JP5260208B2 - 2- (2,4-Dichlorobenzyl) -4- (halogenated phenyl) imidazole compound - Google Patents
2- (2,4-Dichlorobenzyl) -4- (halogenated phenyl) imidazole compound Download PDFInfo
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- JP5260208B2 JP5260208B2 JP2008242949A JP2008242949A JP5260208B2 JP 5260208 B2 JP5260208 B2 JP 5260208B2 JP 2008242949 A JP2008242949 A JP 2008242949A JP 2008242949 A JP2008242949 A JP 2008242949A JP 5260208 B2 JP5260208 B2 JP 5260208B2
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- dichlorobenzyl
- imidazole
- halogenated phenyl
- imidazole compound
- compound
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- -1 2,4-Dichlorobenzyl Chemical group 0.000 title claims description 38
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims description 32
- 239000000126 substance Substances 0.000 claims description 16
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 229910000679 solder Inorganic materials 0.000 description 7
- 238000004381 surface treatment Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- HUKFRPZKURKTQB-UHFFFAOYSA-N 2-(2,4-dichlorophenyl)ethanimidamide Chemical compound NC(=N)CC1=CC=C(Cl)C=C1Cl HUKFRPZKURKTQB-UHFFFAOYSA-N 0.000 description 6
- YWQFUOSTIJIKRY-UHFFFAOYSA-N 2-(2,4-dichlorophenyl)ethanimidamide;hydrochloride Chemical compound Cl.NC(=N)CC1=CC=C(Cl)C=C1Cl YWQFUOSTIJIKRY-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- FLAYZKKEOIAALB-UHFFFAOYSA-N 2-bromo-1-(4-chlorophenyl)ethanone Chemical compound ClC1=CC=C(C(=O)CBr)C=C1 FLAYZKKEOIAALB-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 238000004809 thin layer chromatography Methods 0.000 description 4
- FKJSFKCZZIXQIP-UHFFFAOYSA-N 2-bromo-1-(4-bromophenyl)ethanone Chemical compound BrCC(=O)C1=CC=C(Br)C=C1 FKJSFKCZZIXQIP-UHFFFAOYSA-N 0.000 description 3
- IROVXUYCDDEQPI-UHFFFAOYSA-N 5-(4-bromophenyl)-2-[(2,4-dichlorophenyl)methyl]-1H-imidazole Chemical compound ClC1=CC(Cl)=CC=C1CC1=NC=C(C=2C=CC(Br)=CC=2)N1 IROVXUYCDDEQPI-UHFFFAOYSA-N 0.000 description 3
- NAZCDANAFLNKBC-UHFFFAOYSA-N 5-(4-chlorophenyl)-2-[(2,4-dichlorophenyl)methyl]-1h-imidazole Chemical compound C1=CC(Cl)=CC=C1C(N1)=CN=C1CC1=CC=C(Cl)C=C1Cl NAZCDANAFLNKBC-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- VJARIBGMDPJLCL-UHFFFAOYSA-N 2-(2,4-dichlorophenyl)acetonitrile Chemical compound ClC1=CC=C(CC#N)C(Cl)=C1 VJARIBGMDPJLCL-UHFFFAOYSA-N 0.000 description 2
- WZWWEVCLPKAQTA-UHFFFAOYSA-N 2-bromo-1-(2-chlorophenyl)ethanone Chemical compound ClC1=CC=CC=C1C(=O)CBr WZWWEVCLPKAQTA-UHFFFAOYSA-N 0.000 description 2
- MZBXSQBQPJWECM-UHFFFAOYSA-N 2-bromo-1-(3-bromophenyl)ethanone Chemical compound BrCC(=O)C1=CC=CC(Br)=C1 MZBXSQBQPJWECM-UHFFFAOYSA-N 0.000 description 2
