KR100928055B1 - Arylalkyne compound from dehydrogenation of propionic acid derivative by carbon dioxide reaction and its preparation method - Google Patents

Abstract

The present invention relates to a process for producing an arylalkyne compound, and more particularly, to a process for producing an arylalkyne compound efficiently using Sonogashira reaction and dehydrocarbonation reaction using a propiolic acid derivative in the same reaction vessel .

The arylalkyne compound according to the present invention is economical to the starting material because it is lower in cost than the alkyne compound of the protecting group, which has been widely used in the existing Sonogashira reaction using propionic acid, and the by- Carbon dioxide is generated, which is more environment friendly than conventional metal waste.

Arylalkyne, sonogashira, de-carbon dioxide, propiolic acid

Description

Technical Field [0001] The present invention relates to arylalkyne compounds via dehydrocarbonation reaction from propiolic acid derivatives, and methods for preparing the same. BACKGROUND ART Synthesis of arylalkynyl derivatives from propiolic acid via decarboxylative cross-

The present invention relates to an environmentally friendly preparation method for producing an arylalkyne compound.

The structure of compounds consisting of carbon-carbon double bonds and carbon-carbon triple bonds is very important in modern organic chemistry. It is a skeleton that is widely used in the structure of information-related materials such as conductive polymers while being found in many natural products of nature.

As a method for producing such a carbon-carbon bond compound, a coupling reaction using a transition metal catalyst is mainly used, and reactivity is distinguished depending on the kind of a metal element bonded to a reaction substrate used for bonding. These reactions are named after the chemists who developed them, respectively, Kumada, Neigishi, Stille, Suzuki, Heck, Hiyama, and Sonogashira.

Most of these reactions are used for the sp ² -sp ² carbon bond reaction and the Sonogashira reaction is for the sp ² -sp carbon bond formation (Angew. Chem. Int. Ed. 2007, 46, 834).

The Sonogashira reaction was carried out using palladium as a catalyst and using copper as a cocatalyst to conduct oxidative addition of a palladium catalyst under basic conditions such as an amine, metal transition reaction of copper reacted with alkyne, isomerization reaction , The halogen carbon of the arylhalogen compound and the terminal carbon of the alkyne can be bonded by the mechanism of the reduction elimination reaction.

This reaction has been extended by many researchers not only to extend the range of applications but also to develop improved reaction methods.

This reaction method is not only used for synthesizing organic compounds having various structures, but also is a method in which alkyne groups and aryl groups are alternately arranged by using a reaction between a compound in which two halogen atoms are substituted in the arylhalogen compound and a compound having two terminal alkyne hydrogen It is widely used in the production of polymer compounds.

On the other hand, the Sonogashira reaction has a problem in that a large amount of nitrogen waste is generated by using the copper metal equivalent in spite of its excellent merit, thereby causing environmental pollution.

 In order to introduce an asymmetric aryl compound into the alkyne using such a reaction, one side of the alkyne must be treated with a compound protected with another element (silicon, tin, boron, zinc or aluminum) and then removed again.

Therefore, not only a problem that a compound in which one side of alkyne is protected uses a relatively expensive compound, an increase in production cost due to an increase in protection and elimination reaction steps, but also an economic loss due to the disposal of the protective element And environmental pollution.

The present invention provides a method for producing an arylalkyne compound which is environmentally friendly and cost-competitive because no metal waste is generated.

In order to solve the above problems,

a) reacting a mixture comprising a compound of formula (2) and a compound of formula (3) to produce a compound of formula

b) adding a compound of formula (5) to produce a compound of formula (1);

And a method for producing the arylalkyne compound.

