JP2013170126A - Fluorine-containing aromatic compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic compound adaptable to both a dry process and a wet process, and usable as an organic semiconductor material having high carrier mobility, and to provide a method for producing the same.SOLUTION: A fluorine-containing aromatic compound represented by formula (2-1) or (2-2), and a method for producing the same are provided. [In the formula, Ydenotes a hydrogen atom or -CFCOR, Ydenotes a hydrogen atom or -CFCOR, Rand Reach denote an alkyl group, a hydrogen atom or the like, Z-Zeach denote a hydrogen atom or a halogen atom, R-Reach denote an alkyl group, a hydrogen atom or the like, m denotes an integer of ≥0, n denotes an integer of ≥1, and Land Leach denote an alkyl group, a hydrogen atom or the like].

Description

  The present invention relates to a novel fluorine-containing aromatic compound applicable to organic semiconductor materials and a method for producing the same.

  In recent years, organic semiconductor elements using organic compounds as semiconductor materials are easier to process than semiconductor elements using conventional inorganic semiconductor materials such as silicon. Has been. Further, since organic compound semiconductor materials are structurally flexible, it is expected to realize devices such as flexible displays by using them in combination with a plastic substrate.

  As a semiconductor processing process, a dry process by vapor deposition such as plasma or ion beam, and a wet process using an organic solvent such as coating, printable, and inkjet are known. Conventional organic semiconductor materials have low solubility in organic solvents, and it has been difficult to apply wet processes, and thus dry processes have been widely used. On the other hand, the wet process has an advantage that it can be processed without damaging the semiconductor crystal.

  In general, organic semiconductor materials are required to have improved carrier mobility. In organic semiconductor materials, effective means for improving carrier mobility have not yet been established, but it is considered important to strengthen intermolecular interactions and control molecular arrangements. ing. For example, acene compounds, which are condensed polycyclic compounds, have been tried to be used as organic semiconductor materials because their conjugated systems are expanded by the planar structure and have strong intermolecular interactions due to π-π stacking (non-patented). Reference 1).

An acene compound is a compound having a skeleton in which a benzene ring is linearly condensed, has a smaller theoretical band gap than polyacetylene, etc., and is expected to have an excellent function as an organic semiconductor material, increasing the number of rings. The function can be expected. In addition, there is a possibility that conductivity is changed by a substituent.
However, when an acene compound does not have a substituent, the solubility in an organic solvent decreases as the number of rings increases. Therefore, it is difficult to apply the wet process to the acene compound, and the range of choices such as solvent and temperature conditions is very narrow.

  Thus, an acene compound has been proposed that introduces a substituent such as an alkyl group into the acene skeleton to increase the affinity for an organic solvent and can be applied to a wet process (Patent Document 1). Those having a fluorine-containing ester group are not studied.

JP 2007-13097 A

D. J. et al. Gundlach, S.M. F. Nelson, T .; N. Jachson et al. , Appl. Phys. Lett. , (2002), 80, 2925.

  In the prior art, an organic semiconductor material that can be expected to have a high carrier mobility is obtained mainly by a dry process, and such a material has low solubility in a solvent. On the other hand, an organic semiconductor material obtained by a wet process having high solubility in a solvent has low carrier mobility. In addition, since the acene compound obtained by the conventional technique uses a heavy metal when introducing a substituent, there is a concern that the carrier mobility as an organic semiconductor may be reduced due to the remaining heavy metal.

Therefore, an object of the present invention is to provide a compound that can be applied to both a dry process and a wet process and that is useful as an organic semiconductor material having a high carrier mobility.
Specifically, a first object is to provide a compound that is soluble in a low-polarity solvent and that can have high carrier mobility due to strong intermolecular interaction. It is a second object to provide a compound with less heavy metal contamination that contributes to a decrease in carrier mobility.

  As a result of intensive studies to solve the above-mentioned problems and achieve the object, the present inventors have reduced the contamination of heavy metals and are relatively soluble in low-polar solvents, and have a specific structure of fluorine-containing aromatics. A new compound and a production method thereof have been found, and the present invention has been completed.

That is, the present invention relates to the following.
[1]
A fluorine-containing aromatic compound represented by the following formula (2-1) or (2-2).

[In Formula (2-1) and Formula (2-2), Y ₁ is —CF ₂ CO ₂ R ₁ , and Y ₂ is a hydrogen atom or —CF ₂ CO ₂ R ₂ . Y _{1, Y R} 1 in _{2, R 2} are both, a hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms and may be the same or different.
Z _{3 to} Z ₆ are a hydrogen atom or a halogen atom, and these may be the same or different.
R _{3 to} R ₆ are each a hydrocarbon group having 1 to 12 carbon atoms that may have a substituent, an aromatic hydrocarbon group that may have a substituent, or a heteroaromatic group that may have a substituent. , A halogen atom or a hydrogen atom, which may be the same or different.
m and n are the repeating numbers of the repeating unit structures A and B shown in parentheses, m is an integer of 0 or more, n is an integer of 1 or more, and m + n is an integer of 2 or more and 6 or less.
L ₁ and L ₂ are each a hydrocarbon group having 1 to 12 carbon atoms that may have a substituent, an aromatic hydrocarbon group that may have a substituent, or a heteroaromatic group that may have a substituent. , A halogen atom, or a hydrogen atom, and when m is 2 or more, a plurality of L ₁ present in structure A may be the same or different, and a plurality of L ₁ present in structure A L ₂ may be the same or different.
The order in which the structure A and the structure B are combined may be random and is not limited. ]
[2]
The compound represented by the formula (2-1) is a compound represented by the following formula (3-1) or the formula (4-1), and the compound represented by the formula (2-2) is represented by the following formula: The fluorine-containing aromatic compound according to the above [1], which is a compound represented by (3-2) or formula (4-2).

[In Formula (3-1), Formula (3-2), Formula (4-1), and Formula (4-2), Y ₁ , Y ₂ , Z _{3 to} Z ₆ , and R _{3 to} R ₆ are the same as above. Indicates the same meaning. ]
[3]
R _{3 to} R ₆ are each independently a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, an aromatic hydrocarbon group which may have a substituent, a halogen atom or a hydrogen atom. The fluorine-containing aromatic compound according to [1] or [2].
[4]
The organic-semiconductor material containing the fluorine-containing aromatic compound as described in any one of said [1]-[3].
[5]
Fluorine-containing aromatic represented by the following formula (2-1-1) including the step of reacting the compound represented by the following formula (1) with X ₁ CF ₂ CO ₂ R ₁ and the step of aromatization A method for producing a compound.

