TW201010982A - 2-benzyl-4-(3,4-dichlorophenyl)-5-methylimidazole compound - Google Patents

Abstract

An object is to provide a 2-benzyl-4-(3, 4-dichlorophenyl)-5-methylimidazole compound useful as an antioxidant for copper surface, a curing agent for epoxy resins, or an intermediate for medicaments and agricultural chemicals. A 2-benzyl-4-(3, 4-dichlorophenyl)-5-methylimidazole compound represented by the formula (I). The compound can be synthesized by reacting a 2-halogenated 3', 4'-dichloropropiophenone compound with an arylacetamidine compound under heating in the presence of a dehydrohalogenating agent in an organic solvent. wherein X1 and X2 are the same or different and represent a hydrogen atom, a chlorine atom, or a bromine atom.

Description

201010982 VI. Description of the Invention: [Technical Field to Which the Invention Is Applicable] The present invention relates to a novel 2-membered 4-(3,4-diphenyl)-5-methyl stilbene compound. [Prior Art] An imidazole compound similar to the compound of the present invention, for example, 2-(2,4-dichloro-benzyl)-5-(3,4-dichloro-phenyl)-1 fluorene-imidazole is disclosed in the patent document 丨. However, in this document, the stilbene-based compound in which the thiol group is bonded to the 4 (5) position of the imidazole ring is not disclosed. LISTING FORM Patent Reference [PLT 1] JP-T-2003-500357 (page 7, page 51) [Invention] The object of the present invention is to provide a novel 2-benzyl- 4_(3,4-dichloride Phenyl)-5-methyl" rice salic compound. In order to solve the aforementioned problems, the inventors conducted a comprehensive intensive investigation study. As a result, the inventors have found that the axis of the formula (1) represented by the formula (1) is a group of 24, and the 4, dichlorophenyl)-5-methylimidyl compound can be synthesized, thus completing the present invention. In other words, the present invention includes the following aspects in its broadest configuration: (1) a 2-node-based, 4-dichlorophenyl)-5-methyl-m-salt represented by the formula (1) Compound: 098129659 4 201010982

:中...2 is the same or different ' and represents a hydrogen atom, a gas atom or a desert ❹. The 2m(3,4-diphenyl)-5-methyl-salt compound of the invention may be a metal, especially copper ( Antioxidants on the surface of copper alloys and curing accelerators or curing accelerators of Epoxy resin can also be used as intermediate materials in the fields of pharmaceutical chemicals and agrochemicals. [Embodiment] Details of the present invention will be described later. The 2-mercapto-ice (3,4-dichlorophenyl)j methyl sulphate compound of the present invention is represented by the following formula (I) and examples thereof include: 2-benzyl-4-(3,4- Dichlorophenyl)_5·methylimidazole, 2-(2-chlorobenzyl)_4_(3,4-diphenylphenylimidazole, 2-(3-chlorobenzyl)_4_(3,4_digas Phenyl)_5_ ▼-imidazole, 2-(4-chlorobenzyl)_4-(3,4-dichlorophenyl)-5-methylimidazole, 2-(2,3-dichlorobenzyl)_4_(3 , 4-diphenylphenyl)_5_f-based imidazole, 2·(2,4-dichlorobenzyl)-4-(3,4-dichlorophenyl)-5-methylimidazole, 2-(2,5- Dichlorobenzyl> 4-(3,4-dichlorophenyl)-5-methylimidazole, 098129659 5 201010982 2-(2,6-a-indolyl)-4-(3,4-dichlorobenzene -5-methyl-m-β sitting, 2-(3,4-one agglomerate)_4-(3,4-dichlorophenyl)-5-methyl-flavored β, 2-(3,5- Monochloroindolyl-4-(3,4-diphenyl)-5-indolyl, 2-(2-bromobenzyl)-4-(3,4-diphenyl)-5 - mercapto imidazole, 2-(3-bromobenzyl)-4-(3,4-dichlorophenyl)-5-methylimidazole, 2-(4-bromobenzyl)-4-(3,4 -diphenylphenyl)-5-methylimidazole, 2-(2,3-dibromobenzyl)_4_(3,4-dichlorophenyl)-5-methylimidazole, 2-(2,4- Dibromobenzyl) 4-(3,4-diphenyl)-5-methylimidazole, 2-(2,5- Dibromobenzyl) 4-(3,4-diphenyl)-5-methylimidazole, 2-(2,6-dibromo-benzyl)_4_(3,4-diphenyl)_5_曱Gimidine, 2-(3,4-dibromobenzyl)-4-(3,4-diphenyl)-5-mercaptoimidine, 2-(3,5-dibromobenzyl)- 4-(3,4-Dichlorophenyl)-5-mercaptoimidazole, 2-(3-bromo-2-abenzyl)-4-(3,4-diphenyl)-5-methylimidazole, 2 -(4-bromo-2-chlorobenzyl)_4_(3,4_dioxyl)_5•nonyl imidazole, 2-(5-bromo-2-ylbenzyl)_4-(3,4-di (5) mercapto imidazole, 2-(2-bromo-6-chlorobenzyl)_4·(3,4-diphenyl)-5-methylimidazole, 2-(2-bromo- 3-gas benzyl)_4·(3,4_二气笨基)_5_mercaptoimidazole, 2-(4-bromo-3-indolyl)_4_(3,4_二气笨基)_5_ Methylimidazole, 2-(5-indol-3-gas f-based) bucket (3,4_di-gas), 5-methylimidazole, 2-(2-bromo-5-chlorobenzyl)_4_(3 , 4_dichlorophenyl)_5_methylimidazole, 2-(2-/odor-4-pyloryl)_4_(3,4_digas stupyl)_5_mercapto-oxazole, and 2-( 3- Desert-4-Chlorobenzyl)_4_(3,4_dioxyl)_5-methylimidazole. 098129659 6 201010982

