JP2011183366A - Catalyst composition for c-c coupling reaction - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for C-C coupling reactions suitable for industrial applications which does not need a strict water prohibition and is problem-free in the C-C coupling reaction using the conventional silver nitrate or silver fluoride. <P>SOLUTION: A catalyst composition for C-C coupling reactions includes a palladium complex catalyst and a lithium base. In the palladium complex catalyst, a valency of a palladium atom is zero-valent or bivalent, and the ligand coordinating on the palladium atom is preferably at least one kind of compound or an atom selected from the group consisting of a phosphine compound, an aryl compound, a nitrile compound, and a carbonyl compound a halogen atom. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a novel catalyst composition for CC coupling reaction.

  In conventional CC coupling reactions, hydrocarbon halides, organomagnesium reagents (Grignard reagents), organozinc reagents (Barbière reagents), organotin reagents (stille-coupling) in the presence of transition metal catalysts. Or an organic boronic acid (suzuki-coupling) etc. were made to act, and the coupling body was obtained by that (refer nonpatent literature 1). In this coupling reaction, activation of the C-halogen bond of the halide and activation of the carbon-metal bond of various organometallic reagents occur, thereby producing a coupling product.

  However, the organometallic reagents used in these coupling reactions are unstable to moisture and highly ignitable, so they are difficult to handle in the atmosphere and are strictly monitored under an inert atmosphere such as nitrogen. It needs to be handled below. Therefore, the above coupling reaction cannot be said to be an industrially preferable reaction from the viewpoint of safety of the handler and from the point that the production process becomes complicated.

  On the other hand, in Non-Patent Documents 2 to 4 and Patent Document 1, 2-bromothiophene or 2-formylthiophene and halogen are used using silver nitrate or silver fluoride as a reaction accelerator in the coupling reaction in the presence of a palladium catalyst. By reacting with a halogenated aryl compound, a C—C coupling body is obtained by utilizing the C—H bond of 2-bromothiophene or 2-formylthiophene and the activation of the C-halogen bond of the halogenated aryl compound. It is disclosed.

  In view of conventional knowledge, activation of C-Br bond of 2-bromothiophene or C-CHO bond of 2-formylthiophene should occur, while The formation of a coupling body by the C—H bond activation is observed. Regarding this C—C coupling, the authors of the above literature suggest that the coupling reaction proceeds by a mechanism different from that of the conventional catalytic cycle.

  In such a reaction using silver nitrate or silver fluoride as a reaction accelerator, it is not necessary to use an organometallic reagent, so that strict water prohibition is not required. However, in obtaining a coupling body, it is difficult to remove the by-product (for example, silver halide) generated from the silver nitrate and silver fluoride, and from the environmental aspect, the use of these silver compounds is industrial. This is not preferable.

Patent Document 2 discloses hydrogen that obtains a β-pinene polymer by converting unsaturated bonds in the main chain and / or side chain of a polymer containing 30% by mass or more of β-pinene units into saturated bonds. In the hydrogenation reaction, a “hydrogenation method” of a β-pinene polymer, wherein a heterogeneous hydrogenation catalyst containing a metal is used and M (OR) _n or the like coexists (n is 1 or 2). Is disclosed). [0042] of the document discloses that the metal in the heterogeneous hydrogenation catalyst is preferably palladium, and [0048] includes lithium as an example of M of M (OR) _n. And t-butyl group is mentioned as an example of R.

Japanese Patent Laid-Open No. 2005-220075 JP 2009-270097 A

Tetrahedron Lett. 2008, 49, 1000-1003 Org. Lett. 2005, 7, 5083-5085 J. Am. Chem. Soc. 2004, 126, 5074-5075 Bulletin of the Chemical Society of Japan Vol.81, No.5 548-561

  Therefore, the present invention does not require strict water-absorptiveness, and is a problem when silver nitrate or silver fluoride is used, such as the CC coupling reaction described in Non-Patent Documents 2 to 4 and Patent Document 1. An object of the present invention is to provide a catalyst for CC coupling reaction suitable for industrial use.

The catalyst composition for CC coupling reaction of the present invention is characterized by containing a palladium complex catalyst and a lithium base.
That is, the present inventors have the same catalytic cycle as the CC coupling reaction described in Non-Patent Documents 2 to 4 and Patent Document 1 in the CC coupling reaction using a palladium complex catalyst and a lithium base as a catalyst. In this reaction, strictly water-free water is not required, and it is not difficult to remove by-products generated from the lithium base, and the reaction is environmentally friendly. However, it was found that there is no particular problem, and the present invention has been completed.

  In the palladium complex catalyst, the valence of the palladium atom is zero or divalent, and the ligand coordinated to the palladium atom is selected from the group consisting of phosphine compounds, aryl compounds, nitrile compounds, carbonyl compounds, and halogen atoms. Preferably it is at least one compound or atom.

In the palladium complex catalyst, the ligand is preferably coordinated by 1 to 4 moles per mole of palladium atoms.
The structure of the lithium base is usually a structure in which an anion is ionically bonded to lithium as a cation, and the anion is a carboanion or an alkoxy anion.

The catalyst composition for CC coupling reaction of the present invention can be suitably used for CC coupling reaction of an aryl compound and an aryl halide compound.
The aryl compound is an optionally substituted heteroaromatic ring compound, and at least one carbon atom constituting the heteroaromatic ring adjacent to the heteroatom constituting the heteroaromatic ring is not substituted. It is preferably a heteroaromatic ring compound.

  Examples of the heteroaromatic ring compound include thiophene represented by the following formula (1) or a derivative thereof.