- KJVRURZDIOVSSQ-UHFFFAOYSA-N 2-bromo-1-(3-chlorophenyl)ethanone Chemical compound ClC1=CC=CC(C(=O)CBr)=C1 KJVRURZDIOVSSQ-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KOAMWVFBYULGMQ-UHFFFAOYSA-N (2,4-dichlorophenyl) ethanimidate hydrochloride Chemical compound Cl.C(C)(OC1=C(C=C(C=C1)Cl)Cl)=N KOAMWVFBYULGMQ-UHFFFAOYSA-N 0.000 description 1
- SCZNXLWKYFICFV-UHFFFAOYSA-N 1,2,3,4,5,7,8,9-octahydropyrido[1,2-b]diazepine Chemical compound C1CCCNN2CCCC=C21 SCZNXLWKYFICFV-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SHCPPNUKVMYGIU-UHFFFAOYSA-N 1-(2-bromophenyl)-2-chloroethanone Chemical compound ClCC(=O)C1=CC=CC=C1Br SHCPPNUKVMYGIU-UHFFFAOYSA-N 0.000 description 1
- XBQJXQFAYNWZGY-UHFFFAOYSA-N 1-(3-bromophenyl)-2-chloroethanone Chemical compound ClCC(=O)C1=CC=CC(Br)=C1 XBQJXQFAYNWZGY-UHFFFAOYSA-N 0.000 description 1
- CVWWAGDVPIUJFT-UHFFFAOYSA-N 1-(3-bromophenyl)-2-iodoethanone Chemical compound BrC1=CC=CC(C(=O)CI)=C1 CVWWAGDVPIUJFT-UHFFFAOYSA-N 0.000 description 1
- HCQNNQFCUAGJBD-UHFFFAOYSA-N 1-(4-bromophenyl)-2-chloroethanone Chemical compound ClCC(=O)C1=CC=C(Br)C=C1 HCQNNQFCUAGJBD-UHFFFAOYSA-N 0.000 description 1
- RNUBOFBGXIQXKN-UHFFFAOYSA-N 1-(4-bromophenyl)-2-iodoethanone Chemical compound BrC1=CC=C(C(=O)CI)C=C1 RNUBOFBGXIQXKN-UHFFFAOYSA-N 0.000 description 1
- CEKRQODWEWQQFX-UHFFFAOYSA-N 1-(4-chlorophenyl)-2-iodoethanone Chemical compound ClC1=CC=C(C(=O)CI)C=C1 CEKRQODWEWQQFX-UHFFFAOYSA-N 0.000 description 1
- LAXPJIJQTHJGCK-UHFFFAOYSA-N 2-bromo-1-(2-bromophenyl)ethanone Chemical compound BrCC(=O)C1=CC=CC=C1Br LAXPJIJQTHJGCK-UHFFFAOYSA-N 0.000 description 1
- SOGLGKRIVMZMSK-UHFFFAOYSA-N 2-chloro-1-(2-chlorophenyl)ethanone Chemical compound ClCC(=O)C1=CC=CC=C1Cl SOGLGKRIVMZMSK-UHFFFAOYSA-N 0.000 description 1
- AVUVSYIYUADCKE-UHFFFAOYSA-N 2-chloro-1-(3-chlorophenyl)ethanone Chemical compound ClCC(=O)C1=CC=CC(Cl)=C1 AVUVSYIYUADCKE-UHFFFAOYSA-N 0.000 description 1
- FWDFNLVLIXAOMX-UHFFFAOYSA-N 2-chloro-1-(4-chlorophenyl)ethanone Chemical compound ClCC(=O)C1=CC=C(Cl)C=C1 FWDFNLVLIXAOMX-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- VCDNWGAXQGJWPA-UHFFFAOYSA-N 5-(2-bromophenyl)-2-[(2,4-dichlorophenyl)methyl]-1h-imidazole Chemical compound ClC1=CC(Cl)=CC=C1CC1=NC=C(C=2C(=CC=CC=2)Br)N1 VCDNWGAXQGJWPA-UHFFFAOYSA-N 0.000 description 1
- CXSOEWJVUWLQCD-UHFFFAOYSA-N 5-(2-chlorophenyl)-2-[(2,4-dichlorophenyl)methyl]-1h-imidazole Chemical compound ClC1=CC(Cl)=CC=C1CC1=NC=C(C=2C(=CC=CC=2)Cl)N1 CXSOEWJVUWLQCD-UHFFFAOYSA-N 0.000 description 1
- VTTBEWJHCLCVKI-UHFFFAOYSA-N 5-(3-bromophenyl)-2-[(2,4-dichlorophenyl)methyl]-1H-imidazole Chemical compound ClC1=CC(Cl)=CC=C1CC1=NC=C(C=2C=C(Br)C=CC=2)N1 VTTBEWJHCLCVKI-UHFFFAOYSA-N 0.000 description 1
