¹ and A ³ may be substituted by a substituent derived from the compound represented by the general formula (2). As a result, it is possible to obtain a compound represented by the general formula (3) in which the substituent is introduced at three points.

The compound represented by the general formula (2) is preferably a compound in which R ¹ and R ² are bonded to each other to form a pyridine ring, and X is a halogen atom. It is more preferable that it is a pyridyl halide or a substituted or unsubstituted 4-pyridyl halide.
Further, the compound represented by the general formula (2) has a cyclic structure formed by bonding R ¹ and R ² to each other, and the cyclic structure has two hetero atoms as a ring skeleton constituent atom. It is also preferable to include one or more, and it is more preferable that the cyclic structure contains two or more nitrogen atoms as ring skeleton constituent atoms.
Furthermore, the compound represented by the general formula (2) has a cyclic structure formed by bonding R ¹ and R ² to each other, and the cyclic structure is substituted with two or more aryl groups. It is also preferable that the cyclic structure substituted by two or more aryl groups contain a hetero atom as a ring skeleton constituent atom.

Further, as a preferable combination of the compound represented by the general formula (1) and the compound represented by the general formula (2), one or two of A ^{1 to} A ^{3 in} the general formula (1) are CH The case where the rest is CF and R ¹ and R ^{2 in} the general formula (2) are bonded to each other to form a cyclic structure containing a hetero atom as a ring skeleton constituent atom can be mentioned.

  Below, the specific example of a compound represented by General formula (1) is illustrated. However, the compounds represented by the general formula (1) which can be used in the present invention should not be construed as being limited by these specific examples.

Next, specific examples of the compound represented by the general formula (2) will be illustrated. However, the compounds represented by the general formula (2) which can be used in the present invention should not be construed as being limited by these specific examples. In the following formulas, R ^{11 to} R ¹⁵ each independently represent a hydrogen atom or a substituent. The substituent represented by R ^{11 to} R ¹⁵ is not particularly limited, but preferred examples thereof include an alkyl group such as methyl group, an alkoxy group such as methoxy group, an aryl group such as phenyl group and naphthyl group, cyano group, trifluoromethyl group And halogenated alkyl groups such as carbazolyl group and phenylcarbazolyl group. L represents a single bond or a divalent linking group. The divalent linking group is not particularly limited, and examples thereof include a divalent aromatic ring group such as a phenylene group, a naphthalenediyl group, a biphenyldiyl group, a dibenzofuranyl group, and a thiophenediyl group. X represents a halogen atom or a leaving group. For specific examples of the halogen atom and the leaving group, reference can be made to the specific examples of X in General Formula (2).

  Next, specific examples of the compound represented by the general formula (3) are illustrated. However, the compounds represented by the general formula (3) to be produced in the present invention should not be construed as being limited by these specific examples. In the following formula, Ph represents a phenyl group.

[Reaction conditions]
In the present invention, the compound represented by the general formula (1) as described above and the compound represented by the general formula (2) are 0.3 equivalent or more copper of the compound represented by the general formula (2) The compound represented by general formula (3) is produced by reacting in the presence of a catalyst.

(Supply amount of compound represented by general formula (1) and compound represented by general formula (2))
In the amount of the compound represented by the general formula (1) to be subjected to the reaction, how many molecules of the compound represented by the general formula (2) do you want to react with one molecule of the compound represented by the general formula (1)? It is preferable to change depending on When it is desired to react one molecule of the compound represented by the general formula (2) to one molecule of the compound represented by the general formula (1), the compound represented by one equivalent of the compound represented by the general formula (2) The amount of the compound represented by the general formula (1) is preferably 1 to 5.5 equivalents, more preferably 1.5 to 4 equivalents, and 2 to 3.5 equivalents. More preferable. When it is desired to react a compound represented by the general formula (2) of n molecules (n is an integer of 2 or more) with one molecule of the compound represented by the general formula (1), It is preferable to set it as equivalent. That is, the amount of the compound represented by the general formula (1) is preferably 1 / n equivalent to 5.5 / n equivalent to 1 equivalent of the compound represented by the general formula (2), 1 More preferably, it is from 5 / n equivalent to 4 / n equivalent, more preferably from 2 / n equivalent to 3.5 / n equivalent.

