KR20110073498A - 2-benzyl-4-(2,4-dichlorophenyl)-5-methylimidazole compound - Google Patents

Abstract

상기 식에서 X₁ 과 X₂는 동일하거나 상이하고, 수소 원자, 염소 원자, 또는 브롬 원자이다.It is an object of the present invention to provide 2-benzyl-4- (2,4-dichlorophenyl) -5-methylimidazole compounds useful as antioxidants on copper surfaces, curing agents of epoxy resins, or intermediates of pharmaceuticals and pesticides. will be.
2-benzyl-4- (2,4-dichlorophenyl) -5-methylimidazole compound is represented by formula (I). The compound can be synthesized by reacting a 2-halogenated 2 ', 4'-dichloropropiophenone compound with an arylacetamidine compound under heating conditions in the presence of a dehalogenating agent in an organic solvent.

In the above formula, X ₁ and X ₂ are the same or different and are a hydrogen atom, a chlorine atom, or a bromine atom.

Description

2-benzyl-4- (2,4-dichlorophenyl) -5-methylimidazole compound {2-BENZYL-4- (2,4-DICHLOROPHENYL) -5-METHYLIMIDAZOLE COMPOUND}

The present invention relates to novel 2-benzyl-4- (2,4-dichlorophenyl) -5-methylimidazole compounds.

As an imidazole compound similar to the compound of the present invention, for example, 2- (2,4-dichloro-benzyl) -5- (3,4-dichloro-phenyl) -1 H-imidazole is disclosed in Patent Document 1 . However, this document does not disclose an imidazole compound having a methyl group bonded to position 4 (5) of the imidazole ring.

JP-T-2003-500357 (Page 7, Page 51)

It is an object of the present invention to provide novel 2-benzyl-4- (2,4-dichlorophenyl) -5-methylimidazole compounds.

In order to solve the above problem, the inventors of the present invention conducted extensive and intensive studies. As a result, the inventors of the present invention have found a novel 2-benzyl-4- (2,4-dichlorophenyl) -5-methylimidazole compound of the general formula (I) which can be synthesized, and achieved the present invention.

In other words, the present invention includes the following aspects in its broadest configuration:

(1) 2-benzyl-4- (2,4-dichlorophenyl) -5-methylimidazole compound of formula (I):

In the above formula, X ₁ and X ₂ are the same or different and are a hydrogen atom, a chlorine atom, or a bromine atom.

The 2-benzyl-4- (2,4-dichlorophenyl) -5-methylimidazole compounds of the present invention are antioxidants for metals, especially copper (including copper alloys) surfaces, and as curing agents or curing accelerators of epoxy resins. As an intermediate raw material in the pharmaceutical and pesticide fields.

The present invention will be described in detail below.

The 2-benzyl-4- (2,4-dichlorophenyl) -5-methylimidazole compound of the present invention is a compound represented by the following formula (I), and examples thereof include the following compounds:

2-benzyl-4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (2-chlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (3-chlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (4-chlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (2,3-dichlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (2,4-dichlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (2,5-dichlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (2,6-dichlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (3,4-dichlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (3,5-dichlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (2-bromobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (3-bromobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (4-bromobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (2,3-dibromobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (2,4-dibromobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (2,5-dibromobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (2,6-dibromobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (3,4-dibromobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (3,5-dibromobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (3-bromo-2-chlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (4-bromo-2-chlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (5-bromo-2-chlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (2-bromo-6-chlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (2-bromo-3-chlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (4-bromo-3-chlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (5-bromo-3-chlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (2-bromo-5-chlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole,

2- (2-bromo-4-chlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole, and

2- (3-bromo-4-chlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole.

In the above formula, X ₁ and X ₂ are the same or different and are a hydrogen atom, a chlorine atom, or a bromine atom.

The 2-benzyl-4- (2,4-dichlorophenyl) -5-methylimidazole compound of the present invention can be synthesized according to known methods. For example, the compound is 2-halogenated 2 ', 4'-dichloropropiophenone (2', 4'-dichloropropiophenone) under heating conditions in the presence of a dehalogenating agent in an organic solvent, as shown in the following scheme. ) Compound can be synthesized by reacting with an arylacetamide compound.

Wherein X ₁ and X ₂ are the same or different and are a chlorine atom, bromine atom, or iodine atom.