- WUTBLHNPODFKLR-UHFFFAOYSA-N 5-(3-chlorophenyl)-2-[(2,4-dichlorophenyl)methyl]-1h-imidazole Chemical compound ClC1=CC=CC(C=2NC(CC=3C(=CC(Cl)=CC=3)Cl)=NC=2)=C1 WUTBLHNPODFKLR-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- PUXXTYHYEIQEPR-UHFFFAOYSA-N BrC1=C(C=CC=C1)C(CI)=O Chemical compound BrC1=C(C=CC=C1)C(CI)=O PUXXTYHYEIQEPR-UHFFFAOYSA-N 0.000 description 1
- URKNPMOHYFHGPJ-UHFFFAOYSA-N ClC1=C(C=CC=C1)C(CI)=O Chemical compound ClC1=C(C=CC=C1)C(CI)=O URKNPMOHYFHGPJ-UHFFFAOYSA-N 0.000 description 1
- CFUAHIQTIVNPFG-UHFFFAOYSA-N ClC1=CC=CC(C(=O)CI)=C1 Chemical compound ClC1=CC=CC(C(=O)CI)=C1 CFUAHIQTIVNPFG-UHFFFAOYSA-N 0.000 description 1
- SZQRWBCRMOVIBC-UHFFFAOYSA-N Clc1ccc(Cc2nc(-c3ccccc3)c[nH]2)c(Cl)c1 Chemical compound Clc1ccc(Cc2nc(-c3ccccc3)c[nH]2)c(Cl)c1 SZQRWBCRMOVIBC-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 102220474387 PDZ and LIM domain protein 7_H63A_mutation Human genes 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000006286 dichlorobenzyl group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000026045 iodination Effects 0.000 description 1
- 238000006192 iodination reaction Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
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Description
本発明は、新規な２−（２，４−ジクロロベンジル）−４−（ハロゲン化フェニル）イミダゾール化合物に関するものである。 The present invention relates to a novel 2- (2,4-dichlorobenzyl) -4- (halogenated phenyl) imidazole compound.
本発明に類似のイミダゾール化合物として、例えば特許文献１には、化１の化学式で示されるイミダゾール化合物が開示され、種々のイミダゾール化合物が例示されているが、本願発明の２−（２，４−ジクロロベンジル）−４−（ハロゲン化フェニル）イミダゾール化合物の開示はない。 As an imidazole compound similar to the present invention, for example, Patent Document 1 discloses an imidazole compound represented by the chemical formula of Chemical Formula 1 and exemplifies various imidazole compounds, but 2- (2,4- There is no disclosure of dichlorobenzyl) -4- (halogenated phenyl) imidazole compounds.
本発明は、新規な２−（２，４−ジクロロベンジル）−４−（ハロゲン化フェニル）イミダゾール化合物を提供することを目的とする。 An object of the present invention is to provide a novel 2- (2,4-dichlorobenzyl) -4- (halogenated phenyl) imidazole compound.
本発明者等は、前記の課題を解決するために鋭意検討を重ねた結果、化２の化学式(I)で示される新規な２−（２，４−ジクロロベンジル）−４−（ハロゲン化フェニル）イミダゾール化合物を合成し得ることを認め、本発明を完成するに至ったものである。 As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have obtained a novel 2- (2,4-dichlorobenzyl) -4- (halogenated phenyl) represented by the chemical formula (I) of Chemical Formula 2. ) It has been recognized that an imidazole compound can be synthesized, and the present invention has been completed.
本発明の２−（２，４−ジクロロベンジル）−４−（ハロゲン化フェニル）イミダゾール化合物は、金属、特に銅（銅合金を含む）の表面の酸化防止剤や、エポキシ樹脂の硬化剤または硬化促進剤として、また医農薬分野の中間原料としても有用なものである。 The 2- (2,4-dichlorobenzyl) -4- (halogenated phenyl) imidazole compound of the present invention is an antioxidant on the surface of metals, particularly copper (including copper alloys), a curing agent or curing of an epoxy resin. It is useful as an accelerator and as an intermediate material in the medical and agrochemical field.