Wherein Xi&X2 is the same or different and represents a hydrogen atom, a chlorine atom or a bromine atom. The 2-benzyl-4-(3,4-dichlorophenyl)-5-methylimidazole compound of the present invention can be synthesized according to a known method. For example, as shown in the reaction diagram below, the compound can be

The 3',4'-dioxapropiophenone compound is synthesized by reacting with an aryl acetamidine compound.

Wherein X2 is as previously described, and X3 represents a chlorine atom, a bromine atom or a ruthenium atom. In the foregoing reaction, the amount of the aryl acetamidine compound is preferably from 0.8 to 1.5 times the molar ratio, more preferably from 0.9 to 1.1 moles per mole of the 2-halogenated 3',4'-dichloropropiophenone compound. ratio. The dehydrohalogenating agent is preferably used in an amount of from 1 to 10 equivalents based on the 2-halogenated 3',4'-dichloropropiophenone compound. 098129659 7 201010982 As for the aforementioned 2-halogenated 3',4'-dichloropropiophenone compound, which may be 2-chloro-3', 4'-dioxapropiophenone, 2-bromo-3', 4'-diox Propiophenone and 2-iodo-3',4'-dichlorophenylpropene. The 2-halogenated 3',4'-dichloropropiophenone compound is obtained via the 2 position of the halogenated 3',4'-dichlorophenylacetone. Regarding the halogenation, it may also be chlorination or iodination, but the bromination reaction in which the molar amount of bromine is reacted with 3',4'-dioxapropanone is the simplest and most convenient. Regarding 3',4'-dichloropropiophenone, a commercially available one can be used as a reagent. The above aryl acetamidine compound can be obtained by reacting aryl acetamidine hydrochloride with a strong base agent and removing argon chloride. In the synthesis reaction of the above imidazole compound, an aryl acetamidine hydrochloride or an aryl acetamidine compound and a salt of a conventional inorganic acid or organic acid may be used instead of the aryl acetamidine compound. The aryl acetamidine hydrochloride can be synthesized according to known methods. For example, as shown in the following reaction scheme, conversion to an aryl acetimidate hydrochloride is carried out by reacting a benzyl cyanide compound with a hydrogen chloride gas and a lower alkanol such as ethanol, and further allowing it to react with ammonia, which can be synthesized. Aryl acetamidine hydrochloride.