式（１）において、Ｒ¹、Ｒ²およびＲ³はそれぞれ独立に水素原子、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、置換されていてもよい炭素数６〜１０のアリール基または炭素数５〜１０の脂環族基であり、Ｒ¹およびＲ²は互いに結合して５もしくは６員の芳香環を形成してもよく、該芳香環はヘテロ原子を有していてもよく、該芳香環は置換されていてもよく、Ｒ²およびＲ³は互いに結合して５もしくは６員の脂環構造を形成してもよく、該脂環構造はヘテロ原子を有していてもよく、該脂環構造は置換されていてもよい。

In the formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an optionally substituted carbon number. An aryl group having 6 to 10 carbon atoms or an alicyclic group having 5 to 10 carbon atoms, R ¹ and R ² may be bonded to each other to form a 5- or 6-membered aromatic ring, and the aromatic ring is a heteroatom And the aromatic ring may be substituted, R ² and R ³ may be bonded to each other to form a 5- or 6-membered alicyclic structure, and the alicyclic structure is heterogeneous. It may have an atom and the alicyclic structure may be substituted.

  Examples of the halogenated aryl compound include aryl derivatives represented by the following formula (2).

式（２）において、Ｒａ、ＲｂおよびＲｃはそれぞれ独立に炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、置換されていてもよい炭素数６〜１０のアリール基または炭素数５〜１０の脂環族基であり、Ｘはハロゲン原子であり、置換基数を示すｍ１は０〜３の整数であり、ｍ２は０〜５の整数であり、ｍ３は０〜４の整数であり、ｍ１が２以上の場合、複数存在するＲａは同一でも異なっていてもよく、ｍ２が２以上の場合、複数存在するＲｂは同一でも異なっていてもよく、ｍ３が２以上の場合、複数存在するＲｃは同一でも異なっていてもよい。

In Formula (2), Ra, Rb and Rc are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 10 carbon atoms, or carbon number. 5 to 10 alicyclic groups, X is a halogen atom, m1 indicating the number of substituents is an integer of 0 to 3, m2 is an integer of 0 to 5, and m3 is an integer of 0 to 4. Yes, when m1 is 2 or more, a plurality of Ra may be the same or different, and when m2 is 2 or more, a plurality of Rb may be the same or different, and when m3 is 2 or more, a plurality of Ra The Rc present may be the same or different.

  Furthermore, the C—C coupling reaction using the catalyst composition for C—C coupling reaction of the present invention involves contacting an aryl compound with a halogenated aryl compound, and bonding between carbon-hydrogen atoms of the aryl compound. And a carbon-halogen atom bond in the halogenated aryl compound to activate a C—C coupling reaction to form a bond between the carbon-carbon atoms, a palladium complex catalyst and a lithium base are included. The CC coupling reaction is carried out in a polar protic organic solvent in the presence of the catalyst composition for CC coupling reaction, and a polycyclic aromatic compound is produced by the reaction.

  The aryl compound is preferably an optionally substituted heteroaromatic ring compound, and at least one carbon atom constituting the heteroaromatic ring adjacent to the heteroatom constituting the heteroaromatic ring is substituted. It is not a heteroaromatic ring compound.

  Examples of the heteroaromatic ring compound include thiophene represented by the following formula (1) or a derivative thereof.

式（１）において、Ｒ¹、Ｒ²およびＲ³はそれぞれ独立に水素原子、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、置換されていてもよい炭素数６〜１０のアリール基または炭素数５〜１０の脂環族基であり、Ｒ¹およびＲ²は互いに結合して５もしくは６員の芳香環を形成してもよく、該芳香環はヘテロ原子を有していてもよく、該芳香環は置換されていてもよく、Ｒ²およびＲ³は互いに結合して５もしくは６員の脂環構造を形成してもよく、該脂環構造はヘテロ原子を有していてもよく、該脂環構造は置換されていてもよい。

In the formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an optionally substituted carbon number. An aryl group having 6 to 10 carbon atoms or an alicyclic group having 5 to 10 carbon atoms, R ¹ and R ² may be bonded to each other to form a 5- or 6-membered aromatic ring, and the aromatic ring is a heteroatom And the aromatic ring may be substituted, R ² and R ³ may be bonded to each other to form a 5- or 6-membered alicyclic structure, and the alicyclic structure is heterogeneous. It may have an atom and the alicyclic structure may be substituted.

  In the palladium complex, a compound in which the valence of the palladium atom is 0 or 2 and the ligand coordinated to the palladium atom is selected from the group consisting of a phosphine compound, an aryl compound, a nitrile compound, a carbonyl compound, and a halogen atom Or it is an atom and it is preferable that the said ligand coordinates 1-4 mol with respect to 1 mol of said palladium atoms.

  Examples of the halogenated aryl compound include aryl derivatives represented by the following formula (2).

式（２）においてＲａ、ＲｂおよびＲｃはそれぞれ独立に炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、置換されていてもよい炭素数６〜１０のアリール基または炭素数５〜１０の脂環族基であり、置換基数を示すｍ１は０〜３の整数であり、ｍ２は０〜５の整数であり、ｍ３は０〜４の整数であり、ｍ１が２以上の場合、複数存在するＲａは同一でも異なっていてもよく、ｍ２が２以上の場合、複数存在するＲｂは同一でも異なっていてもよく、ｍ３が２以上の場合、複数存在するＲｃは同一でも異なっていてもよい。

In formula (2), Ra, Rb and Rc are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 10 carbon atoms, or 5 carbon atoms. Is an alicyclic group of 10 to 10, m1 indicating the number of substituents is an integer of 0 to 3, m2 is an integer of 0 to 5, m3 is an integer of 0 to 4, and m1 is 2 or more. A plurality of Ra may be the same or different; when m2 is 2 or more, a plurality of Rb may be the same or different; and when m3 is 2 or more, a plurality of Rc are the same or different. May be.

