KR100424205B1 - Process for preparing aromatic iodo compounds - Google Patents

Abstract

According to the present invention, an aromatic iodine compound of formula 1 is provided.

Aromatic iodine compound (Ar-I) method of the present invention is a bromodimethylsulfonium iodide [Me ₂ (Br) S ⁺ I ^_ ], or iododimethylsulfonium iodide [Me ₂ IS ⁺ I ^_ ] is characterized in that the reaction is carried out in one step.

Formula 1

Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently selected from the group consisting of hydrogen atom, halogen atom, alkyl, alkoxy, nitro, formyl, acetyl, benzoyl, aryl or benzyl group , R ₁ , R ₂ , R ₃ , R _4, and R _{5 may} combine to form a polycyclic aryl group, and X represents a carbon or nitrogen atom.

Description

Process for producing aromatic iodine compound {PROCESS FOR PREPARING AROMATIC IODO COMPOUNDS}

The present invention relates to a method for producing an aromatic iodine compound. More specifically, bromodimethylsulfonium iodide [Me ₂ (Br) S ⁺ I ^_ ] prepared directly during the reaction, or iododimethylsulfonium iodide [Me ₂ IS ⁺ I ^_ ] is used. The present invention relates to a method for producing an aromatic iodine compound which can effectively convert aromatic amine compounds into aromatic iodine compounds.

Aromatic halogen compounds, especially aromatic iodine compounds, used as intermediates in the synthesis of various chemicals, have excellent reactivity compared to aromatic bromo or chloro compounds, which are other aromatic halogen compounds, and thus have various uses. As shown in the following example, the aromatic iodine compound reacts well with acetylene substituted with a silane group under a palladium (Pd) catalyst in the carbon-carbon coupling reaction, but the aromatic bromo compound does not proceed at all.

Among the aromatic halogen compounds, reactions that proceed only by derivatives substituted with iodine are known innumerably. Typical applications for aromatic iodine compounds are as follows (Merkushev, EB Synthesis , 1988 , 923).

(1) the Ullman reaction; Aryl-aryl linkages (Fanta, PE Synthesis , 1974 , 9),

(2) Heck reaction; Vinyl group substitution (Heck, RF, Plevyak, JE J. Org. Chem . 1978 , 43, 2454.), acetyl group substitution (Takahashi. S., et. Al., Synthesis , 1980, 627),

And (3) carbonylation; Carbon monoxide substitution (Heck, RF Adv. In Catalysis, 1977 , 26 , 2323).

That is, the role of the aromatic iodine compound as a reaction intermediate is very important, and various preparation methods for these aromatic iodine compounds have been developed as follows.

First, the direct substitution of the hydrogen element. Friedel-Crafts Aromatic Substitution: using iodine (I ₂ ) and a catalyst (Braendlin, HP and McBee, ET, “Friedel-Crafts and Related Reactions”; Ed. Olah, g., Interscience Publisher, NY, 1964, Vol III, Pt 2, p 1517).

The direct substitution method determines the position selectivity ( o , p -aromatic, or m -aromatic) by the X nature of the aromatic substituent group, and is generally used for the preparation of simple aromatic iodine compounds.

Second, the method of substituting an amino group with iodine, ie, Sandmeyer reaction: making a diazonium salt using NaNO ₂ and an acid followed by I ₂ (“The Chemistry of Diazonium and Diazogroups”, Ed. Patai, S., J. Wiley, NY. 1978, part 1, p 288).

Among the above-described methods, in consideration of the position selectivity, many Sandmeyer reactions in which an amino group is converted to a diazonium salt and the same position is substituted with a halogen element are widely used. However, the Sandmeyer reaction is a two-step reaction in which a diazonium salt is first synthesized and confirmed, and then I ₂ is added to replace the iodine anion. In particular, since the safety of diazonium salts is the most important element of the Sandmeyer reaction, process conditions such as low temperature reactions are required. There is a limit.

Recently, research and development for the simplicity of the industrialization process has been continuously conducted, one of which has been proposed to simplify the process from the two-step process through the existing diazonium salt. In other words, isoamyl nitrite is reacted with an aromatic amine in a diiodomethane solvent to convert it into an iodine compound in a one step process (Smith, WB, Ho, OC J. Org. Chem . 1990 , 55 , 2543.).