Which one! And X2 is as explained above. 098129659 8 201010982 Examples of the hydrochloride salt of the aryl acetamidine compound obtained by such reaction include: phenylacetamidine hydrochloride, (2-chlorophenyl)ethylglycol hydrochloride, (3-chlorophenyl) Acetate hydrochloride, (4-chlorophenyl)acetamidine hydrochloride, (2,3-diphenyl)acetamidine hydrochloride, Q (2,4-dichlorophenyl)acetamidine hydrochloride Salt, (2,5-dichlorophenyl)acetamidine hydrochloride, (2,6-dichlorophenyl)acetamidine hydrochloride, (3,4-diphenyl)acetamidine hydrochloride, (3,5-Dichlorophenyl)acetamidine hydrochloride, (2-bromophenyl)acetamidine hydrochloride, (3-bromophenyl)acetamidine hydrochloride, hydrazine (4-bromophenyl) Acetate hydrochloride, (2,3-dibromophenyl)acetamidine hydrochloride, (2,4-dibromophenyl)acetamidine hydrochloride, (2,5-dibromophenyl)ethyl Hydrochloride, (2,6-dibromophenyl)acetamidine hydrochloride, (3,4-dibromophenyl)acetamidine hydrochloride, (3,5-dibromophenyl)acetamidine hydrochloride Salt, (3-bromo-2-chlorophenyl)acetamidine hydrochloride, 098129659 9 201010982 (4-bromo-2-chlorophenyl)acetamidine hydrochloride, (5-bromo-2-chlorophenyl) Acetate hydrochloride, (2-bromo-6-phenylphenyl)acetamidine hydrochloride, (2-bromo-3-gas) Ethyl hydrazine hydrochloride, (4-bromo-3-chlorophenyl)acetamidine hydrochloride, (5-bromo-3-chlorophenyl)acetamidine hydrochloride, (2-bromo-5-chloro Phenyl)acetamidine hydrochloride, bis (2-bromo-4-phenylphenyl)acetamidine hydrochloride, and (3-bromo-4-chlorophenyl)acetamidine hydrochloride. As the aforementioned dehydrohalogenating agent, any known desulfurizing agent can be used without particular limitation. Examples of such a dehydrogenating agent include inorganic alkalized eight kinds of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, carbonic acid unloading, #sodium, and potassium argonate; and an organic base compound such as triethylamine. And chlorinated hydroquinone 1 5 8 · diterpene Y a ring [5·4.〇]-7-undecene (DBU); metal oxide oxide such as methoxy 4 potassium butoxide; And as far as the above reaction solvent, any known solvent can be used without particular limitation as long as the solvent can dissolve the 2 -i 3 ', 4 dioxapropiophenone compound and the aryl acetophenone compound without being involved in the reaction. . Examples of such a solvent include alkanols such as isopropanol and tert-butanol; hydrocarbons such as hexane and toluene; _hydrocarbons such as gas and gas benzene; esters such as ethyl acetate; nitriles such as acetonitrile Ethers such as tetrahydrofuran, di-alpha u and ethylene glycol dimethyl ether; guanamines such as hydrazine, hydrazine-dimercaptoamine (DMF) and hydrazine, hydrazine-dimethylacetamide (DMAC) ; 二曱亚硪 098129659 10 201010982 (DMSO); and so on. These solvents can be used in combination. The reaction temperature is preferably from room temperature to reflux temperature, and the reaction time is preferably from 1 hour to 10 hours. The reaction is usually carried out under atmospheric pressure. The 2·benzyl-4-(3,4-diphenyl)-5-methylimidazole compound formed under the aforementioned reaction conditions can be isolated by ordinary post treatment. For example, after the reaction is completed, the reaction mixture is dissolved in an aqueous layer and an organic solvent layer, and after washing the organic solvent layer with water, the organic solvent is evaporated to obtain a crude product of the compound hydrazine, and the crude product. Further, it can be purified by a recrystallization operation or the like. [Examples] Hereinafter, the present invention will be specifically described with reference to the examples, but the invention should not be construed as being limited to the examples. Reference Examples 2 and 2 show synthesis examples of phenylephrine hydrochloride and 2-di- 3',4'-dichlorophenylpropylidene steel, respectively. [Reference Example 1] (Synthesis of Benyl Ethyl Hydrochloride) In a solution consisting of 〇〇α6 mol)phenylacetonitrile and S5 = alcohol in 5:4 = i day and iT.22 Ear) gasification of hydrogen gas. When the reaction solution is allowed to stand for acid acid, the acid salt is crushed and added to the ice-cooled bamboo to reduce the amount of the solution. Then, the mixture was chilled under ice cooling for 2 hours at 098,129,659, 201010982, and was allowed to stand at room temperature (iv) overnight. After filtering and removing the white solidity (IV), the phenylethylamine hydrochloride was obtained as a gray-yellow thicker under the pressure of the domain under the pressure of 172·5 g (1·011 mol [yield 1〇〇5%]). Thick syrup form. [Reference Example 2] (Synthesis of 2-bromo-3,4'-dioxapropiophenone) In a solution consisting of 45.8 g (0.226 mol) of 3,4,-diacetophenone* 46 g of methanol From 62t to 65. (: 36 g ❹ (0.2253 mol) was added dropwise over 50 minutes. After the reaction solution was cooled, it was dissolved in 75 g of toluene and 91 g of water. The benzene layer was washed with water and dehydrated with magnesium sulfate. Thereafter, the solvent was evaporated under reduced pressure to give 64.3 g (yield: 0.228 m) yield of </ </ RTI> </ RTI> bromo-3, br. (Synthesis of 2-benzyl-4-(3,4-diphenyl)-5-mercaptoimidazole) from 28.7 g (〇.丨68 mol) phenylacetamidine hydrochloride, 59 g (Μη莫❹ ear) a suspension of potassium carbonate' and 210 ml of N,N-dimethylguanamine at 5 〇. (: After stirring for 30 minutes, at the same temperature 48.8 g (0.173 mol) 2- Indif-3,4,-dichloropropanoid was added to several portions, followed by stirring at the same temperature for 4 hours. Then, after the reaction suspension was cooled, it was dissolved in 800 ml of water and 3 ml of gas. After the chloroform layer was washed twice with water, the chloroform was evaporated under reduced pressure, and the crystals were precipitated by adding 150 ml of toluene to the obtained thick syrup-like concentrated product, and crystals were precipitated. The precipitated crystals were collected by filtration, and Washed with benzene benzene 09812 9659 12 201010982 After drying, a cheese-colored powder was obtained by drying. The powder was recrystallized from acetonitrile to obtain 18.8 g (0.059 mol, yield 35.3%) of milky white powder crystals. The melting point of the obtained crystal, the Rf value of the thin layer chromatography and The 1H-NMR data and mass spectrometry data are as follows.