  The amount of the C—C coupling reaction catalyst composition used is preferably 0.1 to 50 mol% with respect to the charged molar amount of the halogenated aryl compound in terms of the palladium complex catalyst.

Also, in the catalyst composition for CC coupling reaction, the structure of the lithium base is a structure in which an anion is ionically bonded to lithium as a cation, and the anion is a carbanion or an alkoxy anion, It is preferable that the usage-amount of the catalyst composition for CC coupling reaction is 0.1-50 equivalent with respect to 1 equivalent of preparation amount of the said aryl compound in conversion of the said lithium base.
The reaction temperature of the C—C coupling reaction is usually 40 to 150 ° C.

  According to the catalyst composition for CC coupling reaction of the present invention, no strict water prohibition is required, there is no problem from an environmental aspect, and it is difficult to remove a by-product. The reaction can be carried out.

  Hereinafter, each component which comprises the catalyst composition for CC coupling reaction of this invention (henceforth only "the catalyst composition of this invention"), and the usage method of this catalyst composition are demonstrated in detail.

[Palladium complex catalyst]
The palladium complex catalyst constituting the catalyst composition of the present invention is not particularly limited as long as it is a compound obtained by reacting (coordinating) an arbitrary compound or atom serving as a ligand to a palladium atom. The palladium complex catalyst is considered to have an action of generating a carbon-carbon bond between two compounds or structures in the CC coupling reaction.

The valence of the palladium atom is usually zero or divalent.
Examples of the compound serving as the ligand include phosphine compounds, aryl compounds, nitrile compounds, carbonyl compounds, and halogen atoms. The phosphine compound is coordinated by a phosphorus atom, the aryl compound is haptocoordinated by a carbon atom by π electrons, the nitrile compound is coordinated by a nitrogen atom, and the carbonyl compound is oxygen atom-carbon atom- Hapto 3 coordination by oxygen atom.

  Among these ligands, steric hindrance affecting the catalytic activity of the C—C coupling reaction, steric hindrance of the ligand for adjusting the electron density on the palladium atom, and electron donor of the ligand A phosphine compound is preferable from the viewpoint of high extensibility of molecular design, such as adjustment of properties.

Examples of the phosphine compound include tri-tert-butylphosphine and triphenylphosphine.
Examples of the aryl compound include cyclopentadienyl and 1,2,3,4,5-pentamethylcyclopentadienyl.

Examples of the nitrile compound include acetonitrile and benzonitrile.
Examples of the carbonyl compound include acetylacetone and dibenzylideneacetone.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
In the palladium complex catalyst having such a ligand, it is preferable that 1 to 4 mol of the ligand is coordinated with respect to 1 mol of the palladium atom. The ratio is more preferably 2 molar coordination (2 molar coordination of ligand to 1 molar palladium atom).

Some palladium complex catalysts having such a ligand are commercially available, but can be separately synthesized from a palladium precursor raw material by a ligand exchange reaction or the like. Further, by adding each of the palladium precursor and the ligand in the coupling reaction system, it is possible to form a palladium complex catalyst in the reaction system and perform the CC coupling reaction. The catalytic activity of the catalyst composition of the present invention containing a palladium complex catalyst synthesized in such a reaction system is almost the same as that of a palladium complex catalyst obtained by synthesis outside the reaction system. The content of the palladium complex catalyst in the catalyst composition of the present invention will be described in the section <Reaction conditions, etc.> in [Method for producing polycyclic aromatic compound] described later.
In the catalyst composition of the present invention, the palladium complex catalyst may be included singly or in combination of two or more.

[Lithium base]
The lithium base contained in the catalyst composition of the present invention is a strong base that promotes the C—C coupling reaction. The lithium base has a structure in which an anion is ionically bonded to lithium as a cation. Examples of the anion include a carbanion and an alkoxy anion. The carbon number of alkoxy in the alkoxy anion is usually 1-10.

Specific examples of the lithium base include tBuOLi, n-BuLi, t-BuLi, sec-BuLi, LiNH ₂ and lithium pentamethylcyclopentadienide. When this specific strong base is present in the CC coupling reaction, for example, when the catalyst composition of the present invention is used for the CC coupling reaction of an aryl compound and an aryl halide compound described later, It is considered that the C—C coupling reaction is promoted by carbon-hydrogen bond activation of the aryl compound, stabilization of the carbanion of the polycyclic aromatic compound to be generated, and capture of protons desorbed from the aryl compound. . The content of the lithium base in the catalyst composition of the present invention will be described in the section <Reaction conditions, etc.> in [Method for producing polycyclic aromatic compound] described later.

  In the catalyst composition of the present invention, the lithium base may be included singly or in combination of two or more.

[Other ingredients]
The catalyst composition of the present invention may contain a supporting ligand or the like for the purpose of improving the reaction activity of the palladium complex catalyst within a range not impairing the effects of the present invention.
Specific examples of the supporting ligand include the following compounds.

これらの支持配位子を使用する場合、その含有量は、本発明の触媒組成物に含まれるパラジウム錯体触媒１当量あたり、０．１〜１０当量となる量が好ましい。

When using these supporting ligands, the content thereof is preferably 0.1 to 10 equivalents per equivalent of the palladium complex catalyst contained in the catalyst composition of the present invention.