In the above scheme, the amount of the arylacetamide compound used is preferably 0.8 to 1.5 times the molar ratio, and more preferably 0.9 to 1.1 times the molar ratio relative to the 2-halogenated 2'4'-dichloropropiophenone compound. . The amount of the dehalogenating agent used is preferably 1 to 10 times the equivalent of the 2-halogenated 2'4'-dichloropropiophenone compound.

As the 2-halogenated 2'4'-dichloropropiophenone compound, 2,2 ', 4'-trichloropropiophenone, 2-bromo-2', 4'-dichloroprepiophenone, and 2- Iodo-2 ', 4'-dichloropropiophenone.

The 2-halogenated 2'4'-dichloropropiophenone compound is obtained by halogenating the 2'4'-dichloropropiophenone 2-position. As halogenation, chlorination or iodide is also possible, but the bromination reaction which reacts the same molar amount of bromine with 2 ', 4'-dichloropropiophenone is the simplest and most convenient.

Commercially available materials can be used, such as 2 ', 4'-dichloropropiophenone.

The arylacetamidine compound is obtained by reaction of arylacetamidine hydrochloride with an alkali chemicals and removal of hydrogen chloride. In the synthesis scheme of the above imidazole compound, instead of the arylacetamidine compound, salts of commonly known inorganic or organic acids of arylacetamidine hydrochloride or arylacetamidine compound may also be used together.

The arylacetamidine hydrochloride can be synthesized according to known methods. For example, arylacetamidine hydrochloride reacts benzylcyanide compounds with lower alcohols such as hydrogen chloride gas and ethanol to convert to arylacetamide hydrochloride and further reaction with ammonia, as shown in the following scheme. Can be synthesized by

Wherein X ₁ and X ₂ are as described above.

Examples of hydrochlorides of the arylacetamidine compounds obtained through the reaction include the following compounds:

Phenylacetamidine hydrochloride,

(2-chlorophenyl) acetamidine hydrochloride,

(3-chlorophenyl) acetamidine hydrochloride,

(4-chlorophenyl) acetamidine hydrochloride,

(2,3-dichlorophenyl) acetamide hydrochloride,

(2,4-dichlorophenyl) acetamide hydrochloride,

(2,5-dichlorophenyl) acetamidine hydrochloride,

(2,6-dichlorophenyl) acetamidine hydrochloride,

(3,4-dichlorophenyl) acetamidine hydrochloride,

(3,5-dichlorophenyl) acetamidine hydrochloride,

(2-bromophenyl) acetamidine hydrochloride,

(3-bromophenyl) acetamidine hydrochloride,

(4-bromophenyl) acetamide hydrochloride,

(2,3-dibromophenyl) acetamidine hydrochloride,

(2,4-dibromophenyl) acetamidine hydrochloride,

(2,5-dibromophenyl) acetamidine hydrochloride,

(2,6-dibromophenyl) acetamidine hydrochloride,

(3,4-dibromophenyl) acetamidine hydrochloride,

(3,5-dibromophenyl) acetamidine hydrochloride,

(3-bromo-2-chlorophenyl) acetamide hydrochloride,

(4-bromo-2-chlorophenyl) acetamide hydrochloride,

(5-bromo-2-chlorophenyl) acetamidine hydrochloride,

(2-bromo-6-chlorophenyl) acetamidine hydrochloride,

(2-bromo-3-chlorophenyl) acetamide hydrochloride,

(4-bromo-3-chlorophenyl) acetamide hydrochloride,

(5-bromo-3-chlorophenyl) acetamide hydrochloride,

(2-bromo-5-chlorophenyl) acetamidine hydrochloride,

(2-bromo-4-chlorophenyl) acetamidine hydrochloride, and

(3-bromo-4-chlorophenyl) acetamidine hydrochloride.

As the dehalogenating agent, any known dehalogenating agent can be used without limitation. Examples of the dehalogenating agent include inorganic alkali compounds such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate; Organic base compounds such as triethylamine and 1,8-diazabicyclo [5.4.0] -7-undecene (DBU); Metal alkoxides such as methoxy sodium and tert -butoxy potassium and the like.