Looking at the above reaction path, the diazonium salt is not completely made and separated, and the substitution reaction does not proceed, but the diazonium salt is formed by isoamyl nitrite during the reaction, and the substitution reaction of the iodo anion proceeds at the same time. . However, the above reaction also has a limitation in industrial applications due to the following problems. That is, CH ₂ I ₂ , a solvent used, is difficult to remove due to a high boiling point (bp 181 ^o C), and has a problem in that it is not economical by using an excess of isoamyl nitrite.

Therefore, considering the application field of aromatic iodine compounds, a method of preparing an aromatic iodine compound which can be manufactured at a minimum manufacturing cost by a simple step should be developed.

Accordingly, the present inventors have excellent position selectivity in preparing aromatic iodine compounds (Ar-I) from aromatic amine compounds (Ar-NH ₂ ) and can easily prepare aromatic iodine compounds even in a simple step. The discovery of the method has led to the completion of the present invention.

Substitution reactions of aromatic compounds are very important in the nature of the nucleophile to attack. In general, halide anions have nucleophilic functions. However, the function of nucleophiles varies depending on the type of cation shared with the halide anion. Bromodimethylsulfonium bromide [Me ₂ (Br) S ⁺ Br ^_ ], known as a bromide nucleophile with excellent aromatic substitution reaction, is synthesized by hydrobromic acid (HBr) and DMSO as shown in the following reaction (Majetich, g , Hicks, R., Reister, S., J. Org.Chem . 1997 , 62, 4321), using this nucleophile, ie bromodimethylsulfonium cation [Me ₂ (Br) S ⁺ ] If present, an aromatic substitution reaction proceeds, while no other cations such as potassium cations (K ⁺ ), etc., proceed at all.

The present invention is applied to this principle, and by using the iodide nucleophile to substitute the amine group of the aromatic amine compound with iodine, it is possible to easily prepare an aromatic iodine compound in which iodine is substituted at any position.

An object of the present invention is to easily prepare an aromatic iodine compound substituted with an iodo group by reacting an amine group, which is a substituent of an aromatic compound, in a one step process.

Another object of the present invention is to simply prepare an aromatic iodine compound in which iodine is substituted at a predetermined position.

Another object of the present invention is to develop a new iodine nucleophile.

To date amino in a one-step reaction process using bromodimethylsulfonium iodide [Me ₂ (Br) S ⁺ I ^_ ], or iododimethylsulfonium iodide [Me ₂ IS ⁺ I ^_ ] There have been no examples of application to the reaction for converting amino groups of aromatic compounds having substituents into iodine.

The present invention relates to an aromatic amine compound by reacting bromodimethylsulfonium iodide [Me ₂ (Br) S ⁺ I ^_ ] or iododimethylsulfonium iodide [Me ₂ IS ⁺ I ^_ ] It is a method of preparing an iodine compound. The present invention is a method for producing an aromatic iodine compound having a core element of forming a diazonium directly in a stable form in a one-step reaction process and simultaneously causing an iodine substitution reaction.

The present invention is directed by the action of dimethyl sulfoxide (DMSO), hydrobromic acid, and iodine salt (KI, NaI, or NH ₄ I, etc.) to an aromatic compound (aniline derivative or amino pyridine derivative) having an amino group of the formula (2) Bromodimethylsulfonium iodide [Me ₂ (Br) S ⁺ I ^_ ] or dimethylsulfoxide (DMSO) of formula 3, and iododimethylsulfonium urea prepared directly by the action of hydroiodic acid A novel process for preparing the corresponding aromatic iodine compounds of formula (I) by the action of an amide [Me ₂ IS ⁺ I ^_ ].

Wherein Y is Br or I, and R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each a hydrogen atom, a halogen atom, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, nitro, formyl May be independently selected from the group consisting of acetyl, benzoyl, phenyl or benzyl groups, or _{two of} R ₁ , R ₂ , R ₃ , R ₄ and R _{5 may} combine to form a polycyclic aryl group, and X is carbon or nitrogen Represents an atom.

The invention reaction is below reaction scheme I 1a and 1b Pony the bromo dimethyl sulfonic prepared directly in the reactor Titanium as iodide ^{_{[Me 2 (Br) S +}} I _], or iodo dimethyl sulfonic pony Titanium iodide [Me ₂ IS ⁺ I ^_ ]. Bromodimethylsulfonium iodide is produced by hydrobromic acid, DMSO as starting material and by iodide salt (Scheme 1a), and iododimethylsulfonium iodide is produced by hydroiodic acid and DMSO ( Scheme 1b).