[In the above formula, R ₁ is a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom.
X ₁ is a halogen atom.
Y ₁ is —CF ₂ CO ₂ R ₁ . R _{1 in} Y ₁ has the same meaning as described above.
Z _{3 to} Z ₆ are a hydrogen atom or a halogen atom, and these may be the same or different.
m and n are the repeating numbers of the repeating unit structures A and B shown in parentheses, m is an integer of 0 or more, n is an integer of 1 or more, and m + n is an integer of 2 or more and 6 or less.
L ₁ and L ₂ are each a hydrocarbon group having 1 to 12 carbon atoms that may have a substituent, an aromatic hydrocarbon group that may have a substituent, or a heteroaromatic group that may have a substituent. , A halogen atom, or a hydrogen atom, and when m is 2 or more, a plurality of L ₁ present in structure A may be the same or different, and a plurality of L ₁ present in structure A L ₂ may be the same or different.
The order in which the structure A and the structure B are combined may be random and is not limited. ]
[6]
A compound represented by the following formula (1) is reacted with X ₁ CF ₂ CO ₂ R ₁ , reacted with X ₂ CF ₂ CO ₂ R ₂ , and aromatized. A method for producing a fluorine-containing aromatic compound represented by -1-2).

[In the above formula, R ₁ is a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, R ₂ is a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, and these may be the same or different. .
X ₁ and X ₂ are halogen atoms, and these may be the same or different.
Y ₁ is —CF ₂ CO ₂ R ₁ . R _{1 in} Y ₁ has the same meaning as described above.
Z _{3 to} Z ₆ are a hydrogen atom or a halogen atom, and these may be the same or different.
m and n are the repeating numbers of the repeating unit structures A and B shown in parentheses, m is an integer of 0 or more, n is an integer of 1 or more, and m + n is an integer of 2 or more and 6 or less.
L ₁ and L ₂ are each a hydrocarbon group having 1 to 12 carbon atoms that may have a substituent, an aromatic hydrocarbon group that may have a substituent, or a heteroaromatic group that may have a substituent. , A halogen atom, or a hydrogen atom, and when m is 2 or more, a plurality of L ₁ present in structure A may be the same or different, and a plurality of L ₁ present in structure A L ₂ may be the same or different.
The order in which the structure A and the structure B are combined may be random and is not limited. ]
[7]
Including a step of reacting a compound represented by the following formula (1) with X ₁ CF ₂ CO ₂ R ₁ and aromatizing step, and when at least one of Z _{3 to} Z ₆ is a halogen atom, the _Z 3 to Z ₆ are atomic respectively comprising the step of substituting _R 3 to R _6, a method for producing a fluorine-containing aromatic compound represented by the following formula (2-2-1).

[In the above formula, R ₁ is a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom.
X ₁ is a halogen atom.
Y ₁ is —CF ₂ CO ₂ R ₁ . R _{1 in} Y ₁ has the same meaning as described above.
Z _{3 to} Z ₆ are a hydrogen atom or a halogen atom, and these may be the same or different.
R _{3 to} R ₆ are each a hydrocarbon group having 1 to 12 carbon atoms that may have a substituent, an aromatic hydrocarbon group that may have a substituent, or a heteroaromatic group that may have a substituent. , A halogen atom or a hydrogen atom, which may be the same or different.
m and n are the repeating numbers of the repeating unit structures A and B shown in parentheses, m is an integer of 0 or more, n is an integer of 1 or more, and m + n is an integer of 2 or more and 6 or less.
L ₁ and L ₂ are each a hydrocarbon group having 1 to 12 carbon atoms that may have a substituent, an aromatic hydrocarbon group that may have a substituent, or a heteroaromatic group that may have a substituent. , A halogen atom, or a hydrogen atom, and when m is 2 or more, a plurality of L ₁ present in structure A may be the same or different, and a plurality of L ₁ present in structure A L ₂ may be the same or different.
The order in which the structure A and the structure B are combined may be random and is not limited. ]
[8]
Including a step of reacting a compound represented by the following formula (1) with X ₁ CF ₂ CO ₂ R ₁ , a step of reacting with X ₂ CF ₂ CO ₂ R ₂ , and a step of aromatization, and further including Z ₃ If at least one to Z ₆ is a halogen atom, a _Z 3 to Z ₆ are halogen atoms, respectively, including the step of substituting with _R 3 to R _6, fluorine-containing represented by the following formula (2-2-2) A method for producing an aromatic compound.

[In the above formula, R ₁ is a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, R ₂ is a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, and these may be the same or different. .
X ₁ and X ₂ are halogen atoms, and these may be the same or different.
Y ₁ is —CF ₂ CO ₂ R ₁ . R _{1 in} Y ₁ has the same meaning as described above.
Z _{3 to} Z ₆ are a hydrogen atom or a halogen atom, and these may be the same or different.
R _{3 to} R ₆ are each a hydrocarbon group having 1 to 12 carbon atoms that may have a substituent, an aromatic hydrocarbon group that may have a substituent, or a heteroaromatic group that may have a substituent. , A halogen atom or a hydrogen atom, which may be the same or different.
m and n are the repeating numbers of the repeating unit structures A and B shown in parentheses, m is an integer of 0 or more, n is an integer of 1 or more, and m + n is an integer of 2 or more and 6 or less.
L ₁ and L ₂ are each a hydrocarbon group having 1 to 12 carbon atoms that may have a substituent, an aromatic hydrocarbon group that may have a substituent, or a heteroaromatic group that may have a substituent. , A halogen atom, or a hydrogen atom, and when m is 2 or more, a plurality of L ₁ present in structure A may be the same or different, and a plurality of L ₁ present in structure A L ₂ may be the same or different.
The order in which the structure A and the structure B are combined may be random and is not limited. ]
[9]
A fluorine-containing aromatic compound represented by any of the following formulas.

Since the fluorine-containing aromatic compound of the present invention becomes relatively soluble in a low-polarity solvent by introducing a fluorine-containing substituent, application to wet processes such as coating is expected. In addition, since the substituent is a fluorine-containing ester, it has a very strong electron-withdrawing property over a general ester group that does not contain fluorine, so it may prevent deterioration behavior due to oxygen and moisture in the atmosphere. Can be considered. Further, since the heavy metal content can be reduced by a compound synthesis process without using metal coupling, higher mobility is expected.
By these, this fluorine-containing aromatic compound can be utilized as an organic semiconductor material applied to a high performance organic TFT, an organic EL element, etc.

Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented without departing from the gist of the present invention.
The compound represented by the formula (X) is also referred to as “compound (X)”.

