JPWO2017090601A1 - Method for producing aromatic heteropolycyclic halogen compound - Google Patents

Abstract

To provide an industrially advantageous production method capable of producing an aromatic heteropolycyclic halogen compound. A method for producing an aromatic heteropolycyclic halogen compound, comprising reacting an aromatic heteropolycyclic compound and a halogenating agent in the presence of an interhalogen compound.

Description

  The present invention relates to a method for producing an aromatic heteropolycyclic halogen compound.

  An aromatic heteropolycyclic halogen compound is an extremely useful compound as a production intermediate of a light emitting material of an organic electroluminescence (hereinafter sometimes referred to as organic EL) element or an electrophotographic photosensitive member.

  Although the organic EL field is a growth field, the organic EL element still has many problems in practical use, and has been actively researched. Problems in practical use include improvement of light emission efficiency of organic EL elements, reduction of pixel defects, suppression of driving voltage, improvement of heat resistance, and the like. In order to solve these problems, for example, boronate esterification of bromodibenzothiophene, followed by a Suzuki coupling reaction with a halogen compound, a compound having at least one dibenzothienyl group is obtained, which emits light. It has been proposed to be used as a layer host material or a charge transport material for a layer adjacent to the light emitting layer, thereby obtaining an organic electroluminescent device with reduced driving voltage, improved luminous efficiency, and improved heat resistance. Has been reported (for example, see Patent Document 1). Similarly, by using a compound having a dibenzofuranyl group or a dibenzothienyl group as a host material for the light emitting layer or a charge transport material for a layer adjacent to the light emitting layer, an organic electroluminescent device having excellent heat resistance and durability can be obtained. (For example, refer to Patent Document 2). From these, it can be seen that aromatic heteropolycyclic halogen compounds are used as particularly important synthetic intermediates in this field. As a method for producing an aromatic heteropolycyclic halogen compound, for example, a method in which a dibenzofuran derivative is reacted with bromine in a glacial acetic acid solvent to obtain a corresponding monobromodibenzofuran derivative is known (for example, non-patent literature). 1).

  On the other hand, in the organic EL field, it is known that the purity of various organic compounds constituting the organic EL element strongly influences a decrease in light emission efficiency and a decrease in light emission luminance. For example, it has been reported that by controlling the mass concentration of the halogen element, which is an impurity contained in the host material forming the light emitting layer in the organic EL element, to 50 ppm or less, the light emission luminance and the light emission efficiency are high and the lifetime is extended. (For example, refer to Patent Document 3). Furthermore, in a light-emitting element having at least one organic compound layer, by setting the content of impurities by-produced in the cross-coupling reaction to 0.5% by mass or less, the initial luminance is high and the emission luminance associated with long-term driving It is known that attenuation is reduced (see, for example, Patent Document 4).

JP 2012-080063 A JP 2012-049523 A No. 2005-084083 JP 2002-373786 A

J. et al. Org. Chem. 1997, 62, 1348-1355.

  When the above-described method for producing a monobromodibenzofuran derivative is used, there is a problem that a large number of regioisomers and dibromo compounds are by-produced. In particular, regioisomers are difficult to purify and separate even with column chromatography, which is a general purification method, and compounds containing a large amount of such impurities are used in organic EL applications that require a high level of impurity control. Is not efficient because it is expected to require purification with a significant decrease in yield.

  An object of the present invention is to provide a method for producing an aromatic heteropolycyclic halogen compound with little positional isomer impurity that is difficult to purify when synthesizing an aromatic heteropolycyclic halogen compound.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have made an aromatic heteropolycyclic compound and a halogenating agent react with each other in the presence of an interhalogen compound, thereby reducing an aromatic compound having little positional isomer impurity. The present inventors have found that an aromatic heteropolycyclic halogen compound can be obtained and have completed the present invention. That is, the present invention is as follows.