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the formula Ar _1, Ar ₂ are identical or independent of one another (C ₆ -C ₃₀₎ aryl or (C ₄ -C ₃₀₎ heteroaryl, and the aryl or heteroaryl is saturated or unsaturated straight or branched chain (C ₁ -C ₃₀₎ alkyl, (C ₁ -C ₃₀₎ alkoxy, (C ₆ -C ₃₀₎ aryl, (C ₆ -C ₃₀₎ aralkyl (C ₁ -C ₃₀₎ alkyl, linear or saturated or unsaturated grinding (C ₁ -C ₃₀₎ alkyl (C ₆ -C ₃₀₎ aryl, (C ₆ -C ₃₀₎ aralkyl (C ₁ -C ₃₀₎ alkoxy, (C ₄ -C ₃₀₎ heteroaryl, (C ₃ -C ₃₀₎ cycloalkyl Saturated or unsaturated mono- or di (C ₁ -C 6) alkyl, oxygen, nitrogen or sulfur, or a saturated or unsaturated heterocycloalkyl of 3 to 7 members inclusive of the heterocycle, hydroxy, carboxylic acid, amino, ₃₀₎ alkylamino, (C ₆ -C ₃₀₎ arylamino, linear or saturated or unsaturated grinding (C ₁ -C ₃₀₎ alkylcarbonyl, (C ₁ -C ₃₀₎ alkoxycarbonyl, saturated straight or branched chain, or Unsaturated (C ₁ -C ₃₀ ) alkyl acyl, (C _{1 to 30} ) alkylsilyl, benzoyl, diazomino, phenoxy, propyl, cyano, nitro, halogen or a fluorine group, and the linear or branched saturated or unsaturated alkyl , Alkoxy, aryl, aralkyl, aralkoxy, heteroaryl, cycloalkyl, heterocycloalkyl, alkylcarbonyl or alkoxycarbonyl may be further substituted by one or more halogens;

Wherein R _1, R ₂ are the same or alkyl, (C ₆ -C ₃₀₎ aryl, (C ₁ -C ₃₀₎ independently of one another represent hydrogen, straight or branched chain saturated or unsaturated (C ₁ -C ₃₀₎ alkyl (C ₆ -C ₃₀₎ aryl, (C ₃ -C ₃₀₎ cycloalkyl (C ₁ -C ₃₀₎ alkyl, (C ₁ -C ₃₀₎ alkylsilyl, (C ₁ -C ₃₀₎ alkoxy, thio (C ₁ -C ₃₀₎ alkoxy, (C ₁ -C ₃₀₎ alkyl siloxy, amide, hydroxy, amino, carboxylic acid, sulfonyl, (C ₆ -C ₃₀₎ aryl (C ₁ -C ₃₀₎ alkyl, (C ₆ -C ₃₀₎ arylsilyl, (C ₆ -C ₃₀₎ aryloxy, (C ₆ -C ₃₀₎ aryl (C ₁ -C ₃₀₎ alkoxy, thio (C ₆ -C ₃₀₎ aryloxy, (C ₆ -C ₃₀₎ aryl siloxane when, (C ₆ -C ₃₀₎ aryl (C ₁ -C ₃₀₎ alkyl siloxy, (C ₆ -C ₃₀₎ aryl amides, (C ₆ -C ₃₀₎ aryl (C ₁ -C ₃₀₎ alkyl amide, hydroxy hydroxy (C ₆ -C ₃₀₎ aryl amide, or (C ₆ -C ₃₀₎ arylamino (C ₆ -C ₃₀₎ and one selected from aryloxy;

X ₁ and X ₂ are leaving groups.

&Quot; Aryl " and " heteroaryl " refer to any substituent that comprises at least one aromatic or heteroaromatic ring or consists of a ring and is attached via a ring atom. The ring is preferably a mono- or bicyclic 5, 6 or 7 membered ring, but may also be a mono- or polycyclic ring system.

Examples of suitable rings are benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, tetrahydronaphthalene, 1-benzyl naphthalene, atlacene, phenanthracene, dihydroanthracene, dibenzanthracene, benzanthracene, perylene, Benzothiophene, thianthrene, furan, benzofuran, pyrene, isobenzofuran, chromene, xylene, pyrrole, imidazole, thiophene, , Pyrazole, pyrazine, pyrimidine, indole, indolizine, isoindole, purine, quinoline, isoquinoline, phthalazine, quinoxaline, quinazoline, carbazole, carboline, acridine, phenanthroline, , Isothiazole, isoxazole, phenoxazine, oxazole and imidazole, but is not limited thereto.

As used herein, the term "linear or branched saturated or unsaturated (C ₁ -C ₃₀ ) alkyl" refers to, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec- dimethyl-propyl, 4-methylpentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 2-methylpentyl, Dimethylbutyl, 2,2-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl , 1,1,2-trimethylpropyl, heptyl, 5-methoxyhexyl, 1-methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylbutyl, Butyl, 1,2,2-trimethylpropyl, 1,1,2-trimethylpropyl, heptyl, 5-methoxyhexyl, 1-methylhexyl, 2,2-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 1,2,3-trimethylbutyl, 1,1,2-trimethylbutyl, 1,1,3-trimethyl Butyl, octyl, 6-methylhept Butyl, nonyl, 1-, 2-, 3-, 4-, 5-, 6- or 7-methyl-octyl, 1-, 2- -, 3-, 4- or 5-ethylheptyl, 1-, 2- or 3-propylhexyl, decyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 9- or 10-methyl undecyl, 1-, 2-, 3-, 4-, 5-, 6- 7- or 8-ethylhexyl, 1-, 2-, 3-, Propyl nonyl, 1-, 2-, 3- or 4-butyloctyl, 1-2-pentyl heptyl and the like, but are not limited thereto.