<Fluorine-containing aromatic compound>
The fluorine-containing aromatic compound of the present invention is a compound represented by the following formula (2-1) or (2-2).

In compounds (2-1) and (2-2), Y ₁ is —CF ₂ CO ₂ R ₁ , and Y ₂ is —CF ₂ CO ₂ R ₂ or a hydrogen atom. Y _{1, Y R} 1 in _{2, R 2} are both, a hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms, may be the same or different, in particular, hydrocarbon group of 1 to 6 carbon atoms Or it is preferable that it is a hydrogen atom. The longer the alkyl chain of R ₁ and R _2, the higher the solubility in an organic solvent. The hydrocarbon group is preferably a linear, branched or cyclic alkyl group.

m and n are the repeating numbers of the repeating unit structures A and B shown in parentheses, respectively, m is an integer of 0 or more, and n is an integer of 1 or more. m + n is an integer of 2 or more and 6 or less, and preferably 3 or more and 6 or less in terms of achieving compatibility between solubility in an organic solvent and strong intermolecular interaction by π-π stacking.
The order in which the structure A and the structure B are combined may be random and is not limited. Moreover, the structure A and the structure B may be couple | bonded alternately.

Z _{3 to} Z ₆ are a hydrogen atom or a halogen atom, and these may be the same or different. If at least one of Z _{3 to} Z ₆ is a halogen atom, the halogen atom is further substituted with R _{3 to} R ₆ (in this case, R _{3 to} R ₆ are other than a hydrogen atom and a halogen atom). Substituents can be further introduced into the fluoroaromatic compound. As the halogen atom, fluorine, chlorine, bromine and iodine are preferable, and bromine and iodine are particularly preferable from the viewpoint of reactivity.

R _{3 to} R ₆ are each a hydrocarbon group having 1 to 12 carbon atoms that may have a substituent, an aromatic hydrocarbon group that may have a substituent, or a heteroaromatic group that may have a substituent. , A halogen atom or a hydrogen atom, which may be the same or different. In particular, it is preferably a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom.
In R _{3 to} R ₆ , the hydrocarbon group having 1 to 12 carbon atoms is preferably a C 1-12 alkyl group or cycloalkyl group which may be branched, and the aromatic hydrocarbon group may be a phenyl group or a substituent. The heteroaromatic group is preferably a thienyl group, and the halogen atom is preferably a bromine atom or an iodine atom.

Introducing R _{3 to} R ₆ into the fluorine-containing aromatic compound of the present invention is particularly preferable in terms of further improving the solubility in an organic solvent. Further, since R _{3 to} R ₆ can act as an electron withdrawing or electron donating group, the electron transition energy can be controlled. As a result, the conductivity can be controlled, which is preferable as an organic semiconductor material.

L ₁ and L ₂ are each a hydrocarbon group having 1 to 12 carbon atoms that may have a substituent, an aromatic hydrocarbon group that may have a substituent, or a heteroaromatic group that may have a substituent. , A halogen atom, or a hydrogen atom, which may be the same or different.
When m is 2 or more, the plurality of L ₁ present in the structure A may be the same or different, and the plurality of L ₂ present in the structure A are the same or different. It may be.
In L ₁ and L ₂ , the C 1-12 alkyl group and cycloalkyl group which may be branched are preferable as the C 1-12 hydrocarbon group, and the aromatic hydrocarbon group is a phenyl group, and an electron demand. A phenyl group having an attractive or electron-donating substituent is preferable, a thienyl group is preferable as the heteroaromatic group, and bromine and iodine are preferable as the halogen atom. Moreover, as a substituent in L < ₁ > and L < ₂ >, a hydrogen atom is preferable.

In the compounds (2-1) and (2-2), the number of aromatic rings to be condensed is represented by m + n, but as the number of aromatic rings increases, due to strong intermolecular interaction due to π-π stacking Increase in carrier mobility is expected.
In the present invention, m + n is particularly preferably 3 or 5. Moreover, it is particularly preferable that both ends of the compound in which m + n aromatic rings are connected have the structure A.

In particular, when m + n is 3, m = 2 and n = 1 are preferable. In the compounds (2-1) and (2-2), the bonding positions of Y ₁ and Y ₂ are each an acene skeleton. The 9th and 10th positions are preferred. That is, the following compounds (3-1) and (3-2) are preferable.

In Formula (3-1) and Formula (3-2), Y ₁ , Y ₂ , Z _{3 to} Z ₆ , and R _{3 to} R ₆ have the same meaning as described above. Preferably, Y ₁ is a fluorine-containing carboxyl group or fluorine-containing ester group, Y ₂ is a fluorine-containing carboxyl group or fluorine-containing ester group, Z _{3 to} Z ₆ are alkyl groups or hydrogen atoms having 1 to 12 carbon atoms, R ₃ to R ₆ is an alkyl group having 1 to 12 carbon atoms or a hydrogen atom.

Moreover, when m + n is 5, it is preferable that m = 4 and n = 1. In the compounds (2-1) and (2-2), the bonding positions of Y ₁ and Y ₂ are each an acene skeleton. The 6th and 13th positions are preferred. That is, the following compounds (4-1) and (4-2) are preferable.

In Formula (4-1) and Formula (4-2), Y ₁ , Y ₂ , Z _{3 to} Z ₆ , and R _{3 to} R ₆ have the same meaning as described above. Preferably, Y ₁ is a fluorine-containing carboxyl group or fluorine-containing ester group, Y ₂ is a fluorine-containing carboxyl group or fluorine-containing ester group, Z _{3 to} Z ₆ are alkyl groups or hydrogen atoms having 1 to 12 carbon atoms, R ₃ to R ₆ is an alkyl group having 1 to 12 carbon atoms or a hydrogen atom.

  Furthermore, the compounds (2-1) and (2-2) are preferably compounds selected from the group of compounds represented by the following formulae.

<Method for producing fluorine-containing aromatic compound>
The fluorine-containing aromatic compound of the present invention can be produced by the following method.
In the production method of the present invention, the following quinone compound (1) is used as a starting material, and the step (A) of reacting with X ₁ CF ₂ CO ₂ R ₁ is essential. Thereby, one of the carbonyl groups of the compound (1) is converted into a fluorine-containing ester group —CF ₂ CO ₂ R ₁ .
Furthermore, following the step (A), by including the step (B) of reacting with X ₂ CF ₂ CO ₂ R ₂ , the other carbonyl group remaining in the structure B becomes a fluorine-containing ester group —CF ₂ CO _2. It is converted to ₂ R _2.
X ₁ and X ₂ are halogen atoms, and these may be the same or different. R ₁ and R ₂ are each a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, and these may be the same or different.