  The catalyst composition of the present invention may contain a halogen trap agent such as potassium carbonate or a tertiary amine for the purpose of accelerating the palladium catalyst cycle as long as the effects of the present invention are not impaired. When these halogen trapping agents are used, the preferred amount used is a reaction substrate when the catalyst composition of the present invention is used for a CC coupling reaction between an aryl compound and a halogenated aryl compound described later. Is usually from 0.1 to 50 equivalents, more preferably from 1 to 10 equivalents, per equivalent of the charged amount of the halogenated aryl compound or aryl compound.

[Method for Preparing the Catalyst Composition of the Present Invention]
The catalyst composition of the present invention can be prepared, for example, by physically mixing the constituent components described above. In order to facilitate mixing, the palladium complex catalyst or the lithium base may be subjected to mixing in a state where they are dissolved in a soluble solvent. Examples of the solvent include a reaction solvent that can be used in the production of a polycyclic aromatic compound described in the section <Reaction conditions and the like> in [Method for producing polycyclic aromatic compound] described later. The solvents may be used alone or in combination of two or more.

  Moreover, although the catalyst composition of this invention is used for CC coupling reaction, each said component may be thrown into this coupling reaction system, and a catalyst composition may be prepared in a coupling reaction system. Also in this charging, the palladium complex catalyst or lithium base may be in a state dissolved in a solvent.

[Method of using the catalyst composition of the present invention]
The catalyst composition of the present invention contains the above-described palladium complex catalyst and a lithium base, and according to the catalyst composition, the C—C coupling reaction using a conventional silver compound as a reaction accelerator is similar to the C—C coupling reaction. C-coupled bodies can be synthesized. Moreover, the C—C coupling reaction using the catalyst composition does not require strict water prohibition, does not produce a by-product that is difficult to remove, and is not particularly problematic from an environmental aspect.

[Method for producing polycyclic aromatic compound]
The catalyst of the present invention, for example, contacts an aryl compound and a halogenated aryl compound, and activates a bond between the carbon-hydrogen atom of the aryl compound and a bond between the carbon-halogen atom of the halogenated aryl compound. Between carbon-carbon atoms (the carbon atom constituting the activated carbon-hydrogen atom bond in the aryl compound and the activated carbon-halogen atom bond in the halogenated aryl compound). It can be suitably used for a reaction for producing a polycyclic aromatic compound by carrying out a C—C coupling reaction for forming a bond between the constituent carbon atoms).

  Examples of the polycyclic aromatic compound include bithiophene and the like, but these are used as raw materials for organic semiconductors such as organic TFTs, light-emitting elements, and organic solar cells because of their optical characteristics, electrochemical behavior, and liquid crystal characteristics. It is a compound that is attracting attention as an advanced material that can be used. Hereinafter, reaction raw materials, reaction conditions, and the like in the method for producing the polycyclic aromatic compound will be described.

<Reaction raw materials>
(Aryl compound)
An example of the aryl compound is an optionally substituted heteroaromatic ring compound, wherein at least one carbon atom constituting the heteroaromatic ring adjacent to the heteroatom constituting the heteroaromatic ring is substituted. Heteroaromatic ring compounds that are not used are mentioned.

  Examples of the substituent in the heteroaromatic ring compound include a substituent that forms a condensed ring such as a 6-membered ring and a 5-membered ring, and an aromatic group such as a substituted or unsubstituted benzene ring, pyridine ring, and thiophene ring. It is done. Since these substituents are bonded, the carbon-hydrogen bond is not activated at the site where the substituent is bonded, and the carbon-hydrogen bond to which the substituent is not bonded is selectively activated. A coupling body with an aryl compound is obtained.

  Among the substituents exemplified above, benzo [b] thiophene having a substituent that forms a 6-membered condensed ring, a substituted or unsubstituted benzene ring, and a thiophene ring are preferable from the viewpoint of reaction efficiency.

  Furthermore, it is preferable from the viewpoint of reaction efficiency that these substituents are bonded to carbon having high cationicity (low electron density) in the original unsubstituted aromatic ring compound.

  In the heteroaromatic ring compound, the hydrogen atom bonded to the carbon atom constituting the heteroaromatic ring adjacent to the heteroatom constituting the heteroaromatic ring is activated, and the halogen atom of the halogenated aryl compound is bonded to the carbon atom. A C—C coupling reaction proceeds with the atom.

  When the heteroaromatic compound does not have a substituent, the electron density on the two carbons on both sides of the heteroatom constituting the heteroaromatic ring is almost the same, so the carbon-hydrogen bond on both sides is activated. The As a result, a coupled product in which two molecules of a halogenated aryl compound are added to one molecule of a heteroaromatic ring compound is obtained by a CC coupling reaction.

  In order to preferentially obtain a coupled product in which two molecules of such an aryl halide compound are added, the raw material charge ratio is changed, for example, 2.5 equivalents of an aryl halide is charged per 1 equivalent of a heteroaromatic ring compound. In order to improve the effect of deprotonation from the carbon-hydrogen bond in the heteroaromatic ring compound, the amount of lithium base added (that is, the amount of the catalyst composition of the present invention used or the content of lithium base in the composition) is increased. Such a device is necessary.

The heteroaromatic ring compound is usually a 5- to 6-membered cyclic aromatic compound.
Examples of the hetero atom constituting the heterocyclic ring include a sulfur atom, an oxygen atom, and a nitrogen atom. Among these, a sulfur atom is preferable from the viewpoint of deprotonation reactivity.

Furthermore, the number of heteroatoms in the heterocycle may vary depending on the number of ring-constituting atoms of the heterocycle, but is usually 1 to 2.
As the heteroaromatic ring compound described above, thiophene represented by the following formula (1) or a derivative thereof is preferable.