(Copper catalyst)
The "copper catalyst" in the present invention means a catalyst containing copper. As a copper catalyst, a cuprous salt, a cupric salt, a copper complex etc. can be mentioned, It is preferable to use a cuprous salt. Copper (I) (CuI), copper (I) oxide (Cu ₂ O), copper (I) bromide (I) CuBr, copper (I) chloride (CuCl), cyanide as a cuprous salt which can be used for a catalyst Copper (CuCN) etc. can be mentioned, It is preferable to use copper (I) iodide. Copper (II) chloride (CuCl ₂ ), copper acetate (II) (Cu (CH ₃ COO) ₂ ), copper bromide (II) bromide (CuBr), copper oxide (II) as a cupric salt that can be used as a catalyst (CuO) etc. can be mentioned. The ligand constituting the copper complex is preferably an organic ligand having a heteroatom as a ligand atom, and is an organic ligand having a nitrogen atom, an oxygen atom or a sulfur atom as a coordination atom Is more preferred. In addition, the ligand may contain at least any hetero atom of nitrogen atom, sulfur atom, and oxygen atom as a constituent atom other than the coordinating atom. Specific examples of the ligand of the copper complex include dimethylformamide, dimethylacetamide, N-methylpyrrolidone, bipyridine and its derivatives, phenanthroline and its derivatives, cyclohexanediamine and its derivatives, ethylenediamine and its derivatives, etc. And derivatives thereof. Here, a derivative means the ligand by which the host hydrogen atom was substituted by the substituent. One of these copper catalysts may be used alone, or two or more thereof may be used in combination. Further, at least one of the first and second copper salts and the above-mentioned ligand may be combined to form a copper complex as a copper catalyst. In addition, when using 2 or more types of copper catalysts, it is supposed that the total amount of them is a quantity as a compound represented by General formula (2).
In the present invention, a compound represented by the general formula (1) and a compound represented by the general formula (1) in which 0.3 equivalent or more of the copper catalyst as described above is present relative to one equivalent of the compound represented by the general formula (2) The compound represented by (2) is reacted. That is, in the presence of 0.3 times or more equivalent of the copper catalyst as the equivalent of the compound represented by the general formula (2), the respective compounds are reacted with each other. Thus, the compound represented by the target general formula (3) can be reliably obtained by the presence of a large amount of copper catalyst as compared with the conventional method of introducing an aryl group to an aromatic ring. Here, the equivalent of the copper catalyst to be present in the reaction system is, for example, selected from the range of 0.3 to 1.5 equivalents, or 0.1 to 5 equivalents per 1 equivalent of the compound represented by the general formula (2). It is possible to select from within the range of 4 to 1.2 equivalents, or to select from within the range of 0.5 to 1.0 equivalents.
In addition, when a ligand is present together with a copper salt, the amount of the ligand is 0.5 to 1.0 equivalent to 1 equivalent of the compound represented by the general formula (2) The amount is preferably 0.5 to 0.8 equivalents, and more preferably 0.5 to 0.6 equivalents.

(base)
In the reaction system of the compound represented by the above general formula (1) and the compound represented by the general formula (2), a base is preferably present together with a copper catalyst. This can further accelerate the reaction. The base is not particularly limited, but potassium carbonate (K ₂ CO ₃ ), tripotassium phosphate (K ₃ PO ₄ ), potassium tert-butoxide (KOtBu), lithium tert-butoxide (LiOtBu), cesium carbonate (Cs ₂ CO) _3), N, N- diisopropylethylamine (DIPEA), triethylamine _(Et 3 N), sodium tert- butoxide (NaOtBu), potassium fluoride (KF), cesium fluoride (CsF), sodium carbonate _(Na 2 _CO 3) Etc. can be mentioned. One of these bases may be used alone, or two or more of these bases may be used in combination.
The equivalent of the base to be present in the reaction system is preferably 0.1 to 10 equivalents, for example, 3 equivalents or more, or 4 equivalents or more to 1 equivalent of the compound represented by the general formula (2). Can be