（式中、Ｒ^１、Ｒ^３及びＲ^４は、互いに同一であっても異なっていてもよく、水素原子、炭素数１〜６のアルキル、炭素数１〜６のアルコキシ、炭素数３〜６のシクロアルキル、炭素数６〜２０のアリール又は炭素数２〜２０のヘテロアリールであり；Ｒ^２は、水素原子であり；環Ａｒは、置換もしくは無置換の芳香族炭化水素環又は芳香族複素環であり；Ａは、−Ｏ−、−Ｓ−、−Ｓｅ−又は−ＮＲ^５−であり、そしてＲ^５は、水素原子、炭素数１〜６のアルキル又は炭素数６〜２０のアリールである）
で示される化合物とハロゲン化剤を、ハロゲン間化合物の存在下に反応させることを特徴とする、一般式（２）：

（式中、Ｒ^１、Ｒ^３、Ｒ^４、環Ａｒ及びＡは、前記と同義であり、Ｘは、塩素原子又は臭素原子を示す）
で示される化合物の製造方法に関する。That is, the present invention relates to the general formula (1):

(In formula, R < ¹ >, R < ³ > and R < ⁴ > may mutually be same or different, a hydrogen atom, a C1-C6 alkyl, a C1-C6 alkoxy, a C3-C6. Cycloalkyl, aryl having 6 to 20 carbon atoms or heteroaryl having 2 to 20 carbon atoms; R ² is a hydrogen atom; ring Ar is a substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocycle A is —O—, —S—, —Se—, or —NR ⁵ —, and R ⁵ is a hydrogen atom, alkyl having 1 to 6 carbons or aryl having 6 to 20 carbons. is there)
A compound represented by general formula (2) is reacted with a halogenating agent in the presence of an interhalogen compound:

(Wherein R ¹ , R ³ , R ⁴ , ring Ar and A are as defined above, and X represents a chlorine atom or a bromine atom)
It relates to the manufacturing method of the compound shown by these.

  According to the production method of the present invention, aromatic heteropolycyclic halogen compounds which are extremely useful organic synthetic intermediates for light-emitting materials and electrophotographic photoreceptors of organic EL devices are suppressed, and regioisomers that are difficult to purify are suppressed. It can be easily manufactured. Therefore, the production method of the present invention is expected to be industrially applicable.

  Hereinafter, embodiments of the present invention will be described in detail. First, terms used in the present specification and claims will be described. Each term has the following significance unless otherwise specified.

In the present invention, the “alkyl having 1 to 6 carbon atoms” is a monovalent group of a linear or branched aliphatic saturated hydrocarbon having 1 to 6 carbon atoms, alone or in combination with other terms. Meaning, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl or hexyl.
In the present invention, “alkoxy having 1 to 6 carbon atoms” means a group —OR ^a where R ^a is alkyl having 1 to 6 carbon atoms as defined above. Examples include ethoxy, propoxy, isopropoxy, n-butyloxy, isobutyloxy, s-butyloxy, t-butyloxy, pentyloxy, hexyloxy and the like.

  In the present invention, “cycloalkyl having 3 to 6 carbon atoms” means a monovalent group of a cyclic aliphatic saturated hydrocarbon having 3 to 6 carbon atoms, alone or in combination with other terms, , Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

  In the present invention, “aryl having 6 to 20 carbon atoms” means a monovalent group of a monocyclic or condensed polycyclic compound having 6 to 20 carbon atoms and containing at least one aromatic ring. Naphthyl, tetrahydronaphthyl, anthryl, pyrenyl, indenyl, fluorenyl, acenaphthylenyl, phenanthryl or phenalenyl. In addition, these may be substituted with one or more arbitrary substituents that do not participate in the reaction. Examples of such a substituent include alkyl having 1 to 6 carbons, alkoxy having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 20 carbons, and heteroaryl having 2 to 20 carbons. Is mentioned.

  In the present invention, the “heteroaryl having 2 to 20 carbon atoms” means a monovalent group of a monocyclic or condensed polycyclic compound having 2 to 20 carbon atoms containing at least one aromatic heterocycle, For example, furyl, benzofuranyl, dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, pyrrolyl, indolyl, carbazolyl, imidazolyl, benzoimidazolyl, pyrazolyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, furazanyl, pyridyl, pyranyl, pyrazinyl, pyrimidinyl , Pyridazinyl, triazinyl, azepinyl, quinolyl, indolizinyl, cinnolinyl, purinyl, carbonylyl, phenanthrolinyl and imidazopyrimidinyl. In addition, these may be substituted with one or more arbitrary substituents that do not participate in the reaction. Examples of such a substituent include alkyl having 1 to 6 carbons, alkoxy having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 20 carbons, and heteroaryl having 2 to 20 carbons. Is mentioned.