In the above, "alkoxy" includes, but is not limited to, methoxy, ethoxy, normal propoxy, isopropoxy, secributoxy, tertiary butoxy and n-pentoxy.

Also, the above-mentioned "leaving group" means any one selected from halogen (F, Cl, Br, I), trifluoromethanesulfonyloxy, methanesulfonyloxy or toluenesulfonyloxy.

The production method according to the present invention is characterized in that even when the protective group is removed from the alkyne compound having a protecting group, there is no problem of environmental pollution, and the propionic acid derivative which is lower in price than the alkyne compound protected by the conventional silicon, tin, boron, An arylalkyl compound having the same or an asymmetric aryl group can be prepared.

In the production method according to the present invention, the propionic acid derivative is used, the Sonogashira reaction is used for the carbon side of the alkyne having no carboxyl group, and the carbon side reaction for the carbon side of the alkyne having the carboxyl group is used.

The step a) of the above production method further comprises palladium, a base, and a ridged precursor for efficient progress of the reaction.

The palladium may be used as a catalyst for the Sonogashira reaction and may be palladium having oxidation states of 0 and +2. Examples of the palladium include palladium (II) acetate, palladium (II) acetonate, palladium (II) chloride And bis (triphenylphosphine) palladium (II) dichloride, but the present invention is not limited thereto.

The base is not particularly limited as long as it does not seriously inhibit the reaction if it is a base used in a known chemical reaction. Examples of the base include, but are not limited to, tetrabutylammonium fluoride, triethylamine, cesium carbonate, diisopropylethylamine, calcium carbonate, sodium hydroxide, and pyrrolidine.

The ligand precursor does not limit the use of the ligand precursor if it is a ligand precursor that affects the stabilization of the reaction by forming a ligand with the palladium catalyst. As the ligand precursor, an amine or a phosphorus compound can be mainly used. Specific examples thereof include bisdiphenylphosphinomethane, Triphenylphosphine, triphenylphosphine, triphenylphosphine, tri-tert.-butylphosphane, triphenylphosphonium cyclopentadienide, and 2,3,5-triphenyltetoluril chloride.

The step a) of the production process according to the present invention is carried out by stirring at room temperature for 11 to 15 hours. If the reaction time is less than 11 hours, the yield of the compound of formula (4) is lowered. If the reaction time is longer than 15 hours, the formation of side reactants is increased, and 11 to 13 hours is more preferable .

The step b) of the production process according to the present invention utilizes the carbon dioxide reaction of the carboxyl group and proceeds to the same container without the special separation and purification process after the reaction of the step a), thereby reducing the manufacturing cost used in the separation and purification process And it is more effective for industrial use.

The step b) of the production process according to the present invention is carried out at 85 to 95 캜 for 11 to 15 hours. If the temperature in the step b) is less than 85 ° C, the progress of the de-carbonation reaction is insufficient and the yield is poor. If the temperature is higher than 95 ° C, the polymerization by the alkyne can proceed.

The reaction time in step b) is preferably from 11 to 15 hours. If the reaction time is less than 11 hours, the yield of the final compound is decreased. If the reaction time is more than 15 hours, the generated side reaction product is increased. Is more preferably 11 to 13 hours.

The solvent used in the production process according to the present invention is not particularly limited so far as it is a conventional inert solvent so long as it does not seriously inhibit the reaction. Examples of the solvent include aliphatic organic solvents such as acetonitrile, dimethoxyformamide, dimethyl sulfoxide, hexamethylphosphoric triamide, pentane, hexane, heptane and octane, alicyclic organic solvents such as cyclohexane and methylcyclohexane, Aromatic hydrocarbons such as toluene, xylene and chlorobenzene, ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane, dioxane and 1,3-dioxolane, methanol, ethanol, propanol and isopropanol Alcohol solvent, and the like, but the present invention is not limited thereto.

The arylalkyl compound prepared by the process according to the present invention can be used as a medical candidate material or an electronic material material. As medical candidates, various alkene compounds and alkene compounds can be obtained by using an arylalkyl compound prepared by the production method according to the present invention as a precursor.