式（１）において、Ｒ¹、Ｒ²およびＲ³はそれぞれ独立に水素原子、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、置換されていてもよい炭素数６〜１０のアリール基または炭素数５〜１０の脂環族基である。前記ハロゲン原子の例としては、フッ素原子、塩素原子、臭素原子およびヨウ素原子が挙げられる。

In the formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an optionally substituted carbon number. It is a 6-10 aryl group or a C5-C10 alicyclic group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

From the viewpoint of selectively obtaining a hetero cross-coupled product, R ¹ , R ² and R ³ preferably each independently have a substituent, R ¹ and R ² each have a substituent, and R ³ represents hydrogen. More preferably it is an atom.

Further, in the formula (1), R ¹ and R ² may be bonded to each other to form a 5- or 6-membered aromatic ring, the aromatic ring may have a hetero atom, and the aromatic ring is R ² and R ³ may be bonded to each other to form a 5- or 6-membered alicyclic structure, and the alicyclic structure may have a hetero atom. The structure may be substituted.

  Examples of the hetero atom include oxygen, nitrogen, and sulfur atoms. Examples of the substituent bonded to the aromatic ring or alicyclic structure include a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and carbon. The alkoxy group of number 1-10 is mentioned.

The heteroaromatic ring compounds described above are commercially available and can be easily synthesized by known methods.
In the method for producing a polycyclic aromatic compound of the present invention, the heteroaromatic compound may be used alone or in combination of two or more.

(Halogenated aryl compounds)
The halogenated aryl compound is not particularly limited as long as it is substituted with a halogen atom, and may be further substituted with another substituent. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

  In the CC coupling reaction with the heteroaromatic ring compound, the carbon atom to which the halogen atom is bonded in the halogenated aryl compound is activated and adjacent to the heteroatom constituting the heteroaromatic ring in the heteroaromatic ring compound. A coupling reaction proceeds with the activated carbon atom.

Other substituents other than halogen atoms may be bonded to the halogenated aryl compound. Examples thereof include an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms. Examples thereof include an aryl group having 6 to 10 carbon atoms and an alicyclic group having 5 to 10 carbon atoms.
As the halogenated aryl compounds described above, the following compounds are preferred.

式（２）において、Ｒａ、ＲｂおよびＲｃはそれぞれ独立に炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、置換されていてもよい炭素数６〜１０のアリール基または炭素数５〜１０の脂環族基である。

In Formula (2), Ra, Rb and Rc are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 10 carbon atoms, or carbon number. 5 to 10 alicyclic groups.

Moreover, in Formula (2), m1 which shows the number of substituents is an integer of 0-3, m2 is an integer of 0-5, m3 is an integer of 0-4.
When m1 is 2 or more, a plurality of Ra may be the same or different.
When m2 is 2 or more, a plurality of Rb may be the same or different.
When m3 is 2 or more, a plurality of Rc may be the same or different.

The aryl halide compounds described above are commercially available and can be easily synthesized by known methods.
In the method for producing a polycyclic aromatic compound of the present invention, the aryl halide compounds may be used alone for the reaction or in combination of two or more.

<Reaction conditions, etc.>
In the present invention, the CC coupling reaction is carried out by reacting the aryl compound with the aryl halide compound in a polar aprotic organic solvent in the presence of the catalyst composition of the present invention. The For example, when the aryl compound is 2-methylthiophene and the halogenated aryl compound is 1-bromo-4-methylbenzene, the following reaction occurs.

上記式において、Ｘはパラジウム錯体触媒における配位子であり、^tBuOLiはリチウム塩基である。

In the above formula, X is a ligand in the palladium complex catalyst, and ^t BuOLi is a lithium base.

The reaction is carried out in a polar aprotic organic solvent as described above. This is to stabilize the intermediate in the reaction.
Specific examples of the polar aprotic organic solvent include N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dibutylacetamide, N, N-dibutylformamide, N, N, N ′, N '-Tetramethylurea, DMSO, carbon disulfide, THF, cyclopentylmethyl ether, methyl t-butyl ether, 1,4-dioxane, pyridine, 4-N, N-dimethylpyridine, N-methylpyrrolidone, dimethyl carbonate, diethyl carbonate , Acetonitrile and benzonitrile.

  In the CC coupling reaction in the method for producing a polycyclic aromatic compound of the present invention, the polar aprotic organic solvent may be used singly or in combination of two or more.

  The amount of the palladium complex catalyst in the catalyst composition of the present invention is usually 0.1 to 50 mol% with respect to the charged molar amount of the halogenated aryl compound as the reaction substrate in the above reaction, preferably 1 to 1 mol%. The amount is 10 mol%.

  Moreover, the amount of the lithium base in the catalyst composition of the present invention is usually an amount of 0.1 to 50 equivalents, preferably 1 to 10 equivalents, relative to one equivalent of the charged mole number of the aryl compound as the reaction substrate. Is the amount.

  In order to simultaneously achieve the preferred amounts of the palladium complex catalyst and the lithium base described above, the content of the palladium complex catalyst in the catalyst composition of the present invention is preferably 0.1 to 50 mol% with respect to the aryl halide compound. The lithium base content is preferably 0.1 to 50 equivalents and more preferably 1 to 10 equivalents with respect to 1 equivalent of the aryl compound.

  Moreover, the use ratio of the aryl compound and the halogenated aryl compound is usually in the range of aryl compound: halogenated aryl compound = 1: 0.5 to 1: 5.0, preferably 1: The range is 1-1: 3.0.