As the organic solvent, any known organic solvent capable of dissolving 2-halogenated 2 ', 4'-dichloropropiophenone compound, arylacetamidine compound, and salts thereof may be used without limitation in the reaction. Can be. Examples of the solvent include alcohols such as isopropyl alcohol and tert -butanol; Hydrocarbons such as hexane and toluene; Halogenated hydrocarbons such as chloroform and chlorobenzene; Ethers such as ethyl acetate; Nitriles such as acetonitrile; Ethers such as tetrahydrofuran, dioxane and ethylene glycol dimethyl ether; Amides such as N, N-dimethylformamide (DMF) and N, N-dimethylacetamide (DMAC); Such as dimethyl sulfoxide (DMSO) and the like. The solvents may be used in combination.

The temperature of the reaction is preferably room temperature to reflux temperature, and the reaction time is preferably 1 to 10 hours. The reaction is usually carried out at atmospheric pressure.

The 2-benzyl-4- (2,4-dichlorophenyl) -5-methylimidazole compound formed under the above reaction conditions can be separated by post-treatment in general. For example, the crude product of the compound can be obtained by partitioning the reaction mixture after completion of the reaction between the aqueous and organic solvent layers, washing the organic solvent layer with water and then evaporating the organic solvent, and the crude product is recrystallized. It can be further refined by chemical manipulation or the like.

Examples

The invention is described below with reference to the examples, but the invention is not to be construed as being limited thereto. Along with this, Reference Examples 1 and 2 show examples of synthesis of phenylacetamidine hydrochloride and 2-bromo-2 ', 4'-dichloropropiophenone, respectively.

Reference Example 1

(Synthesis of phenylacetamidine hydrochloride)

To a solution consisting of 117.8 g (1.0006 mol) of phenylacetonitrile and 55.8 g (1.12 mol) of dry ethanol, 44.6 g (1.22 mol) of hydrogen chloride gas were injected at 5-10 ° C. over 4 hours. The reaction solution was placed at 4 ° C. for 1 day, further at room temperature for 2 days, and ethylphenylacetimidae hydrochloride precipitated out as a white solid.

Ethylphenylacetimidae hydrochloride collected by filtration was triturated and added in portions to the solution consisting of 36.6 g (2.09 moles) of ammonia and 246 g of dry ethanol with shaking under ice-cooling. The mixture was then stirred for 2 hours under ice cooling and further at room temperature overnight. After filtering the insoluble white solid, the filtrate was dried under reduced pressure and concentrated to give 172.5 g (1.011 mol, 100.5% yield) of pale yellow phenylacetamidine hydrochloride in the form of a thick syrup.

Reference Example 2

(Synthesis of 2-bromo-2 ', 4'-dichloropropiophenone)

To a solution consisting of 62.4 g (0.307 mol) of 2 ', 4'-dichloropropiophenone and 70 g of methanol, 49.8 g (0.132 mol) of bromine were added dropwise at 60-65 DEG C over 45 minutes. The reaction solution was concentrated to 115 g under reduced pressure and the concentrate was partitioned between 120 g toluene and 150 g water. The toluene layer was washed with water and dried over magnesium sulfate, and the solvent was evaporated under reduced pressure to give 84.8 g (0.301 mol, 98.0%) of viscous pale yellow 2-bromo-2 ', 4'-dichloropropiophenone. Obtained.

Example 1

(Synthesis of 2-benzyl-4- (2,4-dichlorophenyl) -5-methylimidazole)

A suspension consisting of 42.7 g (0.250 mol) of phenylacetamidine hydrochloride, 86.4 g (0.625 mol) of potassium carbonate, and 120 ml of N, N-dimethylformamide was stirred at 50 ° C. for 40 minutes, followed by 2-broken A solution consisting of 70.5 g (0.250 mole) of mother-2 ', 4'-dichloropropiophenone and 80 ml of N, N-dimethylformamide was added dropwise to the suspension at the same temperature for 1 hour 20 minutes and then further Stir at 60 ° C. for 3 hours.

The reaction suspension was then cooled and then partitioned between 1000 ml of water and 200 ml of toluene. Thereafter, the toluene layer was washed twice with water, and then toluene was evaporated under reduced pressure. Then 120 ml of acetonitrile were added and the whole was stirred under heating to precipitate the crystals. After cooling, the crystals were collected by filtration and washing with acetonitrile to obtain a milky white powder. The powder was recrystallized from acetonitrile to obtain 28.7 g (0.090 mol, yield 30.0%) of colorless needles.