[Z _{3 to} Z ₆ are a hydrogen atom or a halogen atom, and these may be the same or different.
m and n are the repeating numbers of the repeating unit structures A and B shown in parentheses, m is an integer of 0 or more, n is an integer of 1 or more, and m + n is an integer of 2 or more and 6 or less.
L ₁ and L ₂ are each a hydrocarbon group having 1 to 12 carbon atoms that may have a substituent, an aromatic hydrocarbon group that may have a substituent, or a heteroaromatic group that may have a substituent. , A halogen atom, or a hydrogen atom, and when m is 2 or more, a plurality of L ₁ present in structure A may be the same or different, and a plurality of L ₁ present in structure A L ₂ may be the same or different.
The order in which the structure A and the structure B are combined may be random and is not limited. ]

Furthermore, when at least one of Z _{3 to} Z ₆ of the quinone compound (1) is a halogen atom, a step (C) of substituting Z _{3 to} Z ₆ as a halogen atom with R _{3 to} R ₆ may be included. Thereby, a substituent can be further introduced. Note that all of Z _{3 to} Z ₆ which are halogen atoms may not be substituted, and in this case, the halogen atom corresponds to R _{3 to} R ₆ in the case of being a halogen atom, respectively.

The step (C) of substituting the halogen atoms Z _{3 to} Z ₆ with R _{3 to} R ₆ may be any organic reaction as long as a C—C bond is formed, and is not particularly limited. For example, it can be carried out by Suzuki coupling reaction or Sonogashira coupling reaction.

When the carbonyl group conversion step (B) is not performed and only the step (A) is performed, an aromatization reaction can be performed in order to treat an unreacted carbonyl group. The aromatization reaction is not particularly limited as long as it can be converted into an acene-based aromatic compound (2-1). However, reactions using heavy metals (eg, tin chloride) commonly used in aromatization reactions are excluded. For example, aromatization via dehydration by heat treatment at 220 ° C. or higher in a vacuum can be mentioned. Also, for example, an aromatization reaction using triphenylphosphine / carbon tetrabromide and passing through a dehydration step can be mentioned. The raw material and carbon tetrabromide are added in an amount of 3 to 10 mol / gram equivalent to the raw material, and further triphenylphosphine is added in an amount of 2 to 10 mol / gram equivalent to the raw material and at 0 ° C. The reaction is carried out under reflux for 3 to 24 hours.
The organic solvent is preferably a chlorinated solvent, and examples thereof include dichloromethane, chloroform, and carbon tetrachloride. Dichloromethane is particularly preferred.

The order of the step (C) for substituting the halogen atom may be performed before or after the steps (A) and (B) for converting the carbonyl group into a fluorinated ester group, and is not particularly limited. .
Therefore, as a method for producing the fluorinated aromatic compound of the present invention, for example, the following route can be considered depending on the combination of steps (A) to (C).

In the above formula, Y ₁ is —CF ₂ CO ₂ R ₁ , and Y ₂ is a hydrogen atom or —CF ₂ CO ₂ R ₂ . R _{1 to} R ₆ , Z _{3 to} Z ₆ , m, n, L ₁ , L ₂ , A, and B are as defined above.

That is, by using the compound (1) as a starting material and aromatizing an unreacted carbonyl group after the step (A), a fluorinated aromatic compound (2-1-1) which is a monosubstituted carbonyl group is obtained. ) Is obtained. Furthermore, the fluorine-containing aromatic compound (2-1-2) which is a disubstitution body is obtained by combining a process (B) after a process (A).
And a fluorine-containing aromatic compound (2-2-1) or (2-2-2) into which the substituent was introduce | transduced is obtained by respectively combining a process (C) with said each manufacturing method.

This will be specifically described below.
As the starting material compound (1), a known quinone compound can be used, and the following compound (1-1) or (1-2) is preferred.

In the above formula, Z _{3 to} Z ₆ have the same meaning as described above.

  Preferably, for example, 9,10-anthraquinone, 2-bromo-9,10-anthraquinone, 2-iodo-9,10-anthraquinone, 2,6-dibromo-9,10-anthraquinone, 2,6-diiodo-9 , 10-anthraquinone, 6,13-pentacenequinone, 5,7,12,14-tetrahydropentacene-5,7,12,14-tetraone, and the like.

  Specifically, it can be produced by any of the following methods (a) to (d).

(A) A quinone compound of compound (1) (wherein Z _{3 to} Z ₆ are all hydrogen atoms) is used as a raw material, and X ₁ CF ₂ CO ₂ R ₁ is set to 2.0 to 3. Equivalent amount of 0 mol / gram is added and reacted in an organic solvent under zinc catalyst. This is treated with dilute hydrochloric acid to remove the zinc catalyst as a precipitate. After this step, aromatization can be performed by a conventional method to obtain the target compound (2-1-1) (wherein R _{3 to} R ₆ are all hydrogen atoms).
Here, X ₁ is a halogen atom, particularly preferably iodine or bromine. R ₁ is a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, but a hydrocarbon group having 1 to 6 carbon atoms is particularly preferable, and an ethyl group or the like is preferable. A known compound can be used as X ₁ CF ₂ CO ₂ R ₁ .
Examples of the organic solvent include tetrahydrofuran (THF), diethyl ether, etc. Among them, THF is preferable.

(B) A quinone compound of compound (1) (wherein Z _{3 to} Z ₆ are all hydrogen atoms) is used as a raw material, and X ₁ CF ₂ CO ₂ R ₁ is set to 2.0 to 3. with respect to the raw material. Add 0 mol / gram equivalent, and react in an organic solvent under zinc catalyst. X ₂ CF ₂ CO ₂ R ₂ is added in an amount of 2.0 to 10 mol / gram equivalent to the obtained intermediate, and reacted in an organic solvent under a zinc catalyst. Then, this is treated with dilute hydrochloric acid to remove the zinc catalyst as a precipitate. After this step, aromatization can be carried out by a conventional method to obtain the target compound (2-1-2) (however, Z _{3 to} Z ₆ are all hydrogen atoms).
Here, X ₁ and X ₂ are halogen atoms, and iodine or bromine is particularly preferable. R ₁ and R ₂ are each a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, preferably a hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably an ethyl group. A known compound can be used as X ₂ CF ₂ CO ₂ R ₂ .
Examples of the organic solvent include tetrahydrofuran (THF), diethyl ether, etc. Among them, THF is preferable.

Among _(c) Z 3 ~Z _6, when at least one is a halogen atom, by the same procedure as (a), after synthesis of compound (2-1-1), _Z 3 ~ is a halogen atom The target compound (2-2-1) can be obtained through a step of substituting Z _{6 with} R _{3 to} R ₆ .