The reaction temperature of the reaction is usually 40 to 150 ° C., and preferably 60 to 120 ° C. from the viewpoint of reaction efficiency.
The reaction time of the reaction is usually 3 to 48 hours, and preferably 10 to 24 hours from the viewpoint of reaction efficiency.

  In order to terminate the reaction, water may be added as a quencher. For this reason, in this reaction, strict water prohibition is not required, but care must be taken not to mix water to stop the reaction into the reaction system.

  In the CC coupling reaction described above, since the catalyst composition of the present invention includes a palladium complex catalyst and a lithium base, a CC coupling reaction using a conventional organometallic reagent that is a strong base. In contrast, in the C—C coupling reaction using the catalyst composition of the present invention, strict water prohibition is not required, and care must be taken not to mix water to stop the reaction into the reaction system. It is enough to do. In addition, as a result of performing the C—C coupling reaction, the palladium complex catalyst and the lithium base are changed to an inactive state such as metal palladium and lithium halide, and these are reaction solutions such as filtration and liquid separation extraction. By-products such as CC coupling reactions using silver compounds as reaction accelerators described in Non-Patent Documents 2 to 4 and Patent Document 1 are easily removed at the post-treatment stage. The removal process does not become difficult.

  In the method for producing a polycyclic aromatic compound of the present invention, after synthesizing a polycyclic aromatic compound as described above, a purification step by column chromatography or sublimation for high purity for an organic electronic device material. Steps such as purification may be performed.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
[Example 1]
The reaction shown in the following formula was carried out using the catalyst composition of the present invention.

反応原料として、０．６ｍｍｏｌのベンゾチオフェンおよびそれに対して１．２当量の１−ブロモ−４−メチルベンゼンを使用した。

As reaction raw materials, 0.6 mmol of benzothiophene and 1.2 equivalents of 1-bromo-4-methylbenzene were used.

The 25 mL Schlenk tube was replaced with nitrogen gas, and a solution of 3 equivalents of tert-butoxylithium in 0.5 mL of THF (tetrahydrofuran) was added to the Schlenk tube. Further DMF was added to a 2 mL Schlenk tube. Then, while stirring the contents of the Schlenk tube, orange Pd (P ^t Bu ₃ ) ₂ (manufactured by Aldrich) is added to the 2 mol% Schlenk tube with respect to the raw material benzothiophene, and then the reaction raw material benzothiophene. And 1-bromo-4-methylbenzene was added and reacted at 100 ° C. for 16 hours.

Thereafter, water is added to quench the reaction, extraction is performed using water and diethyl ether, the solvent of the organic layer is distilled off under reduced pressure, and 1-benzothienyl-4-product, which is a product of the CC coupling reaction. Methylbenzene was obtained. When the NMR yield of this was measured, the ¹ H NMR yield was 97%. The NMR measurement conditions are as follows.

¹ H NMR spectrum was measured using JEOL JNM-ECX500M with tetramethylchlorosilane (TMS) as an internal standard in a deuterated chloroform solvent (the same was applied to the following examples and comparative examples).

[Examples 2 to 4]
A CC coupling reaction was carried out in the same manner as in Example 1 except that the amount of palladium complex catalyst and tert-butoxylithium used, the type of reaction solvent, and the reaction time were changed as shown in Table 1 below. . Table 1 also shows the ¹ H NMR yield of the product of the C—C coupling reaction.

［実施例５］
本発明の触媒組成物を用いて、下記式に示す反応を実施した。

[Example 5]
The reaction shown in the following formula was carried out using the catalyst composition of the present invention.

反応原料として、０．５ｍｍｏｌの２−メチルチオフェンおよびそれに対して１．２当量の１−ブロモ−４−メチルベンゼンを使用した。

As reaction raw materials, 0.5 mmol of 2-methylthiophene and 1.2 equivalents of 1-bromo-4-methylbenzene were used.

The 25 mL Schlenk tube was dried and replaced with nitrogen gas. To the Schlenk tube, 3 equivalents of tert-butoxylithium were weighed and added in a solid state. In addition, TMU was added to a 2 mL Schlenk tube. Then, while stirring the liquid content of the Schlenk tube, orange Pd (P ^t Bu _{3) 2} and (Aldrich Co.) was added to 2 mol% Schlenk tube with respect to 2-methylthiophene, then is the reaction feedstock 2-methylthiophene and 1-bromo-4-methylbenzene were added and reacted at 100 ° C. for 15 hours.

Thereafter, water is added to quench the reaction, extraction is performed using water and diethyl ether, the solvent in the organic layer is evaporated under reduced pressure, and 1- (2-methylthienyl) which is a product of the CC coupling reaction. -4-Methylbenzene was obtained. The ¹ H NMR yield of this product was determined under the same conditions as in Example 1, and the yield was 35%.

[Examples 6 to 11]
The CC coupling reaction was carried out in the same manner as in Example 5 except that the kind and amount of the palladium complex catalyst to be used, the kind and amount of the reaction solvent, the reaction temperature and the reaction time were changed as shown in Table 2 below. Carried out. In Example 7 and Example 8, the compound represented by the following formula (A) (Example 7) and the compound represented by the following formula (B) (Example) as the supporting ligand of the palladium complex catalyst. 8) was added to the Schlenk tube at the stage of raw material charging.

（上記式において、Ｃｙはシクロヘキシル基を表す。）。

(In the above formula, Cy represents a cyclohexyl group).

^{The 1} H NMR yield is also shown in Table 2.