• mp. 158-161 °C • TLC (cerium oxide gel, acetone): Rf = 0·70 ^H-NMR (CDC13) δ: 2.28 (s, 3Η&gt;, 3.94 (s, 2Η), 7.12- 7.66 (ία, 7Η). ® -MS m/z (%) : 316 100)/ 301 (3), 281 (3) ^ 239 (4), 198 (2), 171 (4ϊ, 144 (3&gt;, 122 (9&gt;, 103 (6), 91 77 i4J. Based on these spectral data, the obtained compound was identified as 2-benzyl-4-(3,4-diphenyl)-5-methyl represented by the following formula Imidazole.

[Example 2] Synthesis of (2-(2-chlorobenzyl)-4-(3,4-diphenyl)-5-mercaptoimidazole) First, the phenylacetonitrile of Reference Example 1 was changed to ( 2-Chlorophenyl)acetonitrile, (2-chlorophenyl)acetamidine hydrochloride was synthesized according to the method of Reference Example 1. Next, the phenylacetamidine hydrochloride of Example 1 was changed to (2-chlorophenyl)acetamidine hydrochloride, and a synthetic experiment was carried out according to the method of Example 1 to obtain a milky white 098129659 13 201010982 powdery crystal. The melting point of the obtained crystal, the Rf value of the thin layer chromatography, and the 1 h_nmR data and mass spectrum data are as follows. • mp. 150-152〇c • TLC (cerium oxide gel, ethyl acetate): Rf = 〇58 {de-DMSO) δ: 2.3Θ (8, 3Η) , 4.09 (S/ 2») ^ 7.27 -7.80 {m, 7Η&gt; . • MS π»/Ζ (%&gt;: 3S0 (η% 23&gt;, 315 &lt;100), 280 (3), 171 (2), 137 (3), 122 (i〇&gt;, ι〇 2 (4), &lt;3). Based on these spectral data, the obtained compound is identified as 2-(2-gasbenzyl)-4-(3,4-diphenyl)-5-fluorenyl represented by the following formula Imidazole.