(D) When at least one of Z _{3 to} Z ₆ is a halogen atom, compound (2-1-2) is synthesized by the same procedure as (b), and then Z ₃ to The target compound (2-2-2) can be obtained through a step of substituting Z _{6 with} R _{3 to} R ₆ .

By the method (c) or (d), an arbitrary substituent can be introduced into R _{3 to} R ₆ .

The step of substituting halogen atoms Z _{3 to} Z ₆ with R _{3 to} R ₆ may use any organic reaction as long as a C—C bond is formed, and is not particularly limited. For example, it can be carried out by Suzuki coupling reaction or Sonogashira coupling reaction.

As shown in the above methods (a) to (d), the method for synthesizing a fluorine-containing aromatic compound in the present invention does not use a heavy metal coupling reaction when introducing a fluorine-containing ester group. In the zinc catalyst used in the above methods (a) to (d), zinc in the reaction system exists as a suspension and can be removed by centrifugation, filtration, column chromatography, or the like. Therefore, the ratio of heavy metals contained in the synthesized compound can be greatly reduced.
However, when at least one of Z _{3 to} Z ₆ is a halogen atom, a heavy metal may be used in introducing the substituents of R _{3 to} R ₆ .

<Organic semiconductor materials>
Next, the organic semiconductor material of the present invention will be described.
The organic semiconductor material of the present invention is an organic semiconductor material containing the fluorine-containing aromatic compound of the present invention. The organic semiconductor material of the present invention only needs to contain the fluorine-containing aromatic compound of the present invention. For example, the organic semiconductor material may be used by mixing with other organic semiconductor materials, and may contain various dopants. Good. As the dopant, for example, coumarin, quinacridone, rubrene, stilbene derivatives, fluorescent dyes, and the like can be used when used as a light emitting layer of an organic EL element.

  The organic semiconductor of the present invention is stabilized in the molecular arrangement (π-π stacking) in which the surface of the aromatic ring as the main skeleton faces each other due to the presence of the fluorine-containing ester group, and the charge mobility is higher than that of the unsubstituted one. It seems to contribute to the expression of.

  In the case of anthracene, the fluorine-containing ester located at the 9th or 9th, 10th position, and in the case of pentacene at the 6th, 6th or 13th position prevents the dimerization of pentacenes at this position. There are two roles to prevent deterioration behavior that becomes a quinone skeleton such as anthracenequinone or pentacenequinone by oxygen and moisture.

  Moreover, it aggregates due to the affinity between fluorine-containing esters of adjacent molecules (hydrogen bonding and fluorophylic effect), contributing to more efficient charge transfer. Therefore, by using the fluorine-containing aromatic compound of the present invention, it is possible to produce an organic semiconductor thin film having high carrier mobility and an electronic device such as a transistor using the organic semiconductor thin film.

  Usually, anthracene and pentacene which do not have a substituent behave as a p-type semiconductor, but the fluorinated aromatic compound of the present invention into which a fluorinated ester group which is an electron-attracting substituent is introduced is electrically conductive by the substituent. It has the potential to change gender. Therefore, in the fluorine-containing aromatic compound of the present invention, the fluorine-containing ester group in a part of the acene skeleton can control the conductivity type as a result of the change of the electron transition energy, and is preferable as an organic semiconductor material.

  When the organic semiconductor material of the present invention obtained by the above-described manufacturing method is dissolved in a solvent, an organic semiconductor thin film can be formed by coating on a substrate. Examples of film forming methods include spin coating, casting, dipping, ink jet, doctor blade, screen printing, dispensing, and the like. A thin film can be formed by a known wet film forming method. Is possible. Further, depending on the casting method or the like, it is possible to take a form of a flat crystal or a thick film state. Depending on the device to be produced, an appropriate combination is selected from the above-described film forming methods or solvents.

  The film can also be formed by a dry process such as a vacuum evaporation method. These thin films, thick films, or crystals function as charge transporting members for various functional elements such as photoelectric conversion elements, thin film transistors, and light emitting elements, and a variety of electronic devices can be manufactured using this semiconductor material. It is.

  Here, the organic semiconductor thin film is made of the fluorine-containing aromatic material of the present invention and has crystallinity.

  Examples of the organic solvent that can dissolve the fluorine-containing aromatic compound of the present invention include aliphatic hydrocarbons such as pentane, hexane, and heptane; aromatic hydrocarbons such as benzene, toluene, and xylene; Alicyclic hydrocarbons; ethers such as diethyl ether, tert-butyl methyl ether, tetrahydrofuran and dioxane; alcohols such as methanol, ethanol and 2-propanol; esters such as ethyl acetate and ethyl lactate; dichloromethane, chloroform and the like Chlorinated hydrocarbons; nitriles such as acetonitrile; ketones such as acetone and methyl ethyl ketone; cyclic ketones such as cyclopentanone and cyclohexanone; cyclic esters such as γ-butyrolactone; ether alcohols such as butyl cellosolve; N-methyl Cyclic amides of 2-pyrrolidone and the like; amides such as dimethylformamide; sulfone sulfoxides such as dimethyl sulfoxide; or mixtures thereof and the like. Hexane, cyclohexane, toluene, tetrahydrofuran, chloroform and 1,2-dichlorobenzene are preferred.

Other examples of the organic solvent include halogen-containing solvents. Examples thereof include chlorinated hydrocarbons, fluorinated hydrocarbons, chlorinated fluorinated hydrocarbons, and fluorine-containing ether compounds. Specifically, methylene chloride, chloroform, 2,3,3-trichloroheptafluorobutane, 1,1,1,3-tetrachlorotetrafluoropropane, 1,1,1-trichloropentafluoropropane, 1,1- Dichloro-2,2,3,3,3-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, carbon tetrachloride, 1,2-dichloroethane, C ₆ F _{13 -C 2 H 5, C 4 F} 9 OCH 3, C 4 F 9 OC 2 H 5 and the like can be used. Fluorine-containing solvents such as Asahi Clin AK-225 (manufactured by Asahi Glass Co., Ltd., generic name HCFC-225), Asahi Clin AC-6000 (manufactured by Asahi Glass Co., Ltd., generic name HFC-76-13sf) are also used as the fluorinated aromatic compound of the present invention. As an organic solvent capable of dissolving
In addition, you may use the solvent which mixed the mixture of the organic solvent and halogen-containing solvent which were illustrated previously in arbitrary ratios.