以下、本発明について詳細に説明する。
本発明の２−（２，４−ジクロロベンジル）−４−（ハロゲン化フェニル）イミダゾール化合物は、化３の化学式(I)で示されるものであり、
４−（２−クロロフェニル）−２−（２，４−ジクロロベンジル）イミダゾール、
４−（３−クロロフェニル）−２−（２，４−ジクロロベンジル）イミダゾール、
４−（４−クロロフェニル）−２−（２，４−ジクロロベンジル）イミダゾール、
４−（２−ブロモフェニル）−２−（２，４−ジクロロベンジル）イミダゾール、
４−（３−ブロモフェニル）−２−（２，４−ジクロロベンジル）イミダゾールおよび
４−（４−ブロモフェニル）−２−（２，４−ジクロロベンジル）イミダゾールである。
Hereinafter, the present invention will be described in detail.
The 2- (2,4-dichlorobenzyl) -4- (halogenated phenyl) imidazole compound of the present invention is represented by the chemical formula (I) of Chemical Formula 3,
4- (2-chlorophenyl) -2- (2,4-dichlorobenzyl) imidazole,
4- (3-chlorophenyl) -2- (2,4-dichlorobenzyl) imidazole,
4- (4-chlorophenyl) -2- (2,4-dichlorobenzyl) imidazole,
4- (2-bromophenyl) -2- (2,4-dichlorobenzyl) imidazole,
4- (3-bromophenyl) -2- (2,4-dichlorobenzyl) imidazole and 4- (4-bromophenyl) -2- (2,4-dichlorobenzyl) imidazole.
本発明の２−（２，４−ジクロロベンジル）−４−（ハロゲン化フェニル）イミダゾール化合物は、公知の方法に準拠して合成することができる。例えば、化４の反応式に示されるように、ハロゲン化メチルハロゲン化フェニルケトン化合物（化学式(a)）と、（２，４−ジクロロフェニル）アセトアミジン（化学式(b)）とを脱ハロゲン化水素剤の存在下、有機溶媒中で加熱反応させることにより合成することができる。 The 2- (2,4-dichlorobenzyl) -4- (halogenated phenyl) imidazole compound of the present invention can be synthesized according to a known method. For example, as shown in the reaction formula of Chemical Formula 4, a halogenated methyl halogenated phenyl ketone compound (chemical formula (a)) and (2,4-dichlorophenyl) acetamidine (chemical formula (b)) are dehydrohalogenated. It can be synthesized by heating in an organic solvent in the presence of an agent.
前述の反応において、（２，４−ジクロロフェニル）アセトアミジンの使用量は、ハロゲン化メチルハロゲン化フェニルケトン化合物に対して、０．８〜１．５倍モルが好ましく、より好ましくは０．９〜１．１倍モルの割合とすればよい。脱ハロゲン化水素剤の使用量は、ハロゲン化メチルハロゲン化フェニルケトン化合物に対して、１〜１０倍当量の割合が好ましい。 In the above-mentioned reaction, the amount of (2,4-dichlorophenyl) acetamidine used is preferably 0.8 to 1.5 times, more preferably 0.9 to 1.5 moles of the halogenated methyl halogenated phenyl ketone compound. The ratio may be 1.1 times mole. The amount of the dehydrohalogenating agent used is preferably a ratio of 1 to 10 times equivalent to the halogenated methyl halogenated phenyl ketone compound.