(solvent)
The reaction system in the present invention is preferably a reaction liquid in which a substance related to the reaction is dissolved or dispersed. The solvent used in the reaction solution is not particularly limited as long as it is inert to the reaction, and examples thereof include aromatics such as benzene, toluene, xylene and chlorobenzene, diethyl ether, dibutyl ether, tetrahydrofuran, 1,4- Ethers such as dioxane, dimethoxyethane, diethylene glycol dimethyl ether, esters such as methyl acetate, ethyl acetate, butyl acetate, ethyl propionate, acetone, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, hexane, heptane, octane, nonane Etc., halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane, organic acids such as formic acid, acetic acid and propionic acid, N, N-dimethylformamide, N, N-dimethylacetamide It includes polar solvents and water, such as N- methylpyrrolidone, a mixed solvent thereof can be used. The amount of the solvent is preferably 5 to 60 times, and more preferably 10 to 30 times the weight of the compound represented by the general formula (1) to be subjected to the reaction.

(Other reaction conditions)
Other reaction conditions can be appropriately set according to the raw material to be used, the copper catalyst, the type of the solvent, and the like.
For example, the reaction temperature is preferably 20 to 200 ° C., more preferably 80 to 180 ° C., and still more preferably 100 to 160 ° C. The reaction may be performed at atmospheric pressure, or may be performed in a reduced pressure environment or a pressurized environment.

  The reaction time is preferably 1 hour to 300 hours, more preferably 5 hours to 150 hours, and still more preferably 8 hours to 100 hours.

[Uses of Compound Represented by General Formula (3)]
The compound represented by the general formula (3) produced by the method of the present invention has a structure in which a substituent is bonded to an aromatic ring via an sp2 carbon atom, and a π-conjugated system ranging from the aromatic ring to the substituent By further controlling the molecular structure, the light emission property and the charge transportability can be provided by controlling the molecular structure. Therefore, the compound represented by the general formula (3) is very useful as a synthetic intermediate for synthesizing, for example, a material (in particular, a light emitting material, a host material, a charge transporting material) used for an organic light emitting device.

The features of the present invention will be more specifically described below with reference to examples and comparative examples. The materials, amounts used, proportions, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as limited by the specific examples shown below.
Further, among the compounds used in each example and each comparative example, the compounds a1 and a2 correspond to the compounds represented by the general formula (1), and the compounds b1 to b4 are represented by the general formula (2) The compounds 1 to 4 correspond to the compounds represented by the general formula (3). Moreover, the numerical value which makes "eq" shown to each following reaction formula as a unit is a value of an equivalent when the compound represented by General formula (2) is made into 1 equivalent or 2 equivalents.

Example 1 Synthesis of Compound 1

Pentafluorobenzene (compound a1: 0.81 g, 4.83 mmol), 4-bromo-2,6-diphenylpyridine (compound b1: 0.50 g, 1.61 mmol), 1,10-phenanthroline (0.145 g, 0 805 mmol) and tripotassium phosphate (1.36 g, 6.45 mmol) are dissolved in a mixed solvent of xylene (7 mL) and N, N-dimethylformamide (7 mL), and under a stream of nitrogen, copper iodide (copper iodide) I) (0.154 g, 0.805 mmol) was added, and the mixture was heated to 150 ° C. and stirred for 45 hours. The reaction solution was allowed to cool to room temperature, water was added to stop the reaction, and extraction with ethyl acetate was performed. The obtained organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give compound 1.
ASAP mass spectral analysis: theoretical 397.1, observed 397.1

(Examples 2 and 3) Synthesis of compound 1 carried out under other conditions Amount of use of tripotassium phosphate or each amount of use of copper (I) iodide and 1,10-phenanthroline, reaction time shown in Table 1 Compound 1 was synthesized in the same manner as in Example 1 except that changes were made as shown.

Comparative Example 1 Reaction of Compound a1 with Compound b1 Using 0.2 Equivalent of Copper I (I) The amounts of copper (I) iodide and 1,10-phenanthroline used and the reaction times are shown in Table 1 The reaction was carried out in the same manner as in Example 1 except that it was changed as described above.

  The amounts (equivalents) of each compound used in Examples 1 to 3 and Comparative Example 1, the reaction temperature, the reaction time, and the ratio of the unreacted compound b1 to the obtained compound 1 are shown in Table 1. This ratio is a value estimated from 1 H-NMR spectrum.