The arylalkyl compound prepared by the process according to the present invention may be used as a precursor of a compound used in a light emitting diode, a precursor of a luminescent probe material of various optical sensor devices, a precursor of an electrode material compound used in a battery, a conductive compound of an electrically conductive semiconductor device And a precursor of a dye material used for a compact disc or a DVD.

The arylalkyne compound according to the present invention can be obtained at low cost since it is lower in cost than the alkyne compound of the protecting group which has been widely used in the conventional Sonogashira reaction by using the propionic acid derivative, Carbon dioxide is generated, which is more environmentally friendly than metal waste produced using copper in conventional processes.

In addition, the elimination of the carboxylic acid protecting group bonded to the alkynyl group is not only required to be carried out under a special condition or an additional reaction step, but also is easy and efficient in the same reaction vessel using only changes in conditions, and is more effective in reducing the manufacturing cost by simplifying the process.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the present invention.

[Example 1] Synthesis of 1- (2-4-methylphenyl) ethynyl) benzene

0.025 mmol of Pd ₂ (dba) ₃ , 0.10 mmol of bisdiphenylphosphinomethane, 1.0 mmol of iodobenzene and 1.1 mmol of propionic acid were placed in a 15 ml round bottom flask and 6.0 mmol of tetrabutylammonium fluoride was introduced. After injecting 3 mL of dimethylformamide, the mixture was stopped with a septum and then stirred at room temperature. After 12 hours, 1.1 mmol of 4-bromotoluene was added, the temperature was raised to 90 ° C and the mixture was stirred for 12 hours. Then, the reaction mixture was diluted with 200 ml of ether, washed with water, treated with anhydrous magnesium sulfate, and filtered with an organic solvent. The filtered organic solvent was concentrated under reduced pressure and 84% of the product 1- (2-4-methylphenyl) ethynyl) benzene (3a) was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 10: ≪ / RTI >

^{1 H NMR (300 MHz, CDCl} 3) 7.53-7.49 (m, 2H), 7.41 (d, J = 8.0 Hz, 2H), 7.34-7.31 (m, 3H), 7.13 (d, J = 7.9 Hz, 2H ), 2.35 (s, 3 H);

¹³ C NMR (75 MHz, CDCl ₃ ) 138.71, 132.9, 131.9, 129.7, 129.5, 128.8, 128.7, 128.4, 89.1, 83.4, 21.9.

[Example 2] Synthesis of 1- (2- (3-methoxyphenyl) ethynyl) benzene

(3- (3-methoxyphenyl) ethynyl) benzene (3b) was obtained in a yield of 78% using bromoanisol instead of bromotoluene in the same manner as in Example 1.

¹ H NMR (300 MHz, CDCl ₃ ) 7.56-7.49 (m, 2H), 7.35-7.30 (m, 3H), 7.22 (d, J = 5.1 Hz, , ≪ / RTI > 1H), 6.87 (m, 1H), 3.79 (s, 3H);

¹³ C NMR (75 MHz, CDCl ₃ ) 159.32, 131.58, 129.36, 128.30, 128.26, 124.22, 124.14, 123.14, 116.31, 114.89, 89.29, 89.16, 55.29.

[Example 3] Synthesis of 2- (2-phenylethynyl) biphenyl

(2-phenylethynyl) biphenyl (3c) was obtained in a yield of 80% using 2-bromobiphenyl instead of 4-bromotoluene in the same manner as in Example 1.

^{1 H NMR (300 MHz, CDCl} 3) 7.68-7.63 (m, 3H), 7.48-7.24 (m, 11H);

¹³ C NMR (75 MHz, CDCl ₃ ) 143.91, 140.56, 132.83, 131.34, 129.45, 129.38, 128.49, 128.23, 128.08, 127.86, 127.44, 127.03, 123.45, 121.58, 92.92, 89.36.

[Example 4] Synthesis of 1- (2- (2,4,6-trimethylphenyl) ethynyl) benzene

(2- (2,4,6-trimethylphenyl) ethynyl) benzene (3d) was obtained in a yield of 87% using 2-bromobiphenyl instead of 4-bromotoluene in the same manner as in Example 1, ≪ / RTI >

¹ H NMR (300 MHz, CDCl ₃ ) 7.54-7.50 (m, 2H), 7.37-7.30 (m, 3H), 6.89 (s, 2H), 2.47 (s, 6H), 2.29

¹³ C NMR (75 MHz, CDCl ₃ ) 140.05, 137.69, 131.24, 128.244, 127.81, 127.53, 123.96, 119.88, 96.95, 87.27, 21.25, 20.91

[Example 5] Synthesis of 1-naphthylethynylbenzene

1-naphthylethynylbenzene (3e) was obtained in a yield of 83% using 1-bromonaphthalene instead of 4-bromotoluene in the same manner as in Example 1.