On the other hand, the amino group of the aromatic amine compound (Ar-NH ₂ ) can also serve as a strong acid action of hydrobromic acid or hydrogen iodide used in the reaction, and is converted to the diazonium salt by the nitrite salt. DMSO can also serve as a solvent to dissolve nitrite salts.

That is, as shown in Scheme 1 below, the present invention reaction, NO ₂ ^- -HBr acts to prepare the aniline derivatives as Dia Johnny Titanium salt, and DMSO / HBr / I ^- or DMSO / HI is iodide act as a source of the nucleophile Thus, the reaction in which the aryl iodide derivative is produced from the aniline derivative is completed in one step.

In said formula, R <_1> , R <_2> , R <_3> , R <_4> , R <_5> and X are as defined above.

The reaction of the present invention can be applied to all kinds of aniline derivatives or amino pyridine derivatives represented by formula (2), and also to multicyclic aromatic amine compounds or multicyclic amino pyridine derivatives including compounds represented by the following formulas (Ia to Ie) Can be applied.

In the formula, Z represents a hydrogen atom, a halogen atom, an alkyl, alkoxy, nitro, formyl or acetyl group.

The nitrite salt in the reaction of the present invention can be used in the form of all salts in which sodium ions, potassium ions or ammonium ions are bound.

The hydrobromic acid or hydroiodic acid used in the reaction can be used in the form of an aqueous solution, anhydrous gas, or dissolved in carboxylic acid.

The iodine salt used in the reaction can be used in the form of salts of potassium, sodium, or ammonium (KI, NaI, or NH ₄ I).

DMSO used as the reaction solvent may be used in an anhydrous or water-containing state, and may be used in a mixed form with a solvent such as tetrahydrofuran, dimethyl sulfoxide, alcohol, hexane, or the like.

When the reaction temperature is 25 ℃ or less, the reaction rate is slow, productivity is lowered, effective reaction progress is difficult at 160 ℃ or more.

The reaction of the present invention can be promoted by using cuprous iodide or cuprous iodide together.

In the preparation method of the present invention, first, hydrobromic acid is dissolved in DMSO, and then a mixed solution in which iodine salt is added to this solution, or a mixed solution in which hydrogen iodide is added to DMSO, and an aromatic compound having an amino group in DMSO (aniline derivative or amino pyridine). The reaction proceeds by mixing the mixture) and nitrite at a suitable temperature. At this time, it is important to prepare bromodimethylsulfonium iodide [Me ₂ (Br) S ⁺ I ^_ ] in which hydrobromic acid and DMSO are first mixed, and then iodine salt is added to HBr / DMSO / I. ^- to create a mixture. Iododimethylsulfonium iodide [Me ₂ IS ⁺ I ^_ ] mixes iodide acid and DMSO to prepare HI / DMSO mixed solution. Next, the reaction is carried out by making a mixture solution in which aniline derivatives are added to a solution in which nitrous acid is mixed with DMSO, and adding the above-prepared HBr / DMSO / I ^- or HI / DMSO mixture. Next, the production of the compound of formula 1 is confirmed using thin layer chromatography, and then the reaction solution is extracted with a solvent such as ethyl ether to obtain a product. The product is separated by standard methods such as evaporation / extraction, and then purified by standard methods such as recrystallization or column chromatography on silica gel, if necessary.

The mechanism of action of the present invention is described below.

As shown in Scheme 2 below, nitrite anion and hydrobromic acid or hydroiodic acid react to form nitrosyl cations.

The nitrosyl cation obtained above is reacted with an aromatic amine group to form a diazonium salt as shown in Scheme 3 below.

Wherein R ₁ to R ₅ and X are as defined above.

Meanwhile, as described above, hydrobromic acid and DMSO instantly form bromodimethylsulfonium bromide, and then bromodimethylsulfonium iodide in which bromide is substituted with iodine is added by the added iodine salt ( Scheme 1a). In addition, iododimethylsulfonium iodide is produced directly by mixing hydroiodic acid with DMSO (Scheme 1b). The reaction of the present invention is performed by directly attacking the diazonium salt with iodo ions (I ⁻ ), which is a nucleophile of bromodimethylsulfonium iodide, formed almost simultaneously with the formation of the diazonium salt, as shown in Scheme 4 below. As a result, aryl iodide of formula 1 and nitrogen gas are produced.

Wherein R ₁ to R ₅ and X are as defined above.