[Example 3] Synthesis of (2-(4-chlorobenzyl)-4-(3,4-dichlorophenyl)-5-mercaptoimidazole) First, the phenylacetonitrile of Reference Example 1 was changed ( 4-chlorophenyl)acetonitrile was synthesized according to the method of Reference Example 1 (4-phenylphenyl)acetamidine hydrochloride. Next, the phenylacetamidine hydrochloride of Example 1 was changed to (4-chlorophenyl)acetamidine hydrochloride, and a yellow-white powdery crystal was obtained by conducting a synthesis experiment according to the method of Example 1. 098129659 14 201010982 The melting point of the obtained crystal, the Rf value of the thin layer chromatography, and the 1H-NMR data and mass spectrometry data are as follows.

• mp. 180-18TC • TLC (cerium oxide gel, acetone): Rf=0.72 'H-NMR &lt;d«HDMSO&gt; δ: 2.36 &lt;s, 3H), 3·96 (sr 2H&gt;, 7.29 -7.80 (m, 7H). • MS m/z (It) : 350 (M% 100) , 33S (1), 315 (14J, 279 (3), 190 (3), 175 &lt;4&gt;, 164 (4), 137 (7&gt;, 125 &lt;1〇&gt;, 122 (15&gt;, 102 (8), 89 (4), 75 &lt; 3). ® Based on these spectral data, the obtained compound is identified as 2 -(4-Chlorobenzyl)-4-(3,4-diphenyl)-5-mercaptoimidazole.

(Synthesis of 2-(2,4-dioxabenzyl)-4-(3,4-dichlorophenyl)-5-mercaptoimidazole) First, the phenylacetonitrile of Reference Example 1 was changed to (2, 4-Dichlorophenyl)acetonitrile, (2,4-dichlorophenyl)acetamidine hydrochloride was synthesized according to the method of Reference Example 1. Next, the phenylacetamidine hydrochloride of Example 1 was changed to (2,4·dichlorophenyl)acetamidine hydrochloride, and a white powdery crystal was obtained by conducting a synthesis experiment according to the method of Example 1. 098129659 15 201010982 The Rf value of the obtained crystal, the Rf value of the thin layer chromatography and the 1H_NMR data and mass spectrometry data. • mp. 117~h90q • TLC (one gasification gel, acetone): Rf = 0.74

(m, 7HJ. MS m/z (%): 386 (M+2/ l〇〇), 384, 31), 349 (100), 299 (3)# 279 (3)f 1^3 (4) , 171 (7), 159 (9&gt;, 139 (i〇), 121 (6), l〇2 (S)· Based on these spectral data, the obtained compound is identified as 2-(2,4- represented by the following formula ❿ Dichlorobenzyl) 4-(3,4-dichlorophenyl)-5-mercaptoimidazole.

[Example 5] Synthesis of (2-(3,4-dichlorobenzyl)-4-(3,4-dichlorophenyl)-5-methylimidazole) First, the phenylacetonitrile of Reference Example 1 was changed. To (3,4-dichlorophenyl)acetonitrile, (3,4-dioxaphenyl)acetamidine hydrochloride was synthesized according to the method of Reference Example 1. Next, the phenylacetamidine hydrochloride of Example 1 was changed to (3,4-dichlorophenyl)acetamidine hydrochloride. The synthesis experiment was carried out according to the method of Example 1 to obtain milky white powder crystals. 098129659 16 201010982 The melting point of the obtained crystal, the Rf value of the thin layer chromatography and the 1H-NMR data and mass spectrometry data are as follows.