^{1 H NMR (300 MHz, CDCl} 3) 8.45 (m, 1H), 7.83-7.73 (m, 3H), 7.65-7.29 (m, 8H);

¹³ C NMR (75 MHz, CDCl ₃ ) 133.24, 133.18, 131.63, 130.33, 128.72, 128.39, 128.34, 128.28, 126.74, 126.38, 126.18, 125.23, 123.38, 120.87, 94.31, 87.54.

[Example 6] Synthesis of 1- (2- (3-methylphenyl) ethynyl) -2-methylbenzene

(3- (3-methylphenyl) ethynyl) -2-methylbenzene (3f) was obtained in a yield of 71% by using 2-iodotoluene instead of iodobenzene.

^{1 H NMR (300 MHz, CDCl} 3) 7.48 (m, 1H), 7.45-7.40 (m, 2H), 7.24-7.20 (m, 2H), 7.18-7.12 (m, 3H), 2.51 (s, 3H) , 2.36 (s, 3 H);

¹³ C NMR (75 MHz, CDCl ₃ ) 140.07, 138.27, 131.74, 131.37, 129.40, 129.09, 128.09, 125.53, 123.20, 120.46, 93.51, 87.66, 21.48, 20.73.

[Example 7] Synthesis of 2- (2- (2-methylphenyl) ethynyl) biphenyl

(2- (2- (2-methylphenyl) ethynyl) biphenyl (3 g) was obtained by using 2-bromobiphenyl instead of 4-bromotoluene instead of iodobenzene in place of iodobenzene, ) Was obtained in a yield of 95%.

^{1 H NMR (300 MHz, CDCl} 3) 7.60-7.53 (m, 3H), 7.38-7.23 (m, 7H), 7.13-6.99 (m, 3H), 2.36 (s, 3H);

¹³ C NMR (75 MHz, CDCl ₃ ) 143.77, 140.77, 140.13, 132.98, 131.84, 129.51, 129.51, 129.34, 128.35, 128.12, 127.95, 127.39, 127.04, 125.41, 128.18, 121.99, 92.99, 91.22, 20.46.

Table 1. Composite Yield Table in Examples

The method of producing an arylalkyne compound according to the present invention can be easily used for synthesizing a precursor of a medical candidate material and an electronic material by replacing an alkyne derivative which is difficult to handle due to a low boiling point with a propionic acid. It is possible to replace existing synthetic processes in which waste is a problem.

Claims (12)

a) reacting a mixture comprising a compound of formula (2) and a compound of formula (3) to produce a compound of formula (4); And b) adding a compound of formula (5) to produce a compound of formula (1); ≪ / RTI > [Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