In this reaction, DMSO plays a role of two solvents: a solvent for dissolving an aromatic compound having a nitrite salt and an amino group and a reagent for preparing bromodimethylsulfonium iodide or iododimethylsulfonium iodide, an activated nucleophile. Perform. In addition, DMSO is a polar solvent and therefore has a function of stabilizing the diazonium salt produced.

Hereinafter, the present invention will be described in more detail with reference to Examples. The following examples are merely illustrative of the present invention and the present invention is not limited by these examples.

Example 1

Synthesis of 2-iodophenol: How to Use Iododimethylsulfonium Iodide

DMSO (5 ml) was added to a three-necked flask, and 2-aminophenol (0.109 g, 1.0 mmol) and KNO ₂ (0.172 g, 2.0 mmol) were added and dissolved completely at room temperature with vigorous stirring. The reaction is carried out under a nitrogen atmosphere. Then a solution of 57% HI aqueous solution (0.66 ml, 5.0 mmol) in DMSO (5 ml) is slowly added. After the addition is completed, the solution is further stirred at room temperature for 10 minutes. After confirming that the reaction was completed using thin layer chromatography, the mixture was extracted with an organic solvent. After drying over anhydrous magnesium sulfate, the solvent was removed and the mixture obtained was purified by column chromatography to give 2-iodophenol (yield: 85%).

¹ H-NMR (CDCl ₃ ): δ 6.50 (d, 1H), 6.70 (t, 1H), 7.09 (t, 1H), 7.46 (d, 1H)

Example 2

Synthesis of 2-iodophenol: How to Use Bromodimethylsulfonium Iodide

DMSO (5 ml) was added to a three-necked flask, and 2-aminophenol (0.109 g, 1.0 mmol) and KNO ₂ (0.172 g, 2.0 mmol) were added and dissolved completely at room temperature with vigorous stirring. The reaction is carried out under a nitrogen atmosphere. Then, a solution of 47% HBr aqueous solution (0.46ml, 4.0mmol) dissolved in DMSO (5ml) and KI (0.83g, 5.0mmol) dissolved in DMSO (5ml) are added slowly. After the addition is completed, the solution is further stirred at room temperature for 10 minutes. After confirming that the reaction was completed using thin layer chromatography, the mixture was extracted with an organic solvent. After drying over anhydrous magnesium sulfate, the solvent was removed and the mixture obtained was purified by column chromatography to give 2-iodophenol (yield: 84%).

¹ H-NMR (CDCl ₃ ): δ 6.50 (d, 1H), 6.70 (t, 1H), 7.09 (t, 1H), 7.46 (d, 1H)

Example 3

Synthesis of 4-iodobenzophenone: How to Use Iododimethylsulfonium Iodide

DMSO (25 ml) was added to a three-necked flask, and 4-aminobenzophenone (0.986 g, 5 mmol) and KNO ₂ (0.851 g, 10 mmol) were added and dissolved completely at room temperature with vigorous stirring. The reaction is carried out under a nitrogen atmosphere. Then add a solution of 57% HI aqueous solution (3.29ml, 25mmol) in DMSO (25ml) slowly. After the addition is completed, the solution is further stirred at room temperature for 10 minutes. After confirming that the reaction was completed using thin layer chromatography, the mixture was extracted with an organic solvent. The mixture obtained by drying over anhydrous magnesium sulfate and removing the solvent was purified by column chromatography to give 4-iodobenzophenone (yield: 88%).

¹ H-NMR (CDCl ₃ ): δ 7.36 (t, 2H), 7.45 (t, 1H), 7.47 (d, 2H), 7.70 (d, 2H), 7.74 (d, 2H)

Example 4

Synthesis of 4-iodobenzophenone: How to Use Bromodimethylsulfonium Iodide

DMSO (25 ml) was added to a three-necked flask, and 4-aminobenzophenone (0.986 g, 5 mmol) and KNO ₂ (0.851 g, 10 mmol) were added and dissolved completely at room temperature with vigorous stirring. The reaction is carried out under a nitrogen atmosphere. Then, a solution of 47% HBr aqueous solution (2.31ml, 20mmol) dissolved in DMSO (25ml) and KI (4.15g, 25mmol) dissolved in DMSO (25ml) are added slowly. After the addition is completed, the solution is further stirred at room temperature for 10 minutes. After confirming that the reaction was completed using thin layer chromatography, the mixture was extracted with an organic solvent. The mixture obtained by drying over anhydrous magnesium sulfate and removing the solvent was purified by column chromatography to give 4-iodobenzophenone (yield: 90%).