  As shown in Table 1, in Comparative Example 1 in which the reaction was carried out in the presence of 0.2 equivalent of copper (I) iodide, compound 1 was not obtained at all, but 0.3 equivalent or more of iodine was obtained. Compound 1 was able to be obtained in Examples 1 to 3 in which the reaction was carried out in the presence of copper (I) oxide. From this, to ensure that the compound represented by the general formula (3) is obtained by reacting the compound represented by the general formula (1) with the compound represented by the general formula (2), the general formula It turned out that it is necessary to make a copper catalyst more than 0.3 equivalent with respect to 1 equivalent of the compound represented by (2).

Example 4 Synthesis of Compound 2

1,2,4,5-tetrafluorobenzene (compound a2: 1.89 g, 12.52 mmol), 2-iodo-4,6-diphenyl-1,3,5-triazine (compound b2: 1.62 g, 4 .17 mmol), 1,10-phenanthroline (0.225 g, 1.25 mmol), and tripotassium phosphate (3.54 g, 16.68 mmol) in xylene (40 mL) and N, N-dimethylformamide (40 mL) The mixture was dissolved in a mixed solvent, copper (I) iodide (0.39 g, 1.25 mmol) was added under a nitrogen stream, the temperature was raised to 100 ° C., and the mixture was stirred for 90 hours. The reaction solution was allowed to cool to room temperature, water was added to stop the reaction, and extraction with ethyl acetate was performed. The obtained organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give compound 2.
ASAP mass spectral analysis: theoretical value 381.1, observed value 382.2

Example 5 Synthesis of Compound 3

Pentafluorobenzene (compound a1: 3.17 g, 18.87 mmol), 2-bromopyrimidine (compound b3: 1.0 g, 6.29 mmol), 1,10-phenanthroline (0.341 g, 1.89 mmol), and phosphorus Tripotassium acid (4.00 g, 18.87 mmol) was dissolved in a mixed solvent of xylene (35 mL) and N, N-dimethylformamide (35 mL), and copper (I) iodide (0.36 g) was used under a nitrogen stream. The mixture was heated to 130 ° C. and stirred for 16 hours. The reaction solution was allowed to cool to room temperature, water was added to stop the reaction, and extraction with ethyl acetate was performed. The obtained organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a concentrate. The concentrate is purified by silica gel column chromatography using a mixed solvent of toluene: hexane = 1: 2 as a developing solvent to give 1.08 g (4.39 mmol) of a white solid of compound 3 in 70% yield. Obtained.
¹ H-NMR (500 MHz, CDCl _3, δ): 8.93 (d, J = 5.0 Hz, 2 H), 7.40 (t, J = 5.0 Hz, 1 H)
ASAP mass spectral analysis: theoretical 246.0, observed 246.1

Example 6 Synthesis of Compound 4

  Under a nitrogen stream, 1,2,4,5-tetrafluorobenzene (1.89 g, 12.59 mmol), 4-bromopyridine (4.77 g, 30.19 mmol), 1,10-phenanthroline (1.13 g, 6) .27 mmol) and tripotassium phosphate (25.6 g, 120.6 mmol) are dissolved in a mixed solvent of xylene (100 mL) and N, N-dimethylformamide (100 mL), and copper (I) iodide (1. Add 19 g, 6.27 mmol), raise to 150 ° C., and stir for 90 hours. The reaction solution is returned to room temperature, water is added to stop the reaction, and extraction with ethyl acetate is performed. The resulting organic layer is washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give compound 4.

Example 7 Synthesis of Compound 5

2,3,5,6-tetrafluoropyridine (3.73 g, 24.72 mmol), 3-bromobenzonitrile (1.5 g, 8.24 mmol), 1,10-phenanthroline (0.74 g, 4.12 mmol) And tripotassium phosphate (5.24 g, 24.7 mmol) were dissolved in a mixed solvent of xylene (20 mL) and N, N-dimethylformamide (20 mL), and copper (I) iodide (I 0.78 g (4.12 mmol) was added, the temperature was raised to 110 ° C., and the mixture was stirred for 20 hours. The reaction solution was allowed to cool to room temperature, water was added to stop the reaction, and extraction with ethyl acetate was performed. The obtained organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a concentrate. The resulting mixture was purified by silica gel column chromatography (hexane: chloroform = 7: 3) to give compound 5 in a yield of 0.51 g (2.02 mmol) in 24.5%.
¹ H-NMR (500 MHz, CDCl _3, δ): 7.86 to 7.84 (m, 2 H), 7.79 to 7.76 (m, 1 H), 7.72 to 7.68 (m, 1 H) ),
ASAP mass spectral analysis: theoretical 252.0, observed 251.9