［実施例１２〜１８］
使用するパラジウム錯体触媒の種類及び量、反応溶媒の種類および使用量、反応温度および反応時間を下記表３に示すように変更した以外は、実施例６と同様にしてＣ−Ｃカップリング反応を実施した。なお、実施例１２〜１８においては、パラジウム錯体触媒の支持配位子として下記式（Ｃ）で表される化合物（実施例１２、１４、１６）および下記式（Ｄ）で表される化合物（実施例１３、１５、１７、１８）を原料仕込みの段階でシュレンク管に添加した。

[Examples 12 to 18]
The CC coupling reaction was carried out in the same manner as in Example 6 except that the kind and amount of the palladium complex catalyst to be used, the kind and amount of the reaction solvent, the reaction temperature and the reaction time were changed as shown in Table 3 below. Carried out. In Examples 12 to 18, compounds (Examples 12, 14, and 16) represented by the following formula (C) and compounds represented by the following formula (D) (as a supporting ligand for the palladium complex catalyst) Examples 13, 15, 17, 18) were added to the Schlenk tube at the stage of raw material charging.

［実施例１９］
本発明の触媒組成物を用いて、下記式に示す反応を実施した。

[Example 19]
The reaction shown in the following formula was carried out using the catalyst composition of the present invention.

反応原料として、式（１ａ）で表される２−メチルチオフェンを０．６ｍｍｏｌ、および式（２ａ）で表される１−（２−ブロモ−３−ヘキシルチエニル）−４−メトキシベンゼンを０．５ｍｍｏｌ使用した。

As reaction raw materials, 0.6 mmol of 2-methylthiophene represented by the formula (1a) and 0. 1- (2-bromo-3-hexylthienyl) -4-methoxybenzene represented by the formula (2a) 5 mmol was used.

The 25 mL Schlenk tube was dried and then replaced with nitrogen gas. To the Schlenk tube, 0.5 mL of THF and tert-butoxylithium with respect to 1- (2-bromo-3-hexylthienyl) -4-methoxybenzene were added. Equivalently dissolved solution was added. In addition, DMF was added to a 2 mL Schlenk tube. While stirring the contents of the Schlenk tube, 2 mol of orange Pd (P ^t Bu ₃ ) ₂ (Aldrich) was added to 1- (2-bromo-3-hexylthienyl) -4-methoxybenzene. % Of the Schlenk tube, and then the compound of the formula (1a) and the compound of the formula (2a) as reaction raw materials were added and reacted at 100 ° C. for 15 hours.

As a result, a compound represented by the formula (3a) which is a product of the CC coupling reaction, and a compound represented by the formula (4a) and a compound represented by the formula (5a) which are by-products are obtained. Obtained. The ¹ H NMR yields of these three compounds were determined under the same conditions as in Example 1. As a result, the yield of the compound of formula (3a) was 11%, the yield of the compound of formula (4a) was 10%, and The yield of the compound of formula (5a) was 50%.

[Examples 20 to 25]
Example 19 except that the amount of the compound of the formula (1a) and the compound of the formula (2a) which are the reaction raw materials, the kind and amount of the reaction solvent, the reaction temperature and the reaction time were changed as shown in Table 4 below. The C—C coupling reaction was carried out in the same manner as above.

It represents with the < ¹ > H NMR yield of the compound of Formula (3a)-Formula (5a).

［比較例１］
実施例１と同様の条件で、パラジウム錯体触媒をニッケル錯体触媒NiCl₂(dppe) (dppe：1,2-ビス（ジフェニルホスフィノ）エタン)に変更し、NiCl₂(dppe)の添加触媒量は同量で反応を行ったが、¹H NMR収率で１％以下であった。

[Comparative Example 1]
Under the same conditions as in Example 1, the palladium complex catalyst was changed to the nickel complex catalyst NiCl ₂ (dppe) (dppe: 1,2-bis (diphenylphosphino) ethane), and the added catalyst amount of NiCl ₂ (dppe) was The reaction was carried out in the same amount, but the ¹ H NMR yield was 1% or less.

[Comparative Example 2]
Under the same conditions as in Example 1, the lithium base was changed to cesium carbonate and the reaction was carried out in the same molar amount of cesium carbonate, but the ¹ H NMR yield was 1% or less.

[Comparative Example 3]
Under the same conditions as in Example 1, the solvent was changed to dehydrated ethanol (manufactured by Kanto Chemical Co., Inc.) and the reaction was carried out, but the ¹ H NMR yield was 1% or less.

[Comparative Example 4]
Under the same conditions as in Example 1, the solvent was changed to acetic acid (manufactured by Kanto Chemical Co., Inc.) and the reaction was carried out, but the ¹ H NMR yield was 1% or less.

[Comparative Example 5]
Under the same conditions as in Example 7, the palladium complex catalyst was changed to the nickel complex catalyst NiCl ₂ (dppe) (dppe: 1,2-bis (diphenylphosphino) ethane), and the reaction was carried out with the same amount. However, the ¹ H NMR yield was 1% or less.

[Comparative Example 6]
Under the same conditions as in Example 19, the palladium complex catalyst was changed to the nickel complex catalyst NiCl ₂ (dppe) (dppe: 1,4-bis (diphenylphosphino) butane), and the reaction was carried out with the same addition amount. However, the ¹ H NMR yield was 1% or less.

[Comparative Example 7]
Under the same conditions as in Example 19, the solvent was changed to acetic acid (manufactured by Kanto Chemical Co., Inc.) and the reaction was performed, but the ¹ H NMR yield was 1% or less.