  In the present invention, the “aromatic hydrocarbon ring” means a monocyclic or condensed polycyclic compound having 6 to 20 carbon atoms containing at least one aromatic ring. For example, benzene, naphthalene, tetrahydronaphthalene, anthracene , Pyrene, indene, fluorene, acenaphthylene, phenanthrene or phenalene. In addition, these may be substituted with one or more arbitrary substituents that do not participate in the reaction. Examples of such a substituent include alkyl having 1 to 6 carbons, alkoxy having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 20 carbons, and heteroaryl having 2 to 20 carbons. Is mentioned. The monovalent group of the “aromatic hydrocarbon ring” is synonymous with the above “aryl having 6 to 20 carbon atoms”, and both can be used interchangeably.

  Similarly, “aromatic heterocycle” means a monocyclic or condensed polycyclic compound having 2 to 20 carbon atoms containing at least one aromatic heterocycle, such as furan, benzofuran, dibenzofuran, thiophene. , Benzothiophene, dibenzothiophene, pyrrole, indole, carbazole, imidazole, benzimidazole, pyrazole, oxazole, benzoxazole, thiazole, benzothiazole, furazane, pyridine, pyran, pyrazine, pyrimidine, pyridazine, triazine, azepine, quinoline, indolizine Cinnoline, purine, carboline, phenanthroline and imidazopyrimidine. In addition, these may be substituted with one or more arbitrary substituents that do not participate in the reaction. Examples of such a substituent include alkyl having 1 to 6 carbons, alkoxy having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 20 carbons, and heteroaryl having 2 to 20 carbons. Is mentioned. The monovalent group of the “aromatic heterocycle” has the same meaning as the “heteroaryl having 2 to 20 carbon atoms”, and both can be used interchangeably.

  Next, the production method of the present invention will be described in detail.

（式中、Ｒ^１、Ｒ^３及びＲ^４は、互いに同一であっても異なっていてもよく、水素原子、炭素数１〜６のアルキル、炭素数１〜６のアルコキシ、炭素数３〜６のシクロアルキル、炭素数６〜２０のアリール又は炭素数２〜２０のヘテロアリールであり；Ｒ^２は、水素原子であり；環Ａｒは、置換もしくは無置換の芳香族炭化水素環又は芳香族複素環であり；Ａは、−Ｏ−、−Ｓ−、−Ｓｅ−又は−ＮＲ^５−であり、そしてＲ^５は、水素原子、炭素数１〜６のアルキル基又は炭素数６〜２０のアリールである）
で示される化合物とハロゲン化剤を、ハロゲン間化合物触媒の存在下、反応させることを特徴とする、一般式（２）：

（式中、Ｒ^１、Ｒ^３、Ｒ^４、環Ａｒ及びＡは、前記と同義であり、Ｘは、塩素原子又は臭素原子を示す。）
で示される化合物を得るものである。The present invention relates to a general formula (1):

(In formula, R < ¹ >, R < ³ > and R < ⁴ > may mutually be same or different, a hydrogen atom, a C1-C6 alkyl, a C1-C6 alkoxy, a C3-C6. Cycloalkyl, aryl having 6 to 20 carbon atoms or heteroaryl having 2 to 20 carbon atoms; R ² is a hydrogen atom; ring Ar is a substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocycle A is —O—, —S—, —Se—, or —NR ⁵ —, and R ⁵ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl having 6 to 20 carbon atoms. Is)
A compound represented by general formula (2) is reacted with a halogenating agent in the presence of an interhalogen compound catalyst:

(Wherein R ¹ , R ³ , R ⁴ , ring Ar and A are as defined above, and X represents a chlorine atom or a bromine atom.)
Is obtained.