前記のハロゲン化メチルハロゲン化フェニルケトン化合物としては、
２，２′−ジクロロアセトフェノン、
２，３′−ジクロロアセトフェノン、
２，４′−ジクロロアセトフェノン、
２′−ブロモ−２−クロロアセトフェノン、
３′−ブロモ−２−クロロアセトフェノン、
４′−ブロモ−２−クロロアセトフェノン、
２−ブロモ−２′−クロロアセトフェノン、
２−ブロモ−３′−クロロアセトフェノン、
２−ブロモ−４′−クロロアセトフェノン、
２，２′−ジブロモアセトフェノン、
２，３′−ジブロモアセトフェノン、
２，４′−ジブロモアセトフェノン、
２′−クロロ−２−ヨードアセトフェノン、
３′−クロロ−２−ヨードアセトフェノン、
４′−クロロ−２−ヨードアセトフェノン、
２′−ブロモ−２−ヨードアセトフェノン、
３′−ブロモ−２−ヨードアセトフェノンおよび
４′−ブロモ−２−ヨードアセトフェノンが挙げられる。
As the halogenated methyl halogenated phenyl ketone compound,
2,2'-dichloroacetophenone,
2,3'-dichloroacetophenone,
2,4'-dichloroacetophenone,
2'-bromo-2-chloroacetophenone,
3'-bromo-2-chloroacetophenone,
4'-bromo-2-chloroacetophenone,
2-bromo-2'-chloroacetophenone,
2-bromo-3'-chloroacetophenone,
2-bromo-4'-chloroacetophenone,
2,2'-dibromoacetophenone,
2,3'-dibromoacetophenone,
2,4'-dibromoacetophenone,
2'-chloro-2-iodoacetophenone,
3'-chloro-2-iodoacetophenone,
4'-chloro-2-iodoacetophenone,
2'-bromo-2-iodoacetophenone,
3'-bromo-2-iodoacetophenone and 4'-bromo-2-iodoacetophenone are mentioned.
これらのハロゲン化メチルハロゲン化フェニルケトン化合物は、ハロゲン化アセトフェノン化合物の２位をハロゲン化することにより得られる。ハロゲン化としては、塩素化またはヨウ素化も可能であるが、ハロゲン化アセトフェノン化合物１モルに対し、１モルの臭素を反応させる臭素化反応が最も簡便である。 These halogenated methyl halogenated phenyl ketone compounds are obtained by halogenating the 2-position of the halogenated acetophenone compound. As the halogenation, chlorination or iodination can be performed, but the bromination reaction in which 1 mol of bromine is reacted with 1 mol of the halogenated acetophenone compound is the simplest.
２−ブロモ−２′−クロロアセトフェノン、２−ブロモ−３′−クロロアセトフェノン、２−ブロモ−４′−クロロアセトフェノンや、２，３′−ジブロモアセトフェノン、２，４′−ジブロモアセトフェノンは試薬として市販されているものを使用することができる。 2-Bromo-2'-chloroacetophenone, 2-bromo-3'-chloroacetophenone, 2-bromo-4'-chloroacetophenone, 2,3'-dibromoacetophenone, and 2,4'-dibromoacetophenone are commercially available as reagents. Can be used.
前記の（２，４−ジクロロフェニル）アセトアミジンは、公知の方法に準拠して合成することができる。例えば、化５の反応式に示されるように、（２，４−ジクロロフェニル）アセトニトリルを塩化水素ガスおよびエタノール等の低級アルコールと反応させ、（２，４−ジクロロフェニル）アセトイミデート塩酸塩に変換し、更にアンモニアと反応させることによって、（２，４−ジクロロフェニル）アセトアミジン塩酸塩を合成することができる。 The (2,4-dichlorophenyl) acetamidine can be synthesized according to a known method. For example, as shown in the reaction formula of Chemical Formula 5, (2,4-dichlorophenyl) acetonitrile is reacted with a lower alcohol such as hydrogen chloride gas and ethanol to convert it to (2,4-dichlorophenyl) acetimidate hydrochloride. Further, (2,4-dichlorophenyl) acetamidine hydrochloride can be synthesized by further reacting with ammonia.
（２，４−ジクロロフェニル）アセトアミジンとして、前記の反応で得られる（２，４−ジクロロフェニル）アセトアミジン塩酸塩を使用できるが、これに限らず、（２，４−ジクロロフェニル）アセトアミジンと従来公知の無機酸や有機酸との塩も使用可能である。 As (2,4-dichlorophenyl) acetamidine, (2,4-dichlorophenyl) acetamidine hydrochloride obtained by the above reaction can be used, but not limited thereto, (2,4-dichlorophenyl) acetamidine and conventionally known A salt with an inorganic acid or an organic acid can also be used.