Claims (16)

  A catalyst composition for CC coupling reaction comprising a palladium complex catalyst and a lithium base. In the palladium complex catalyst, the valence of the palladium atom is zero or divalent,
The ligand coordinated to the palladium atom is at least one compound or atom selected from the group consisting of phosphine compounds, aryl compounds, nitrile compounds, carbonyl compounds and halogen atoms. A catalyst composition for CC coupling reaction.   The catalyst composition for CC coupling reaction according to claim 1 or 2, wherein in the palladium complex catalyst, 1 to 4 moles of the ligand are coordinated with respect to 1 mole of palladium atoms. .   The structure of the lithium base is a structure in which an anion is ion-bonded to lithium as a cation, and the anion is a carboanion or an alkoxy anion. -C coupling reaction catalyst composition.   It is used for CC coupling reaction of an aryl compound and an aryl halide compound, The catalyst composition for CC coupling reaction in any one of Claims 1-4 characterized by the above-mentioned.   The aryl compound is an optionally substituted heteroaromatic ring compound, and at least one carbon atom constituting the heteroaromatic ring adjacent to the heteroatom constituting the heteroaromatic ring is not substituted It is a heteroaromatic ring compound, The catalyst composition for CC coupling reaction of Claim 5 characterized by the above-mentioned. The catalyst composition for CC coupling reaction according to claim 6, wherein the heteroaromatic ring compound is thiophene represented by the following formula (1) or a derivative thereof:

(In Formula (1),
R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an optionally substituted aryl group having 6 to 10 carbon atoms. Or an alicyclic group having 5 to 10 carbon atoms,
R ¹ and R ² may be bonded to each other to form a 5- or 6-membered aromatic ring, the aromatic ring may have a hetero atom, and the aromatic ring may be substituted;
R ² and R ³ may be bonded to each other to form a 5- or 6-membered alicyclic structure, the alicyclic structure may have a hetero atom, and the alicyclic structure may be substituted. Good. ). The catalyst composition for CC coupling reaction according to any one of claims 5 to 7, wherein the halogenated aryl compound is any aryl derivative represented by the following formula (2):

(In the formula (2), Ra, Rb and Rc are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryl group or carbon having 6 to 10 carbon atoms. An alicyclic group of formula 5-10, X is a halogen atom,
M1 which shows the number of substituents is an integer of 0-3, m2 is an integer of 0-5, m3 is an integer of 0-4,
When m1 is 2 or more, a plurality of Ras may be the same or different. When m2 is 2 or more, a plurality of Rbs may be the same or different. When m3 is 2 or more, there are a plurality of Ras. Rc may be the same or different. ). An aryl compound and a halogenated aryl compound are contacted to activate a bond between the carbon-hydrogen atom of the aryl compound and a bond between the carbon-halogen atom of the halogenated aryl compound. In carrying out the CC coupling reaction to form a bond of
A polycyclic aromatic compound characterized by carrying out the CC coupling reaction in a polar aprotic organic solvent in the presence of a catalyst composition for CC coupling reaction containing a palladium complex catalyst and a lithium base. Manufacturing method.   The aryl compound is an optionally substituted heteroaromatic ring compound, and at least one carbon atom constituting the heteroaromatic ring adjacent to the heteroatom constituting the heteroaromatic ring is not substituted It is a heteroaromatic ring compound, The manufacturing method of the polycyclic aromatic compound of Claim 9 characterized by the above-mentioned. The method for producing a polycyclic aromatic compound according to claim 10, wherein the heteroaromatic ring compound is thiophene represented by the following formula (1) or a derivative thereof:

(In the formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an optionally substituted carbon. An aryl group having 6 to 10 carbon atoms or an alicyclic group having 5 to 10 carbon atoms,
R ¹ and R ² may be bonded to each other to form a 5- or 6-membered aromatic ring, the aromatic ring may have a hetero atom, and the aromatic ring may be substituted;
R ² and R ³ may be bonded to each other to form a 5- or 6-membered alicyclic structure, the alicyclic structure may have a hetero atom, and the alicyclic structure may be substituted. Good. ). In the palladium complex catalyst, the valence of the palladium atom is zero or divalent,
The ligand coordinated to the palladium atom is a compound or atom selected from the group consisting of phosphine compounds, aryl compounds, nitrile compounds, carbonyl compounds, halogen atoms,
The method for producing a polycyclic aromatic compound according to any one of claims 9 to 11, wherein 1 to 4 moles of the ligand are coordinated with respect to 1 mole of the palladium atom. The method for producing a polycyclic aromatic compound according to any one of claims 9 to 12, wherein the halogenated aryl compound is any aryl derivative represented by the following formula (2):

(In the formula (2), Ra, Rb and Rc are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 10 carbon atoms, or a carbon number. 5-10 alicyclic groups,
M1 which shows the number of substituents is an integer of 0-3, m2 is an integer of 0-5, m3 is an integer of 0-4,
When m1 is 2 or more, a plurality of Ras may be the same or different. When m2 is 2 or more, a plurality of Rbs may be the same or different. When m3 is 2 or more, there are a plurality of Ras. Rc may be the same or different. ).   The amount of the C—C coupling reaction catalyst composition used is 0.1 to 50 mol% in terms of the palladium complex catalyst with respect to the charged molar amount of the halogenated aryl compound. Item 14. A method for producing a polycyclic aromatic compound according to any one of Items 9 to 13. The structure of the lithium base is a structure in which anions are ionically bonded to lithium as a cation,
The anion is a carbanion or an alkoxy anion;
The amount of the C—C coupling reaction catalyst composition used is 0.1 to 50 equivalents per 1 equivalent of the charged amount of the aryl compound in terms of the lithium base. 14. The method for producing a polycyclic aromatic compound according to any one of 14 above.   The method for producing a polycyclic aromatic compound according to any one of claims 9 to 15, wherein a reaction temperature of the CC coupling reaction is 40 to 150 ° C.