  The solubility of the fluorine-containing aromatic compound of the present invention in these organic solvents is high, and in particular, it shows very high solubility in hexane and cyclohexane, which are known as low polarity solvents. Therefore, the fluorine-containing aromatic compound can be easily purified by a simple method such as column chromatography or recrystallization.

  Since the fluorine-containing aromatic compound of the present invention dissolves very well in the organic solvent, an organic semiconductor thin film can be produced by applying or printing this solution on a substrate. The thickness of the organic semiconductor thin film layer used for the organic semiconductor element is usually 10 to 1,000 nanometers, and the concentration of the compound in the solution is 0.1 to 10% by weight.

  Since various concentrations of the solution can be prepared due to the excellent solubility of the fluorine-containing aromatic compound of the present invention, the crystallinity depending on the concentration of the solution can be varied. When the crystallinity of the fluorinated aromatic compound varies, the carrier mobility affected by the crystallinity also varies. As described above, since the crystallinity in a wide range from crystal to amorphous can be easily adjusted, necessary element characteristics such as the thickness of the organic semiconductor film and carrier mobility can be stably reproduced.

  Examples of the substrate on which the fluorine-containing aromatic compound of the present invention and the solution thereof can be applied or printed include various substrates. Examples of the substrate to be used include a glass substrate, a metal substrate such as gold, copper and silver, a crystalline silicon substrate, an amorphous silicon substrate, a triacetyl cellulose substrate, a norbornene substrate, a polyethylene terephthalate substrate, a polyester substrate, a polyvinyl substrate, and a polypropylene substrate. And a polyethylene substrate.

  As a method for applying the fluorine-containing aromatic compound and the solution thereof of the present invention, various methods are exemplified, and examples thereof include a spin coating method, a dip coating method, a blade method, and a drop casting method. There are various methods for printing the solution of the fluorine-containing aromatic compound, and examples thereof include screen printing, ink jet printing, planographic printing, intaglio printing, letterpress printing and the like.

  The fluorine-containing aromatic compound of the present invention has high carrier mobility and excellent properties as a semiconductor material. As described above, since the fluorine-containing aromatic compound of the present invention has high solubility in an organic solvent, a simple film forming process such as a casting method or a printing method can be used. An organic semiconductor thin film or an organic semiconductor element can be manufactured without impairing carrier mobility.

  EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples.

In this example, the structure of the compound was determined by the analysis method shown below.
For the nuclear magnetic resonance analysis, a Fourier transform high resolution nuclear magnetic resonance apparatus (NMR) manufactured by Bruker, AVANCE III400 was used. The multiplicity is abbreviated as singlet: s, doublet: d, triplet: t, quartert: q, multiplet: m, and broadcast: br.
¹ H NMR (400 MHz)
Solvent: chloroform-d (CDCl ₃ ) or acetone-d ₆ (Aceton-d ₆ )
Internal standard: Tetramethylsilane (TMS)
¹³ C NMR (100 MHz)
Solvent: chloroform-d (CDCl ₃ ) or acetone-d ₆ (Aceton-d ₆ )
Internal standard: Chloroform-d (CDCl ₃ )
¹⁹ F NMR (400 MHz)
Solvent: chloroform-d (CDCl ₃ ) or acetone-d ₆ (Aceton-d ₆ )
Internal standard: hexafluorobenzene (C ₆ F ₆ ) is set to −163 ppm (CFCl _{3 is set} to 0 ppm)

  For infrared absorption spectroscopy, a Fourier transform infrared spectrophotometer (FT-IR) manufactured by Shimadzu Corporation and Shimadzu IRAffinity were used.

<Example 1-a: Synthesis of compound (a)>
Under an argon atmosphere, chlorotrimethylsilane (manufactured by Tokyo Chemical Industry Co., Ltd., 0.03 g) as a zinc activator was added to a suspension of zinc (manufactured by Kanto Chemical Co., Ltd., 0.43 g, 6.6 mmol) in tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd., 3 mL). 1 mL) was added dropwise. Under reflux, a tetrahydrofuran solution (5 mL) of ethyl difluoroacetate (manufactured by Wako Pure Chemical Industries, 0.67 g, 3.3 mmol) was added dropwise and refluxed for 2 hours. Next, a tetrahydrofuran solution (3 mL) of anthraquinone (manufactured by Kanto Chemical Co., Ltd., 0.31 g, 1.5 mmol) was added dropwise and refluxed for 12 hours. After the reaction mixture was cooled to room temperature, 1N aqueous hydrochloric acid solution (10 mL) was added, and the precipitate was removed by centrifugation. To the solution was added saturated brine (10 mL), and the mixture was extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was separated and purified by flash column chromatography (manufactured by Kanto Chemical Co., Silica gel 60FC (Spherical), hexane / ethyl acetate = 7: 3). The obtained crystals were recrystallized from hexane to obtain the target compound (a) (0.36 g, 36% yield) as a white solid.

(result of analysis)
¹ H-NMR (CDCl ₃ ), δH (ppm): 1.02 (3H, t, J = 7.20 Hz), 4.03 (2H, q, J = 7.13 Hz), 4.20 (1H, br), 7.50 (2H, ddd, J = 7.58, 7.58, 1.25 Hz), 7.58 (2H, ddd, J = 7.77, 7.58, 1.50 Hz), 7 .82 (2H, d, J = 7.77 Hz), 8.13 (2H, dd, J = 7.58, 1.25 Hz);
¹³ C-NMR (CDCl ₃ ), δC (ppm): 13.53 (s), 63.43 (s), 74.47 (t, J = 24.18 Hz), 113.10 (t, J = 265) .62 Hz), 126.84 (s), 127.24 (s), 129.65 (s), 132.64 (s), 132.75 (s), 138.34 (s), 163.06 ( t, J = 31.58 Hz), 183.50 (s);
¹⁹ F-NMR (CDCl ₃ ), δF (ppm): −113.13 (s);
_{HRMS (ESI-MS), m} / z: 355.07544 (C 18 H 14 O 4 F 2 Na) (0.20 mmu) [Na was caused by glass sample tube];
IR (KBr, cm < ^-1 >): 3575-3350, 1755.