• mp. 194-195〇C • TLC (cerium oxide gel, acetone): Rf = 0.67 ^H-NMR (de-DMSO) δ: 2.33 (s, 3Η), 3.96 &lt;s, 2Η), 7.25 -7.77 (m, 6Η). • MS m/z (%J; 386 (M+2, 100), 384 {it, 78), 371 (1), 349 &lt;7ϊ, 314 (9), 239 (7) , 212 (3), 198 (3), 171 (7), 159 (9), L39 (10&gt;, 122 {1), 102 &lt;4), 89 (2». Based on these spectral data, the obtained compound It is identified as 2-(3,4-dichlorobenzyl)-4-(3,4-diphenyl)-5-mercaptoimidazole represented by the following formula.

[Example 6] Synthesis of (2-(4-bromo-based)-4-(3,4-diphenyl)-5-mercaptoimidazole) First, the phenylacetonitrile of Reference Example 1 was changed ( 4-(Bromophenyl)acetonitrile, (4-bromophenyl)acetamidine hydrochloride was synthesized according to the method of Reference Example 1. Next, the phenylacetamidine hydrochloride of Example 1 was changed to (4-bromophenyl)acetamidine hydrochloride, and a white powdery crystal was obtained by conducting a synthesis experiment according to the method of Example 1. 098129659 17 201010982 The melting point of the obtained crystal, the Rf value of the thin layer chromatography, and the 1H-NMR data and mass spectrometry data are as follows.

• mp. 207-208〇C • TLC (cerium oxide gel, hexane: ethyl acetate = 1 : i) : Rf = 〇 • • H-NMR (de-DMSO) δ: 2.07 &lt;s, 3Η ), 3.92 (s, 2Η), 7.21-7.73⁄4 (m, 7ΗΪ . MS οι/ζ (%&gt;: 398 46&gt;, 396 (Μ+2, 100), 394 Μ, 62}, 361 (2) , 315 (11), 299 (3), 279 (3), 239 (4), 198 (5), 183 (3), 171 U0&gt; , 140 (8), 122 &lt;20} , 102 (14), 89 (6), 75(3). Based on these spectral data, 'the obtained compound is identified as bromobenzyl)-4-(3,4-diphenyl)-5-methylimidazole represented by the following formula.