In the general formula (1), R ¹ , R ³ and R ⁴ may be the same or different from each other, and are a hydrogen atom, alkyl having 1 to 6 carbons, alkoxy having 1 to 6 carbons, carbon A cycloalkyl having 3 to 6 carbon atoms, an aryl having 6 to 20 carbon atoms or a heteroaryl having 2 to 20 carbon atoms, preferably a hydrogen atom or an alkyl having 1 to 6 carbon atoms, and all being hydrogen atoms. More preferred.

  In the general formula (1), the ring Ar is a substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocyclic ring. Ring Ar means a substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocyclic ring further condensed to the 5-membered ring of the [6-5] condensed ring skeleton of the general formula (1), and is substituted or unsubstituted Benzene is preferred, benzene substituted with alkyl having 1 to 6 carbon atoms or unsubstituted benzene is more preferred, and unsubstituted benzene is particularly preferred.

In the general formula (1), A is —O—, —S—, —Se—, —NR ⁵ — (R ⁵ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 6 to 20 carbon atoms. And is preferably -O- or -S-.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、環Ａｒ及びＡは、前記と同義であり、Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９は、互いに同一であっても異なっていてもよく、水素原子、炭素数１〜６のアルキル、炭素数１〜６のアルコキシ、炭素数３〜６のシクロアルキル、炭素数６〜２０のアリール又は炭素数２〜２０のヘテロアリールである）で示される化合物である。その中でも、一般式（１ａ）において、Ａが−Ｏ−又は−Ｓ−であり、Ｒ^１、Ｒ^３、Ｒ^４、Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９が水素原子又は炭素数１〜６のアルキルであるものが好ましく、Ａが−Ｏ−又は−Ｓ−であり、Ｒ^１、Ｒ^３、Ｒ^４、Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９が全て水素原子であるものがより好ましい。Therefore, a preferred embodiment of the compound represented by the general formula (1) is the following general formula (1a):

(Wherein R ¹ , R ² , R ³ , R ⁴ , rings Ar and A are as defined above, and R ⁶ , R ⁷ , R ⁸ and R ⁹ are the same as or different from each other. Or a hydrogen atom, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, aryl having 6 to 20 carbon atoms, or heteroaryl having 2 to 20 carbon atoms) It is a compound shown by these. Among them, in the general formula (1a), A is —O— or —S—, and R ¹ , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each a hydrogen atom or a carbon number of 1 to 6 is preferred, A is —O— or —S—, and R ¹ , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are all hydrogen atoms. preferable.

The manufacturing method of General formula (1) used for the manufacturing method of this invention is not specifically limited, It can synthesize | combine by any well-known method. For example, a compound in which R ¹ , R ² , R ³ and R ⁴ in formula (1) are hydrogen atoms, ring Ar is unsubstituted benzene, and A is an oxygen atom (ie, dibenzofuran) is commercially available. It can be obtained from suppliers such as Tokyo Chemical Industry Co., Ltd. Moreover, it is also possible to synthesize | combine according to a well-known method (For example, the method of J.Am.Chem.Soc., 2006,128,581-590).

  The kind of the halogenating agent used in the production of the present invention can be appropriately selected from a chlorinating agent and a brominating agent for the target compound. Examples of the chlorinating agent include chlorine, N-chlorosuccinimide, 1,3-dichloro-5,5-dimethylhydantoin and the like. From the viewpoint of reactivity, chlorine is preferred. Examples of the brominating agent include bromine, N-bromosuccinimide, 1,3-dibromo-5,5-dimethylhydantoin and the like. Bromine is preferred from the viewpoint of reactivity.

  Although the usage-amount of the halogenating agent used for manufacture of this invention is not specifically limited, It is preferable to use in 0.5-3.0 mol with respect to 1 mol of compounds shown by General formula (1). From the viewpoint of reaction rate, it is more preferable to use in the range of 0.5 to 1.5 mol, and from the viewpoint of impurity suppression, it is more preferable to use in the range of 0.5 to 1.2 mol.

The interhalogen compound used in the production of the present invention is a compound composed of two kinds of halogens. Preferably, the general formula (3)
I-X (3)
(Wherein X represents a chlorine atom or a bromine atom)
And a compound in which X is a bromine atom is more preferable from the viewpoint of impurity suppression. Specific examples include iodine monochloride and iodine monobromide, and these compounds may be used alone or in admixture of two or more.