<Example 1-b: Synthesis of compound (b)>
After adding a 0.5 M sodium borohydride / 2-methoxyethyl ether solution (0.5 mL) dropwise to a tetrahydrofuran (3 mL) solution of the compound (a) (0.33 g, 1 mmol) at 0 ° C. in an argon atmosphere. Reflux was performed for 2 hours. 1 mol / L hydrochloric acid (5 mL) was added, and extraction operation was performed 3 times with diethyl ether. The extract was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was separated and purified by column chromatography (manufactured by Kanto Chemical Co., Silica gel 60FC (Spherical), hexane / ethyl acetate = 9: 1) to obtain a reduced product (0.12 g, 30% yield). . Subsequently, the reduction product (0.12 g), carbon tetrabromide (manufactured by Wako Pure Chemical, 0.2 g, 0.6 mmol), triphenylphosphine (manufactured by Aldrich, 0.18 g, 0.7 mmol) in dichloromethane (Kanto) The chemical, 5 ml) solution was stirred at room temperature for 15 hours. Dichloromethane was distilled off under reduced pressure, followed by separation and purification by column chromatography (manufactured by Kanto Chemical Co., Silica gel 60FC (Spherical), hexane / isopropyl alcohol = 95: 5) to obtain the desired compound (b) (0.06 g, 67% Yield (from reduced product)) was obtained as a pale yellow solid.

(result of analysis)
¹ H-NMR (CDCl ₃ ), δH (ppm): 0.92 (3H, t, J = 7.0 Hz), 4.02 (2H, q, J = 7.0 Hz), 7.16-7. 21 (2H, m), 7.68-7.72 (2H, m), 8.34-8.45 (4H, m), 8.73 (1H, s);
¹³ C-NMR (CDCl ₃ ), δC (ppm): 13.51, 64.77, 112.95 (t, J = 260.0 Hz), 121.23 (t, J = 48.0 Hz), 124. 84, 127.95, 129.65, 130.48, 136.63, 145.84, 162.26 (t, J = 24.0 Hz);
¹⁹ F-NMR (CDCl ₃ ), δF (ppm): −98.26;

<Example 2-a: Synthesis of compound (c)>
The same operation as in Example 1-a was carried out except that 0.86 g (13.2 mmol) of zinc and 1.34 g (6.6 mmol) of difluoroethyl acetate were changed to obtain the target compound (c). It was.

<Example 3-a: Synthesis of compound (d)>
The same operation was performed except that the anthraquinone of Example 1-a was changed to pentacenequinone (manufactured by Aldrich, 0.31 g, 1.0 mmol), 1N hydrochloric acid aqueous solution (10 mL) was added, and the precipitate was removed by centrifugation. It was. Saturated brine (10 mL) was added to the solution, the extract extracted with dichloromethane was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was separated and purified by flash column chromatography (manufactured by Kanto Chemical Co., Silica gel 60FC (Spherical), hexane / diethyl ether = 3: 1). The obtained crystals were recrystallized from hexane to obtain the target compound (d) (0.10 g, 22% yield) as a light brown solid.

(result of analysis)
¹ H-NMR (CDCl ₃ ), δH (ppm): 0.82 (3H, t, J = 7.16 Hz), 4.00 (2H, q, J = 7.16 Hz), 4.50 (1H, br), 7.62 (4H, m), 7.91 (2H, d, J = 7.8 Hz), 8.02 (2H, d, J = 7.8 Hz), 8.37 (2H, s) , 8.76 (2H, s);
¹³ C-NMR (CDCl ₃ ), δC (ppm): 13.51, 64.77, 75.02 (t, J = 24.9 Hz), 113.53 (t, J = 265.0 Hz), 126. 90, 127.70, 128.28, 129.06, 129.22, 129.76, 130.31, 132.84, 133.49, 134.89, 163.31 (t, J = 31.9 Hz) , 183.31;
¹⁹ F-NMR (CDCl ₃ ), δF (ppm): −112.85 (s);

<Compound solubility test>
In order to examine the applicability of the compound obtained above to a wet process, a solubility test of the compound in various solvents was performed. For comparison, anthracene solubility tests were also conducted.
Specifically, 20 mg of a sample was measured, and it was visually determined whether or not it was dissolved in 10 g of a solvent at room temperature (0.2% by mass).
The results are shown in Table 3.

In Table 3, ○ indicates dissolution and × indicates insolubility.
As a result of the solubility test, it was revealed that the compound synthesized in the present invention has higher solubility in an organic solvent than anthracene. In particular, it was found to dissolve in low polarity solvents such as hexane and cyclohexane.

The present invention provides a fluorine-containing aromatic compound that can be used in either a dry process or a wet process and is expected to have high mobility.
By using an acene skeleton exhibiting high mobility due to π-π interaction as a core and introducing a fluorine-containing ester group, the mobility can be further improved and the solubility in a low-polar solvent can be enhanced. In addition, by introducing the fluorine-containing ester group without using a metal coupling reaction or introducing the fluorine-containing ester group under conditions that facilitate removal of the metal, it is also possible to reduce heavy metal contamination that contributes to a decrease in carrier mobility. be able to.
With the improvement of solubility in organic solvents by introducing substituents and the improvement of high carrier mobility by introducing fluorine atoms and ester groups, organic semiconductor materials containing the compounds are used as organic EL elements for next-generation flat panel displays, The possibility of being used for an organic thin film solar cell, an organic thin film transistor, etc. as a lightweight and flexible power source is very high.

Claims (9)

A fluorine-containing aromatic compound represented by the following formula (2-1) or (2-2).

[In Formula (2-1) and Formula (2-2), Y ₁ is —CF ₂ CO ₂ R ₁ , and Y ₂ is a hydrogen atom or —CF ₂ CO ₂ R ₂ . Y _{1, Y R} 1 in _{2, R 2} are both, a hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms and may be the same or different.
Z _{3 to} Z ₆ are a hydrogen atom or a halogen atom, and these may be the same or different.
R _{3 to} R ₆ are each a hydrocarbon group having 1 to 12 carbon atoms that may have a substituent, an aromatic hydrocarbon group that may have a substituent, or a heteroaromatic group that may have a substituent. , A halogen atom or a hydrogen atom, which may be the same or different.
m and n are the repeating numbers of the repeating unit structures A and B shown in parentheses, m is an integer of 0 or more, n is an integer of 1 or more, and m + n is an integer of 2 or more and 6 or less.
L ₁ and L ₂ are each a hydrocarbon group having 1 to 12 carbon atoms that may have a substituent, an aromatic hydrocarbon group that may have a substituent, or a heteroaromatic group that may have a substituent. , A halogen atom, or a hydrogen atom, and when m is 2 or more, a plurality of L ₁ present in structure A may be the same or different, and a plurality of L ₁ present in structure A L ₂ may be the same or different.
The order in which the structure A and the structure B are combined may be random and is not limited. ] The compound represented by the formula (2-1) is a compound represented by the following formula (3-1) or the formula (4-1), and the compound represented by the formula (2-2) is represented by the following formula: The fluorine-containing aromatic compound of Claim 1 which is a compound represented by (3-2) or Formula (4-2).