前記の脱ハロゲン化水素剤は公知のものを制限なく使用できる。このような脱ハロゲン化水素剤としては、例えば、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、炭酸ナトリウム、炭酸カリウム、重炭酸ナトリウム、重炭酸カリウムのような無機アルカリ類、トリエチルアミン、１，８−ジアザビシクロ［５，４，０］−７−ウンデセン（ＤＢＵ）のような有機塩基類、ナトリウムメトキシド、カリウムｔｅｒｔ−ブトキシドのような金属アルコキシド化合物などが挙げられる。 Any known dehydrohalogenating agent can be used without limitation. Examples of such a dehydrohalogenating agent include inorganic alkalis such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, triethylamine, 1,8 -Organic bases such as diazabicyclo [5,4,0] -7-undecene (DBU), metal alkoxide compounds such as sodium methoxide, potassium tert-butoxide, and the like.
前記の反応溶媒は、ハロゲン化メチルハロゲン化フェニルケトン化合物と（２，４−ジクロロフェニル）アセトアミジンまたはその塩を溶解することができ、かつ反応に関与しないものであれば公知のものを制限なく使用できる。このような溶媒として、例えば、イソプロピルアルコール、ｔｅｒｔ−ブタノールなどのアルコール類、ヘキサン、トルエンなどの炭化水素類、クロロホルム、クロロベンゼンなどのハロゲン化炭化水素類、酢酸エチルなどのエステル類、アセトニトリルなどの二トリル類、テトラヒドロフラン、ジオキサン、エチレングリコールジメチルエーテルなどのエーテル類、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡＣ）などのアミド類、ジメチルスルホキシド（ＤＭＳＯ）などが挙げられ、これらの溶媒を組み合わせて使用してもよい。 As the reaction solvent, any known solvent can be used without limitation as long as it can dissolve a halogenated methyl halogenated phenyl ketone compound and (2,4-dichlorophenyl) acetamidine or a salt thereof and does not participate in the reaction. it can. Examples of such solvents include alcohols such as isopropyl alcohol and tert-butanol, hydrocarbons such as hexane and toluene, halogenated hydrocarbons such as chloroform and chlorobenzene, esters such as ethyl acetate, and acetonitrile. Tolyls, tetrahydrofuran, dioxane, ethers such as ethylene glycol dimethyl ether, amides such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), etc. These solvents may be used in combination.
反応温度は室温〜還流温度が好ましく、反応時間は１〜１０時間が好ましい。反応は、通常大気圧下で行えばよい。 The reaction temperature is preferably room temperature to reflux temperature, and the reaction time is preferably 1 to 10 hours. The reaction may be usually performed under atmospheric pressure.
以上の反応条件下で生成した２−（２，４−ジクロロベンジル）−４−（ハロゲン化フェニル）イミダゾール化合物は、通常の後処理によって単離することができる。
例えば、反応終了後の反応混合物を水層と有機溶媒層に分配し、有機溶媒層を水洗浄後、シュウ酸塩等として有機溶媒から析出させ、アルカリでフリー化して粗製の当該化合物を得ることができ、さらに再結晶操作等により精製することができる。
The 2- (2,4-dichlorobenzyl) -4- (halogenated phenyl) imidazole compound produced under the above reaction conditions can be isolated by ordinary post-treatment.
For example, the reaction mixture after completion of the reaction is divided into an aqueous layer and an organic solvent layer, the organic solvent layer is washed with water, precipitated from the organic solvent as oxalate, etc., and freed with alkali to obtain the crude compound. It can be further purified by recrystallization operation or the like.
以下、本発明を実施例によって具体的に説明するが、本発明はこれらに限定されるものではない。なお、（２，４−ジクロロフェニル）アセトアミジン塩酸塩の合成例を、参考例１に示す。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. A synthesis example of (2,4-dichlorophenyl) acetamidine hydrochloride is shown in Reference Example 1.