[Example 7] Preparation contains examples! Each of the sulphur compounds synthesized in Example 6 and a surface treatment liquid containing a 2-phenylate as an active ingredient in addition to these compounds. Each of the treatment liquids was brought into contact with copper to form a chemical film on the surface of the copper, and the oxidation time of the molten solder to the copper was measured, thereby measuring the oxidation resistance of the copper surface on which the mimetic compound acts. In this case; under the brother, the wet time 098129659 201010982 is shorter, the better the antioxidant effect of the imidazole compound. The evaluation test details are as follows. (1) Preparation of surface treatment liquid: The imidazole compound, the acid, the metal salt, and the halogen compound are dissolved in ion-exchanged water to obtain the composition described in Table 1, and the surface treatment liquid is prepared by adjusting the pH with ammonia water. (2) Surface treatment method: ❹ The material is a test piece of metallic copper (5 mm X 50 mm x 〇.3 mm size copper plate) [to remove and then accept soft button engraving. The test piece is immersed in the surface treatment liquid. After forming a chemical film on the copper surface at a predetermined temperature for a predetermined time, the test piece is washed with water and dried. (3) Measurement of the wet time: The test piece subjected to the surface treatment was immersed in the post flux [trade name "JS-64MSS"' manufactured by Koki Co., Ltd.] 'By soft solder wet tester ❹ (SAT-2000, Rhesca) Manufactured by Corporation) measures the soft solder wet time (seconds). The soft solder used was tin-lead eutectic soft solder (trade name: H63A, manufactured by Senju Metal Industry Co., Ltd.), and the measurement conditions were as follows: soft solder temperature 240 ° C, immersion depth 2 mm, immersion speed 16 mm / second. In this respect, the soft solder wet time measured by the test piece is (A) immediately after surface treatment; (B) constant temperature and humidity indoor at 40 ° C temperature and humidity of 90% 4 mesh to humidity (rh) After 96 hours; and (C) at 20 (TC further heated for 10 minutes. 098129659 19 201010982 The test results are shown in Table 1. 098129659 20 201010982 ° Test No. Ο Τ-Η ο I 0.80 I CD C= 5 LO Ο Ο* C=5 ΟΟ g § ιΉ &lt;=&gt; oa cd 〇1—^ CO L〇oa c=&gt; ο r—Η s &lt;35 &lt;=) CO § 0.29 CD 0.72 m 0.20 C3 isi LO CNI &lt;3&gt;&lt;〇◦ ^Η LO 〇&lt;=&gt; CO CO § , &lt; 〇3 c=&gt; LO CO &lt;〇S C3 inch 0.20 S o 0.10 cz&gt; τ-Η 0.04 C&lt;i CO § 0.28 οο CO CD CO LO CD CO LO CO d LO 1—&lt; o LO οο CD c6 C3 CO 1_·&lt; ΟΟ Οί &lt;ζ&gt; CO but c=&gt; ΟΟ &lt;=i LO &lt;N1 Ο LO &lt;N1 CD o &lt;=&gt; LO CO S r &lt; CO 〇· CD o* 0.25 LO 〇&gt;&lt;=&gt; 〇C£5 OQ § LO CO C&gt; oa oo CD * 骏 1 - £ φ! • Ifttil ηβη {[»•1 sv shout V0 'Sw/ Ψ S- Λ Ί CO Ϋ Talk · Q ψ S- 人Ί CO Λ V V&amp; X 雄&lt; Ψ &- Λ t4 Ί Λ Λ CO Λ Λ Λ X IK Ψ 砩 &- Λ t-4 Ί Λ CO Λ Ψ - Ί Ί 〇 J IK Ψ s 丄Λ 丄Λ Ί Λ CO 寸 Ί Λ CO X s 鸯 IK 'w/ Ψ δ ιό Λ Ί Λ Λ CO Λ Λ Λ 2-Phenyl imidazolium formic acid t-lactic acid Copper propionate copper acetate vaporized copper bromide 0; bismuth vaporized ammonium bromide % Jj moth Ϊ Ϊ 丨 铜 D D=! a fhll w shout iD / - NP W1.1 W shout / - N is s« % r~N is E 赍W 实 孩 格 格 · · wt seven CO σ> Μ Thai tX3 〇ά g 03 P m pier φ &lt;3&gt; 严·Η Ρ Ρ 衾 衾7 CO CJi Μ § g 05 Ρ ψ ψ Μ ιγ*7 6S96-860

V 201010982 According to the test results not shown in Table 1, the surface treatment liquid containing the 2_ _ _ 4_(3,4_-gas phenyl) 5 methyl quinone compound of the present invention as an active ingredient can be formed on the copper surface to be waterproof. It is a chemical film with excellent heat resistance and heat resistance, so it can be used for oxidation resistance on copper surfaces. (Industrial Applicability) According to the present invention, there is provided a 2_based ice-based (chlorinated phenyl)-5 methyl methane bismuth compound which can be used as an antioxidant for metals, particularly copper (including copper alloy) surfaces, and epoxy A curing agent or curing accelerator can also be used as an intermediate material in the fields of pharmaceutical chemicals and agrochemicals. Although the present invention has been described in detail with reference to the specific embodiments thereof, it is obvious to those skilled in the art that various changes and modifications can be made therein without departing from the scope of the invention. This application is based on Japanese Patent Application No. 2_225632, filed on September 3, 2008, Japanese Patent Application No. 2〇〇9·13〇〇22, applied for May 29, 2009, Japanese patent Application No. 2009-140655, Application Date June 12, 2009, the full text of each case is hereby incorporated by reference. 098129659 22

Claims (1)

201010982. VII. Patent application scope: 1. A 2-benzyl-4-(3,4-dichlorophenyl)-5-mercaptoimidazole compound represented by the formula (I): ® where Xi&amp;X2 is the same or different and represents a hydrogen atom, a chlorine atom or a bromine atom. 098129659 23 201010982 IV. Designation of representative drawings: (1) The representative representative of the case is: None (2) Simple description of the symbol of the representative figure: None 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 098129659 3