Melting points of the obtained crystals, Rf values in thin layer chromatography, and ¹ H-NMR and mass spectrometry data are as follows.

Melting Point: 167-169 ℃

TLC (silica gel, acetone): Rf = 0.59

¹ H-NMR (d ₆ -DMSO) δ: 2.09 (s, 3H), 3.95 (s, 2H), 7.21-7.62 (m, 8H).

MS m / z (%): 318 (M + 2, 62), 316 (M ⁺ , 100), 301 (3), 281 (8), 239 (3), 190 (2), 171 (5), 136 (3), 122 (7), 103 (6), 91 (6), 77 (3).

According to the spectral data, the obtained product is 2-benzyl-4- (2,4-dichlorophenyl) -5-methylimidazole represented by the following formula.

Example 2

(Synthesis of 2- (2-chlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole)

First, (2-chlorophenyl) acetamidine hydrochloride was synthesized according to the method of Reference Example 1 using (2-chlorophenyl) acetonitrile instead of phenylacetonitrile of Reference Example 1.

Next, white powder form crystals were obtained by performing the synthesis procedure according to the method of Example 1 using (2-chlorophenyl) acetamidine hydrochloride instead of the phenylacetamidine hydrochloride of Example 1.

Melting points of the obtained crystals, Rf values in thin layer chromatography, and ¹ H-NMR and mass spectrometry data are as follows.

Melting Point: 161-163 ℃

TLC (silica gel, ethyl acetate): Rf = 0.85

¹ H-NMR (d ₆ -DMSO) δ: 2.09 (s, 3H), 4.06 (s, 2H), 7.26-7.60 (m, 7H).

MS m / z (%): 352 (M + 2, 16), 350 (M +, 16), 317 (63), 315 (100), 279 (3), 243 (2), 171 (2), 137 (3), 122 (6), 101 (4).

According to the spectral data, the obtained product is 2- (2-chlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole represented by the following formula.

Example 3

(Synthesis of 2- (3-chlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole)

First, (3-chlorophenyl) acetamidine hydrochloride was synthesized according to the method of Reference Example 1 using (3-chlorophenyl) acetonitrile instead of phenylacetonitrile of Reference Example 1.

Next, white powder form crystals were obtained by performing the synthesis procedure according to the method of Example 1 using (3-chlorophenyl) acetamide hydrochloride instead of phenylacetamidine hydrochloride.

Melting points of the obtained crystals, Rf values in thin layer chromatography, and ¹ H-NMR and mass spectrometry data are as follows.

Melting Point: 143-146 ℃

TLC (silica gel, ethyl acetate): Rf = 0.75

¹ H-NMR (d ₆ -DMSO) δ: 2.09 (s, 3H), 3.96 (s, 2H), 7.24-7.62 (m, 7H).

MS m / z (%): 352 (M + 2, 93), 350 (M +, 100), 315 (18), 279 (3), 239 (5), 190 (2), 173 (3), 164 (5), 137 (6), 122 (9), 102 (6), 89 (4).

According to the spectral data, the obtained product is 2- (3-chlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole represented by the following formula.

Example 4

(2- (4-chlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole)

First, (4-chlorophenyl) acetamidine hydrochloride was synthesized according to the method of Reference Example 1 using (4-chlorophenyl) acetonitrile instead of phenylacetonitrile of Reference Example 1.

Next, white powder form crystals were obtained by carrying out the synthesis procedure according to the method of Example 1 using (4-chlorophenyl) acetamidine hydrochloride instead of the phenylacetamidine hydrochloride of Example 1.

Melting points of the obtained crystals, Rf values in thin layer chromatography, and ¹ H-NMR and mass spectrometry data are as follows.

Melting Point: 198-199 ℃

TLC (silica gel, ethyl acetate): Rf = 0.85

¹ H-NMR (d ₆ -DMSO) δ: 2.08 (s, 3H), 3.93 (s, 2H), 7.28-7.60 (m, 7H).

MS m / z (%): 352 (M + 2, 91), 350 (M +, 100), 315 (20), 279 (3), 239 (3), 190 (3), 164 (4), 137 (7), 122 (10), 102 (6), 89 (3).