Wherein Ar ₁ and Ar ₂ are the same or different from each other (C ₆ -C ₃₀ ) aryl or (C ₄ -C ₃₀ ) heteroaryl, wherein said aryl or heteroaryl is a straight or branched saturated or unsaturated (C (C ₁ -C ₃₀ ) alkyl, (C ₁ -C ₃₀ ) alkoxy, (C ₆ -C ₃₀ ) aryl, (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀ ) alkyl, linear or branched saturated or unsaturated C ₁ -C ₃₀₎ alkyl (C ₆ -C ₃₀₎ aryl, (C ₆ -C ₃₀₎ aralkyl (C ₁ -C ₃₀₎ alkoxy, (C ₄ -C ₃₀₎ heteroaryl, (C ₃ -C ₃₀₎ Saturated or unsaturated mono- or di (C ₁ -C ₆₎ alkyl, hydroxy, carboxylic acid, amino, straight- or branched-chain saturated or unsaturated heterocycloalkyl of 3 to 7 members inclusive of cycloalkyl, oxygen, nitrogen or sulfur in the heterocycle, C ₃₀₎ alkylamino, (C ₆ -C ₃₀₎ arylamino, a straight or branched chain saturated or unsaturated (C ₁ -C ₃₀₎ alkylcarbonyl, (C ₁ -C ₃₀₎ alkoxycarbonyl, saturated straight or branched chain Or an unsaturated (C ₁ -C ₃₀ ) alkyl acyl, (C _{1 to 30} ) alkylsilyl, benzoyl, diazamino, phenoxy, propyl, cyano, nitro, halogen or a fluorine group, and the linear or branched saturated or unsaturated Alkyl, alkoxy, aryl, aralkyl, aralkoxy, heteroaryl, cycloalkyl, heterocycloalkyl, alkylcarbonyl or alkoxycarbonyl may be further substituted with one or more halogens; Wherein R _1, R ₂ are the same or alkyl, (C ₆ -C ₃₀₎ aryl, (C ₁ -C ₃₀₎ independently of one another represent hydrogen, straight or branched chain saturated or unsaturated (C ₁ -C ₃₀₎ alkyl (C ₆ -C ₃₀₎ aryl, (C ₃ -C ₃₀₎ cycloalkyl (C ₁ -C ₃₀₎ alkyl, (C ₁ -C ₃₀₎ alkylsilyl, (C ₁ -C ₃₀₎ alkoxy, thio (C ₁ -C ₃₀₎ alkoxy, (C ₁ -C ₃₀₎ alkyl siloxy, amide, hydroxy, amino, carboxylic acid, sulfonyl, (C ₆ -C ₃₀₎ aryl (C ₁ -C ₃₀₎ alkyl, (C ₆ -C ₃₀₎ arylsilyl, (C ₆ -C ₃₀₎ aryloxy, (C ₆ -C ₃₀₎ aryl (C ₁ -C ₃₀₎ alkoxy, thio (C ₆ -C ₃₀₎ aryloxy, (C ₆ -C ₃₀₎ aryl siloxane when, (C ₆ -C ₃₀₎ aryl (C ₁ -C ₃₀₎ alkyl siloxy, (C ₆ -C ₃₀₎ aryl amides, (C ₆ -C ₃₀₎ aryl (C ₁ -C ₃₀₎ alkyl amide, hydroxy hydroxy (C ₆ -C ₃₀₎ aryl amide, or (C ₆ -C ₃₀₎ arylamino (C ₆ -C ₃₀₎ and one selected from aryloxy; X &_lt; ₁ > and X &_lt; ₂ > The method according to claim 1, Wherein Ar ₁ and Ar ₂ are the same or different and are independently selected from the group consisting of (C ₆ -C ₃₀ ) aryl, linear or branched, saturated or unsaturated (C ₁ -C ₃₀ ) alkyl, (C ₁ -C ₃₀ ) (C ₆ -C ₃₀ ) aryl, wherein R ₁ and R ₂ may be the same or different and are independently selected from the group consisting of hydrogen, straight or branched, saturated or unsaturated (C ₁ -C ₃₀ ) alkyl, (C ₆ -C ₃₀ ) aryl, (C ₁ -C ₃₀ ) alkyl (C ₆ -C ₃₀ ) aryl, and X ₁ and X ₂ are independently selected from the group consisting of halogen, trifluoromethanesulfonyloxy, methane Sulfonyloxy, or toluenesulfonyloxy. ≪ RTI ID = 0.0 > 11. < / RTI > 3. The method of claim 2, Wherein Ar ₁ and Ar ₂ are any one selected from benzene, toluene, biphenyl, naphthalene, 2,4,6-trimethylphenyl and anisole, R ₁ and R ₂ are both hydrogen, and X ₁ and X ₂ are Wherein R < 1 > The method according to claim 1, Wherein the step a) is carried out by stirring at room temperature for 11 to 15 hours. The method according to claim 1, and b) reacting at 85 to 95 캜 for 11 to 15 hours. The method according to claim 1, Wherein the mixture of step a) further comprises palladium having an oxidation state of 0 and +2 as a catalyst. The method according to claim 6, Wherein the palladium is at least one selected from the group consisting of palladium (II) acetate, palladium (II) acetonate, palladium (II) chloride and bis (triphenylphosphine) palladium (II) dichloride. The method according to claim 1, Wherein the mixture in step a) is selected from the group consisting of bisdiphenylphosphinomethane, triphenylphosphine, tri-tert.-butylphosphane, triphenylphosphonium cyclopentadienide and 2,3,5-triphenyltetrazolium chloride And further comprising at least one selected from the group consisting of an alkyl group and an aryl group. The method according to claim 1, Wherein the mixture in step a) further comprises at least one selected from the group consisting of tetrabutylammonium fluoride, triethylamine, cesium carbonate, diisopropylethylamine, calcium carbonate and sodium hydroxide . The method according to claim 1, Wherein the steps a) and b) are carried out without separation in the same vessel. (delete) (delete)