  The interhalogen compounds are commercially available and can be obtained from suppliers such as Aldrich. Moreover, it is also possible to synthesize according to a known method. Specifically, as a method for synthesizing iodine monobromide, iodine is mixed with bromine in a solvent and heated until iodine is dissolved (for example, J. Am. Chem. Soc., 1938, 60, 256). But the production method is not particularly limited. Further, in the production method of the present invention, as the interhalogen compound, iodine generated in a reaction system and generated in situ by reaction with the halogenating agent may be used.

  The amount of the interhalogen compound catalyst used in the production of the present invention is not particularly limited, but it is preferably used in the range of 0.01 to 50 mol% with respect to 1 mol of the compound represented by the general formula (1). More preferably, it is used in the range of 0.01 to 20 mol%.

  A solvent may be used in the reaction of the present invention. The solvent to be used is not particularly limited as long as it is inert to the reaction, and is appropriately selected depending on the desired reaction temperature. Solvents may be used alone or in admixture of two or more at any ratio. Specifically, halogenated aromatic hydrocarbon solvents such as monochlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, methylene bromide, chloroform, carbon tetrachloride, ethylene dichloride, 1,1,1-trichloroethane, trichloroethylene, etc. And halogenated aliphatic hydrocarbon solvents. The usage-amount of a solvent is 0.5-100 times amount (weight basis) with respect to 1g of aromatic heteropolycyclic compounds of General formula (1), Preferably, it is 0.5-20 times amount.

  The reaction temperature of the present invention is preferably in the range of -80 to 200 ° C. In the point which suppresses a side reaction, -80-25 degreeC is preferable and -80--40 degreeC is more preferable.

  The reaction time of the present invention can be appropriately set according to the conditions such as the amount and type of starting material used, the presence or absence of a solvent, the type thereof, and the reaction temperature. Usually, 10 minutes to 48 hours are preferable, and from the viewpoint of workability, 10 minutes to 24 hours are more preferable.

  After completion of the reaction, the obtained reaction solution can be post-treated by a usual method. The post-treatment method is not particularly limited. For example, the reaction solution obtained with water or an alkaline aqueous solution (sodium hydroxide aqueous solution, sodium hydrogen carbonate aqueous solution, etc.) is washed to remove the acid component and inorganic salt from the reaction system. For example, a process of removing from the inside. Furthermore, if desired, according to the properties of the target aromatic heteropolycyclic halogen compound of the general formula (1), further separation and purification may be performed by a general method such as distillation, recrystallization, chromatography, and the like.

  Examples are shown below to clarify aspects of the present invention, but the present invention is not limited only to the contents of the examples shown here.

  The purity of the reaction solution and the target product obtained in Examples and Comparative Examples was measured using high performance liquid chromatography (HPLC).

The measurement conditions are as follows.
Detector: SPD20A (manufactured by Shimadzu Corporation)
Oven: CTO-20A (manufactured by Shimadzu Corporation)
Pump: LC-20AD (manufactured by Shimadzu Corporation)
Column: ODS-80Tm (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Eluent: acetonitrile: water = 75: 25
Flow rate: 1.0 ml / min
Wavelength: 254 nm

[Example 1]
Under an argon atmosphere, 4.0 g (23.8 mmol) of dibenzofuran (manufactured by Tokyo Chemical Industry Co., Ltd.) and 40 g of methylene chloride were added to a four-necked flask and cooled to an internal temperature of about −50 to −40 ° C. with stirring. After cooling, 0.1 g (0.5 mmol) of iodine monobromide (manufactured by Aldrich) was added, and a solution containing 3.8 g (23.8 mmol) of bromine and 7.7 g of methylene chloride was added dropwise at the same temperature. And allowed to react for 1 hour. The HPLC purity of the obtained reaction solution was 82.4% 2-bromodibenzofuran (10.5% 3-bromodibenzofuran).
The obtained reaction solution was reduced with an aqueous sodium sulfite solution, and the organic layer was separated. The obtained organic layer was washed with water, the solvent was distilled off by concentration, and 5 ml of monochlorobenzene and 25 ml of isopropyl alcohol were added to the obtained solid residue. Next, crystals were precipitated by ice water cooling, followed by filtration and drying to obtain 4.5 g of 2-bromodibenzofuran having a HPLC purity of 99% (yield 77%, non-detection of 3-bromodibenzofuran). Appearance: White powdery crystal.