¹ H-NMR (CDCl ₃ ): δ 7.36 (t, 2H), 7.45 (t, 1H), 7.47 (d, 2H), 7.70 (d, 2H), 7.74 (d, 2H)

Example 5

Synthesis of 2,4-difluoro-1-iodobenzene: using iododimethylsulfonium iodide and cuprous iodide

DMSO (30 ml) was added to a three-necked flask, and 2,4-difluoroaniline (1.29 g, 10 mmol) and KNO ₂ (1.72 g, 20 mmol) were added to dissolve completely at room temperature with vigorous stirring. The reaction is carried out under a nitrogen atmosphere. Then, a solution of 57% HI aqueous solution (6.38 ml, 50 mmol) and CuI (1.92 g, 20 mmol) dissolved in DMSO (30 ml) is slowly added. After the addition is completed, the solution is further stirred at room temperature for 10 minutes. After confirming that the reaction is completed by using thin layer chromatography, the mixture is extracted with an organic solvent. The mixture obtained by drying over anhydrous magnesium sulfate and then removing the solvent was purified by column chromatography to give 2,4-difluoro-1-iodobenzene (yield: 92%). When CuI was not added in the same reaction, the final compound 2,4-difluoro-1-iodobenzene was obtained in a yield of 85%.

¹ H-NMR (CDCl ₃ ): δ 6.51 (d, 1H), 6.44 (s, 1H), 7.60 (d, 1H).

Example 6

Synthesis of 2,4-difluoro-1-iodobenzene: method using bromodimethylsulfonium iodide

DMSO (30 ml) was added to a three-necked flask, and 2,4-difluoroaniline (1.29 g, 10 mmol) and KNO ₂ (1.72 g, 20 mmol) were added to dissolve completely at room temperature with vigorous stirring. The reaction is carried out under a nitrogen atmosphere. Then, a solution of 47% HBr aqueous solution (4.62ml, 40mmol) dissolved in DMSO (30ml) and KI (8.30g, 50mmol) dissolved in DMSO (30ml) are added slowly. After the addition is completed, the solution is further stirred at room temperature for 10 minutes. After confirming that the reaction was completed using thin layer chromatography, the mixture was extracted with an organic solvent. The mixture obtained by drying over anhydrous magnesium sulfate and then removing the solvent was purified by column chromatography to give 2,4-difluoro-1-iodobenzene (yield: 90%).

¹ H-NMR (CDCl ₃ ): δ 6.51 (d, 1H), 6.44 (s, 1H), 7.60 (d, 1H).

Example 7

Synthesis of 2,6-dimethyliodobenzene:

Except for using 2,6-dimethylaniline (0.606g, 5.0mmol) instead of 4-aminobenzophenone (0.986g, 5mmol) as starting material 2,6-dimethyliodobenzene (yield) in the same manner as in Example 4 : 89%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 2.35 (s, 6H), 6.69 (d, 2H), 7.01 (t, 1H)

Example 8

Synthesis of 1-iodo-2-methoxy-5-nitrobenzene:

1-iodo- in the same manner as in Example 3, except that 2-methoxy-5-nitroaniline (0.840 g, 5.0 mmol) was used instead of 4-aminobenzophenone (0.986 g, 5 mmol) as a starting material. 2-methoxy-5-nitrobenzene was obtained (yield: 93%).

¹ H-NMR (CDCl ₃ ): δ 3.76 (s, 3H), 6.85 (d, 1H), 8.09 (d, 1H), 8.46 (s, 1H).

Example 9

Synthesis of 1-iodo-4-nitrobenzene:

Except for using 4-nitroaniline (0.691g, 5.0mmol) instead of 4-aminobenzophenone (0.986g, 5mmol) as a starting material 1-iodo-4-nitrobenzene ( Yield: 89%).

¹ H-NMR (CDCl ₃ ): δ 7.88 (d, 2H), 8.01 (d, 2H).

Example 10

Synthesis of 2-iodoanthracene:

2-iodoanthracene (yield: 86%) in the same manner as in Example 4 except that 2-aminoanthracene (0.966 g, 5.0 mmol) was used instead of 4-aminobenzophenone (0.986 g, 5 mmol) as a starting material. ) Was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.39 (t, 2H), 7.64 (d, 1H), 7.95 (d, 1H), 7.91 (d, 2H), 8.16 (s, 1H), 8.22 (s, 1H ), 8.32 (s, 1 H).