Example 8 Synthesis of Compound 6

2,3,5,6-tetrafluoropyridine (1.66 g, 11.04 mmol), 4-iodobenzotrifluoride (1.0 g, 3.68 mmol), 1,10-phenanthroline (0.331 g, 1.84 mmol) And tripotassium phosphate (3.12 g, 14.7 mmol) are dissolved in a mixed solvent of xylene (10 mL) and N, N-dimethylformamide (10 mL), and copper (I) iodide under nitrogen stream (0.35 g, 1.84 mmol) was added, the temperature was raised to 120 ° C., and the mixture was stirred for 18 hours. The reaction solution was allowed to cool to room temperature, water was added to stop the reaction, and extraction with ethyl acetate was performed. The obtained organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a concentrate. The resulting mixture was purified by silica gel column chromatography (hexane: chloroform = 5: 1) to give compound 6 in a yield of 0.587 g (1.98 mmol) in a yield of 53.8%.
¹ H-NMR (500 MHz, CDCl _3, δ): 7.82 (d, J = 8.0 Hz, 2 H), 7.67 (d, J = 8.0 Hz, 2 H)
ASAP mass spectral analysis: theoretical value 295.0, observed value 295.0

  According to the method for producing a compound of the present invention, a substituent bonded to an sp2 carbon atom is efficiently introduced in place of a hydrogen atom of an aromatic ring, and a substituent bonded to an sp2 carbon atom is attached to the target position of the aromatic ring. The bound compound can be efficiently obtained. The compound thus produced can be effectively used as a light emitting material or a charge transporting material by further controlling the molecular structure. Therefore, the present invention has high industrial applicability.

Claims (8)

The compound represented by the following general formula (1) and the compound represented by the following general formula (2) in the presence of 0.3 equivalent or more of a copper catalyst of the compound represented by the following general formula (2) The method to manufacture the compound represented by General formula (3) by making it react.

[Wherein, A ¹ , A ² and A ³ each independently represent C (R ³ ) or N, and R ¹ represents C (R ⁴ ) (R ⁵ ) or N (R ⁶ ), R ² represents C (R ⁷ ) (R ⁸ ) (R ⁹ ) or N (R ¹⁰ ) (R ¹¹ ), R ^{3 to} R ¹¹ each independently represent a hydrogen atom or a substituent, and X is a halogen Represents an atom or a leaving group. R ¹ and R ² may be bonded to each other to form a cyclic structure. Also, when two or more of A ¹ , A ² and A ³ represent C (R ³ ), two or more R ³ may be bonded to each other to form a cyclic structure. ]   The method according to claim 1, wherein the compound represented by the general formula (2) is a substituted or unsubstituted 3-pyridyl halide or a substituted or unsubstituted 4-pyridyl halide. The method according to claim 1, wherein R ¹ and R ^{2 in} the general formula (2) are bonded to each other to form a cyclic structure containing two or more hetero atoms as ring skeleton constituent atoms. The compound according to any one of claims 1 to 3, wherein R ¹ and R ^{2 in} the general formula (2) are bonded to each other to form a cyclic structure, and the cyclic structure is substituted with two or more aryl groups. Method described in Section.   The method according to claim 4, wherein the cyclic structure contains a hetero atom as a ring skeleton constituent atom. All of A ¹ , A ² and A ^{3 in} the general formula (1) are each independently C (R ³ ), or ^{two of} A ¹ , A ² and A ³ are each independently C (R ³ The method according to claim 1, wherein the remaining one is N). The method according to claim 1, wherein the general formula (1) satisfies any one of the following conditions.
<1> A ¹ and A ³ are CF and A ² is CH.
<2> A ² is CF, A ¹ is CH, A ³ is C (R ³ ), and R ³ is a substituent.
<3> A ² is CF, and A ¹ and A ³ are CH. One or two of A ^{1 to} A ^{3 in} the general formula (1) are CH, and the remainder is CF, and R ¹ and R ^{2 in} the general formula (2) are bonded to each other to form a ring skeleton The method according to claim 1, which forms a cyclic structure containing a hetero atom as a constituent atom.