[Example 2]
The same operation was performed except that iodine monobromide in Example 1 was changed to iodine monochloride 0.1 g (0.6 mmol) (manufactured by Wako Pure Chemical Industries, Ltd.). The HPLC purity of the obtained reaction solution was 79.2% 2-bromodibenzofuran (11.6% 3-bromodibenzofuran).

[Example 3]
The same operation was performed except that iodine monobromide in Example 1 was changed to 0.06 g (0.2 mmol) iodine (manufactured by Wako Pure Chemical Industries, Ltd.) and iodine monobromide was adjusted in the reaction solution. . The HPLC purity of the obtained reaction liquid was 82.8% of 2-bromodibenzofuran (3-bromodibenzofuran 10.3%).

[Example 4]
The same operation was performed except that iodine monobromide in Example 1 was changed to 0.6 g (2.4 mmol) iodine (manufactured by Wako Pure Chemical Industries, Ltd.) and iodine monobromide was adjusted in the reaction solution. . The HPLC purity of the resulting reaction solution was 82.9% 2-bromodibenzofuran (7.8% 3-bromodibenzofuran).

[Example 5]
The same operation was performed except that the dibenzofuran of Example 3 was changed to 4.0 g (21.8 mmol) of dibenzothiophene (Aldrich). The HPLC purity of the obtained reaction liquid was 90.9% of 2-bromodibenzothiophene (1.3% of 3-bromodibenzothiophene).

[Comparative Example 1]
Dibenzofuran 5.0 g (29.7 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) and acetic acid 30 ml were added to a four-necked flask, and the temperature was raised to 50 ° C. with stirring. At the same temperature, 6.3 g (39.2 mmol) of bromine was added dropwise over about 20 minutes. After dropping, the mixture was cooled to room temperature and reacted overnight. The HPLC purity of the obtained reaction liquid was 58.7% of 2-bromodibenzofuran (3-bromodibenzofuran 16.5%).

[Comparative Example 2]
The same operation was performed except that the iodine monobromide in Example 1 was changed to 0.04 g (0.2 mmol) of iron (III) chloride (manufactured by Wako Pure Chemical Industries, Ltd.). The HPLC purity of the obtained reaction liquid was 66.2% 2-bromodibenzofuran (17.5% 3-bromodibenzofuran).

Claims (7)

General formula (1):

(In formula, R < ¹ >, R < ³ > and R < ⁴ > may mutually be same or different, a hydrogen atom, a C1-C6 alkyl, a C1-C6 alkoxy, a C3-C6. Cycloalkyl, aryl having 6 to 20 carbon atoms or heteroaryl having 2 to 20 carbon atoms; R ² is a hydrogen atom; ring Ar is a substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocycle A is —O—, —S—, —Se—, or —NR ⁵ —, and R ⁵ is a hydrogen atom, alkyl having 1 to 6 carbons or aryl having 6 to 20 carbons. is there)
A compound represented by general formula (2) is reacted with a halogenating agent in the presence of an interhalogen compound:

(Wherein R ¹ , R ³ , R ⁴ , ring Ar and A are as defined above, and X represents a chlorine atom or a bromine atom)
The manufacturing method of the compound shown by these. The interhalogen compound has the general formula (3):
I-X (3)
(Wherein X represents a chlorine atom or a bromine atom)
The manufacturing method of Claim 1 which is a compound shown by these.   The manufacturing method of Claim 2 whose X of the said General formula (3) is a bromine atom.   The manufacturing method in any one of Claims 1-3 whose A is -O- or -S- in the said General formula (1).   The production method according to any one of claims 1 to 4, wherein in the general formula (1), the ring Ar is substituted or unsubstituted benzene.   The production method according to claim 1, wherein the halogenating agent is a brominating agent.   The production method according to claim 6, wherein the brominating agent is bromine, N-bromosuccinimide or 1,3-dibromo-5,5-dimethylhydantoin.