According to the spectral data, the obtained product is 2- (4-chlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole represented by the following formula.

Example 5

(2- (2,4-dichlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole)

First, (2,4-dichlorophenyl) acetamidine hydrochloride was synthesized according to the method of Reference Example 1 using (2,4-dichlorophenyl) acetonitrile instead of phenylacetonitrile of Reference Example 1.

Next, a milky white powder was formed by carrying out the synthesis according to the method of Example 1 using (2,4-dichlorophenyl) acetamidine hydrochloride instead of phenylacetamidine hydrochloride of Example 1. Crystals were obtained.

Melting points of the obtained crystals, Rf values in thin layer chromatography, and ¹ H-NMR and mass spectrometry data are as follows.

Melting Point: 164-165 ℃

TLC (silica gel, acetone): Rf = 0.66

¹ H-NMR (d ₆ -DMSO) δ: 2.10 (s, 3H), 4.06 (s, 2H), 7.35-7.60 (m, 6H).

MS m / z (%): 388 (M + 4, 14), 386 (M + 2, 29), 384 (M ⁺ , 22), 351 (94), 349 (100), 316 (20), 314 31, 299 (2), 279 (2), 193 (2), 171 (5), 159 (5), 136 (7), 121 (4), 101 (3).

According to the spectral data, the obtained product is 2- (2,4-dichlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole represented by the following formula.

Example 6

(Synthesis of 2- (2,6-dichlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole)

First, (2,6-dichlorophenyl) acetamidine hydrochloride was synthesized according to the method of Reference Example 1 using (2,6-dichlorophenyl) acetonitrile instead of phenylacetonitrile of Reference Example 1.

Next, white powder form crystals were obtained by carrying out the synthesis according to the method of Example 1 using (2,6-dichlorophenyl) acetamidine hydrochloride instead of the phenylacetamidine hydrochloride of Example 1. It was.

Melting points of the obtained crystals, Rf values in thin layer chromatography, and ¹ H-NMR and mass spectrometry data are as follows.

Melting Point: 240-241 ℃

TLC (silica gel, hexane: ethyl acetate = 1: 1): Rf = 0.52

¹ H-NMR (d ₆ -DMSO) δ: 2.05 (s, 3H), 4.25 (s, 2H), 7.31-7.62 (m, 6H).

MS m / z (%): 388 (M + 4, 13), 386 (M + 2, 27), 384 (M ⁺ , 21), 351 (99), 349 (100), 314 (32), 299 (3), 279 (3), 243 (3), 193 (4), 171 (7), 159 (7), 139 (11), 121 (9), 101 (6), 89 (2), 75 (3).

According to the spectral data, the obtained product is 2- (2,6-dichlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole represented by the following formula.

Example 7

(Synthesis of 2- (3,4-dichlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole)

First, (3,4-dichlorophenyl) acetamidine hydrochloride was synthesized according to the method of Reference Example 1 using (3,4-dichlorophenyl) acetonitrile instead of phenylacetonitrile of Reference Example 1.

Next, white powder form crystals were obtained by carrying out the synthesis according to the method of Example 1 using (3,4-dichlorophenyl) acetamidine hydrochloride instead of the phenylacetamidine hydrochloride of Example 1. It was.

Melting points of the obtained crystals, Rf values in thin layer chromatography, and ¹ H-NMR and mass spectrometry data are as follows.

Melting Point: 184-185 ℃

TLC (silica gel, ethyl acetate): Rf = 0.80

¹ H-NMR (d ₆ -DMSO) δ: 2.08 (s, 3H), 3.96 (s, 2H), 7.26-7.61 (m, 6H).

MS m / z (%): 388 (M + 4, 48), 386 (M + 2, 100), 384 (M +, 80), 349 (13), 314 (9), 239 (5), 212 ( 2), 190 (3), 171 (8), 159 (6), 136 (10), 121 (5), 101 (3).

According to the spectral data, the obtained product is 2- (3,4-dichlorobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole represented by the following formula.

Example 8

(Synthesis of 2- (4-bromobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole)

First, (4-bromophenyl) acetamidine hydrochloride was synthesized according to the method of Reference Example 1 using (4-bromophenyl) acetonitrile instead of phenylacetonitrile of Reference Example 1.