[In Formula (3-1), Formula (3-2), Formula (4-1), and Formula (4-2), Y ₁ , Y ₂ , Z _{3 to} Z ₆ , and R _{3 to} R ₆ are the same as above. Indicates the same meaning. ] R _{3 to} R ₆ are each independently a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, an aromatic hydrocarbon group which may have a substituent, a halogen atom or a hydrogen atom. The fluorine-containing aromatic compound according to claim 1 or 2.   The organic-semiconductor material containing the fluorine-containing aromatic compound as described in any one of Claims 1-3. Fluorine-containing aromatic represented by the following formula (2-1-1) including the step of reacting the compound represented by the following formula (1) with X ₁ CF ₂ CO ₂ R ₁ and the step of aromatization A method for producing a compound.

[In the above formula, R ₁ is a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom.
X ₁ is a halogen atom.
Y ₁ is —CF ₂ CO ₂ R ₁ . R _{1 in} Y ₁ has the same meaning as described above.
Z _{3 to} Z ₆ are a hydrogen atom or a halogen atom, and these may be the same or different.
m and n are the repeating numbers of the repeating unit structures A and B shown in parentheses, m is an integer of 0 or more, n is an integer of 1 or more, and m + n is an integer of 2 or more and 6 or less.
L ₁ and L ₂ are each a hydrocarbon group having 1 to 12 carbon atoms that may have a substituent, an aromatic hydrocarbon group that may have a substituent, or a heteroaromatic group that may have a substituent. , A halogen atom, or a hydrogen atom, and when m is 2 or more, a plurality of L ₁ present in structure A may be the same or different, and a plurality of L ₁ present in structure A L ₂ may be the same or different.
The order in which the structure A and the structure B are combined may be random and is not limited. ] A compound represented by the following formula (1) is reacted with X ₁ CF ₂ CO ₂ R ₁ , reacted with X ₂ CF ₂ CO ₂ R ₂ , and aromatized. A method for producing a fluorine-containing aromatic compound represented by -1-2).

[In the above formula, R ₁ is a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, R ₂ is a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, and these may be the same or different. .
X ₁ and X ₂ are halogen atoms, and these may be the same or different.
Y ₁ is —CF ₂ CO ₂ R ₁ . R _{1 in} Y ₁ has the same meaning as described above.
Z _{3 to} Z ₆ are a hydrogen atom or a halogen atom, and these may be the same or different.
m and n are the repeating numbers of the repeating unit structures A and B shown in parentheses, m is an integer of 0 or more, n is an integer of 1 or more, and m + n is an integer of 2 or more and 6 or less.
L ₁ and L ₂ are each a hydrocarbon group having 1 to 12 carbon atoms that may have a substituent, an aromatic hydrocarbon group that may have a substituent, or a heteroaromatic group that may have a substituent. , A halogen atom, or a hydrogen atom, and when m is 2 or more, a plurality of L ₁ present in structure A may be the same or different, and a plurality of L ₁ present in structure A L ₂ may be the same or different.
The order in which the structure A and the structure B are combined may be random and is not limited. ] Including a step of reacting a compound represented by the following formula (1) with X ₁ CF ₂ CO ₂ R ₁ and aromatizing step, and when at least one of Z _{3 to} Z ₆ is a halogen atom, the _Z 3 to Z ₆ are atomic respectively comprising the step of substituting _R 3 to R _6, a method for producing a fluorine-containing aromatic compound represented by the following formula (2-2-1).

[In the above formula, R ₁ is a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom.
X ₁ is a halogen atom.
Y ₁ is —CF ₂ CO ₂ R ₁ . R _{1 in} Y ₁ has the same meaning as described above.
Z _{3 to} Z ₆ are a hydrogen atom or a halogen atom, and these may be the same or different.
R _{3 to} R ₆ are each a hydrocarbon group having 1 to 12 carbon atoms that may have a substituent, an aromatic hydrocarbon group that may have a substituent, or a heteroaromatic group that may have a substituent. , A halogen atom or a hydrogen atom, which may be the same or different.
m and n are the repeating numbers of the repeating unit structures A and B shown in parentheses, m is an integer of 0 or more, n is an integer of 1 or more, and m + n is an integer of 2 or more and 6 or less.
L ₁ and L ₂ are each a hydrocarbon group having 1 to 12 carbon atoms that may have a substituent, an aromatic hydrocarbon group that may have a substituent, or a heteroaromatic group that may have a substituent. , A halogen atom, or a hydrogen atom, and when m is 2 or more, a plurality of L ₁ present in structure A may be the same or different, and a plurality of L ₁ present in structure A L ₂ may be the same or different.
The order in which the structure A and the structure B are combined may be random and is not limited. ] Including a step of reacting a compound represented by the following formula (1) with X ₁ CF ₂ CO ₂ R ₁ , a step of reacting with X ₂ CF ₂ CO ₂ R ₂ , and a step of aromatization, and further including Z ₃ If at least one to Z ₆ is a halogen atom, a _Z 3 to Z ₆ are halogen atoms, respectively, including the step of substituting with _R 3 to R _6, fluorine-containing represented by the following formula (2-2-2) A method for producing an aromatic compound.

[In the above formula, R ₁ is a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, R ₂ is a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, and these may be the same or different. .
X ₁ and X ₂ are halogen atoms, and these may be the same or different.
Y ₁ is —CF ₂ CO ₂ R ₁ . R _{1 in} Y ₁ has the same meaning as described above.
Z _{3 to} Z ₆ are a hydrogen atom or a halogen atom, and these may be the same or different.
R _{3 to} R ₆ are each a hydrocarbon group having 1 to 12 carbon atoms that may have a substituent, an aromatic hydrocarbon group that may have a substituent, or a heteroaromatic group that may have a substituent. , A halogen atom or a hydrogen atom, which may be the same or different.
m and n are the repeating numbers of the repeating unit structures A and B shown in parentheses, m is an integer of 0 or more, n is an integer of 1 or more, and m + n is an integer of 2 or more and 6 or less.
L ₁ and L ₂ are each a hydrocarbon group having 1 to 12 carbon atoms that may have a substituent, an aromatic hydrocarbon group that may have a substituent, or a heteroaromatic group that may have a substituent. , A halogen atom, or a hydrogen atom, and when m is 2 or more, a plurality of L ₁ present in structure A may be the same or different, and a plurality of L ₁ present in structure A L ₂ may be the same or different.
The order in which the structure A and the structure B are combined may be random and is not limited. ] A fluorine-containing aromatic compound represented by any of the following formulas.