Example 11

Synthesis of 2-iodoanthraquinone:

The 2-iodoanthraquinone (yield: yield: the following procedure was used in the same manner as in Example 4 except for using 2-aminoanthraquinone (1.116g, 5.0mmol) instead of 4-aminobenzophenone (0.986g, 5mmol) as starting material. 90%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.55 (t, 2H), 7.57 (d, 1H), 7.80 (d, 2H), 7.93 (d, 1H), 8.18 (s, 1H).

Example 12

Synthesis of 2-iodo-3-nitropyridine:

2-iodo-3 in the same manner as in Example 3 except for using 2-amino-3-nitropyridine (0.696 g, 5.0 mmol) instead of 4-aminobenzophenone (0.986 g, 5 mmol) as starting material. Nitropyridine (yield: 90%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.76 (t, 1H), 8.49 (d, 1H), 8.86 (d, 1H).

Example 13

Synthesis of 5-iodosalicylic Acid:

5-iodosalicylic acid (yield: 94%) in the same manner as in Example 3 except that 5-aminosalicylic acid (0.766 g, 5.0 mmol) was used instead of 4-aminobenzophenone (0.986 g, 5 mmol) as a starting material. ) Was obtained.

¹ H-NMR (CDCl ₃ ): δ 6.61 (d, 1H), 6.67 (d, 1H), 7.14 (s, 1H).

According to the present invention, since the iodide substitution reaction of all aromatic amine compounds is possible, and is made in a one-step process under mild reaction conditions (for example, about 10 minutes at room temperature), the manufacturing method is simple, and a separate apparatus cost There is an effect that can minimize the environmental pollution without this need.

Claims (11)

A method for producing an aromatic iodine compound characterized by reacting bromodimethylsulfonium iodide or iododimethylsulfonium iodide with an aromatic amine compound. The bromodimethylsulfonium iodide according to claim 1, wherein said reaction is prepared directly in a reaction vessel by treating an aromatic amine compound with nitrite and reacting with dimethyl sulfoxide (DMSO), hydrobromic acid, and iodine salt. A method for producing an aromatic iodine compound, characterized in that the reaction is carried out in one step by reacting iododimethylsulfonium iodide prepared directly in a reaction vessel by a reaction of id or dimethyl sulfoxide (DMSO) and hydroiodic acid. The method of claim 2, wherein the aromatic iodine compound is a compound of formula 1 below. Formula 1 In the formula, R _1, R _2, R _3, R ₄ and R ₅ are each a hydrogen atom, a halogen atom, a C ₁ ~C ₄ alkyl, C ₁ ~C ₄ alkoxy, nitro, formyl, acetyl, benzoyl, phenyl Or be independently selected from the group consisting of benzyl groups, or _{two of} R ₁ , R ₂ , R ₃ , R ₄ and R _{5 may} combine to form a polycyclic aryl group, and X represents a carbon or nitrogen atom. The method of claim 3, wherein the aromatic amine compound is a compound of formula 2 below. Formula 2 Wherein R ₁ to R ₅ and X are as defined in Formula 1 above. The method of claim 2, wherein the aromatic amine compound is one selected from the following compounds. Wherein, Z represents a hydrogen atom, a halogen atom, a C ₁ ~C ₄ alkyl, C ₁ ~C ₄ alkoxy, nitro, formyl or acetyl. 6. The method of claim 2, wherein the nitrite salt is a salt in which one ion selected from sodium ions, potassium ions, and ammonium ions is bound. 7. The method for producing an aromatic iodine compound according to claim 6, wherein the hydrobromic acid or hydroiodic acid is one of an aqueous solution, an anhydrous gas, or a form dissolved in carboxylic acid. 8. The method of claim 7, wherein the iodine salt is one selected from KI, NaI or NH ₄ I. The method of claim 8, wherein the dimethyl sulfoxide (DMSO) is an aromatic, characterized in that used in the state containing anhydrous or water, or mixed with one solvent selected from tetrahydrofuran, dimethyl sulfoxide, alcohol, hexane Method for preparing an iodine compound. 10. The method of claim 9, wherein the reaction is carried out at 25 to 160 ° C. The method for producing an aromatic iodine compound according to claim 10, wherein the reaction is promoted by using cuprous iodide or cuprous iodide together in the reaction.