Next, white powder form crystals were obtained by performing the synthesis procedure according to the method of Example 1 using (4-bromophenyl) acetamidine hydrochloride instead of the phenylacetamidine hydrochloride of Example 1. .

Melting points of the obtained crystals, Rf values in thin layer chromatography, and ¹ H-NMR and mass spectrometry data are as follows.

Melting Point: 206-207 ℃

TLC (silica gel, hexane: ethyl acetate = 1: 1): Rf = 0.38

¹ H-NMR (d ₆ -DMSO) δ: 2.07 (s, 3H), 3.92 (s, 2H), 7.24-7.63 (m, 7H).

MS m / z (%): 398 (M + 4, 47), 396 (M + 2, 100), 394 (M ⁺ , 64), 361 (6), 315 (11), 299 (3), 279 (3), 239 (5), 198 (4), 183 (3), 171 (11), 136 (6), 122 (20), 102 (17), 89 (8), 75 (5).

According to the spectral data, the obtained product is 2- (4-bromobenzyl) -4- (2,4-dichlorophenyl) -5-methylimidazole represented by the following formula.

Example 9

In Example 1 to 8, 2-phenylimidazole was prepared as an active ingredient in addition to the surface treatment solution containing each imidazole compound and the above compounds. Chemical films were formed on the copper surface by contacting each treatment solution with copper, and the wetting time of the solder dissolved in copper was measured to determine the antioxidant performance of the imidazole compound on the copper surface. . In this case, it was judged that the shorter the wetting time, the better the antioxidant performance of the imidazole compound.

The specifics of the evaluation experiment are as follows.

(1) Preparation of Surface Treatment Solution:

In order to achieve the composition shown in Table 1, after dissolving an imidazole compound, an acid, a metal salt, and a halogen compound in ion-exchanged water, the surface treatment solution was prepared by adjusting pH with ammonia water.

(2) surface treatment method:

The experimental piece of metallic copper material (copper plate having a size of 5 mm x 50 mm x 0.3 mm) was degreased and then soft etched. After immersing the test pieces in the surface treatment solution at a predetermined temperature for a predetermined time for forming a chemical film on the copper surface, the test pieces were washed with water and dried.

(3) measurement of wetting time:

Surface treated test pieces were immersed in post-flux (trade name "JS-64MSS" produced by KoKi Co., Ltd.) and the solder wetting time (seconds) was determined by the solder wetting tester (SAT-2000). Produced by Rhesca, Inc.). The solder used was a tin-lead eutectic solder (trade name: H63A, produced by Senju Metal Industry Co., Ltd.) and the measurement conditions were as follows: solder temperature 240 ° C., immersion depth 2 mm, immersion rate. 16 mm / sec.

In this regard, the measurement of the solder wetting time of the test pieces is (A) immediately after surface treatment, (B) after 96 hours at 40 ° C. and 90% relative humidity in a constant-temperature constant-humidity space, and ( C) further heating at 200 ° C. for 10 minutes.

The results obtained in the above experiments are shown in Table 1.

According to the experimental results shown in Table 1, the moisture resistance to the copper surface is due to the surface treatment liquid containing the 2-benzyl-4- (2,4-dichlorophenyl) -5-methylimidazole compound of the present invention as an effective component. A chemical film excellent in heat resistance can be formed, which is useful as a copper surface antioxidant.

2-benzyl-4- (2,4-) is useful as an antioxidant for metal surfaces, especially copper surfaces, including copper alloys, and as curing or curing accelerators for epoxy resins, and also as an intermediate raw material in the medical and pesticide applications. Dichlorophenyl) -5-methylimidazole compound may be provided.

Having described the present invention in detail and with reference to specific embodiments, it is understood by those skilled in the art that various changes and modifications can be made within the present invention without departing from the scope of the invention.

This application is filed under Japanese Patent No. 6/08/2008. Japanese Patent Nos. Filed on 2008-259661 and June 10, 2009. Based on 2009-138853, the entire contents of the above patent documents are incorporated herein by reference.

Claims (1)

2-benzyl-4- (2,4-dichlorophenyl) -5-methylimidazole compound of formula (I)

In the above formula, X ₁ and X ₂ are the same or different and are a hydrogen atom, a chlorine atom, or a bromine atom.