〔参考例１〕
＜（２，４−ジクロロフェニル）アセトアミジン塩酸塩の合成＞
（２，４−ジクロロフェニル）アセトニトリル１３０．２ｇ（０．７０ｍｏｌ）、クロロホルム２６２ｇ及び脱水エタノール３５．０ｇ（０．７６ｍｏｌ）からなる溶液へ、冷却下、５〜１０℃にて、塩化水素ガス２７．３ｇ（０．７５ｍｏｌ）を８０分間かけて吹き込み、５〜１０℃にて１０時間、さらに室温に戻して２日間放置することにより結晶が析出した。減圧下に溶媒を留去することにより、白色固体として（２，４−ジクロロフェニル）アセトイミド酸エチル塩酸塩が得られた。該固体を砕き、氷冷下に振とうしながら、アンモニア１７．４ｇ（１．０１ｍｏｌ）及び脱水エタノール１２２ｇからなる溶液を少しずつ加えた。加え終わった後、氷冷下にて２時間、さらに室温に戻して一晩撹拌した後の懸濁液を、２００ｇまで減圧濃縮し、冷却後、結晶をろ取し、クロロホルムで洗浄した後乾燥し、白色粉末状の（２，４−ジクロロフェニル）アセトアミジン塩酸塩１３１ｇ（０．５４７ｍｏｌ、収率７８．１％）を得た。
[Reference Example 1]
<Synthesis of (2,4-dichlorophenyl) acetamidine hydrochloride>
Hydrogen chloride gas 27. under cooling to a solution consisting of 130.2 g (0.70 mol) of (2,4-dichlorophenyl) acetonitrile, 262 g of chloroform and 35.0 g (0.76 mol) of dehydrated ethanol at 5-10 ° C. under cooling. Crystals were precipitated by blowing 3 g (0.75 mol) over 80 minutes and allowing to return to room temperature for 10 hours at 5 to 10 ° C. and for 2 days. By distilling off the solvent under reduced pressure, ethyl (2,4-dichlorophenyl) acetimidate hydrochloride was obtained as a white solid. The solid was crushed and a solution consisting of 17.4 g (1.01 mol) of ammonia and 122 g of dehydrated ethanol was added little by little while shaking under ice cooling. After the addition was completed, the suspension after stirring for 2 hours under ice-cooling and returning to room temperature overnight was concentrated to 200 g under reduced pressure. After cooling, the crystals were collected by filtration, washed with chloroform, and then dried. As a result, 131 g (0.547 mol, yield 78.1%) of white powdery (2,4-dichlorophenyl) acetamidine hydrochloride was obtained.
〔実施例１〕
＜４−（４−クロロフェニル）−２−（２，４−ジクロロベンジル）イミダゾールの合成＞
（２，４−ジクロロフェニル）アセトアミジン塩酸塩３５．９ｇ（０．１５ｍｏｌ）、炭酸カリウム５２ｇ（０．３８ｍｏｌ）及びＮ，Ｎ−ジメチルホルムアミド１２０ｍｌからなる懸濁液を５０℃にて３０分撹拌後、同温度にて、２−ブロモ−４′−クロロアセトフェノン３５．０ｇ（０．１５ｍｏｌ）、クロロホルム５０ｍｌ及びＮ，Ｎ−ジメチルホルムアミド３０ｍｌからなる溶液を１時間かけて滴下し、さらに６０℃にて３時間撹拌した。次いで、反応懸濁液を冷却後、水８００ｍｌ及びクロロホルム２００ｍｌに分配し、クロロホルム層を水で２回洗浄した後、減圧下にクロロホルムを留去してアメ状の濃縮物を得た。該アメ状物をアセトンに溶解し、シュウ酸を系が弱酸性になるまで加え、析出した結晶をろ取、アセトンで洗浄して、灰色結晶として目的物のシュウ酸塩が得られた。該シュウ酸塩をメタノールに加温下懸濁し、２８％ナトリウムメトキシド−メタノール溶液をアルカリになるまで十分加えたのち、メタノールを減圧留去し、アメ状の濃縮物を３回熱水で洗浄さらにアセトニトリルで撹拌処理することにより、黄褐色粉末状の粗製物が得られた。該粉末ををアセトニトリルより再結晶して、黄白色粉末状の結晶１１．６ｇ（０．０３５ｍｏｌ、収率２３％）を得た。
[Example 1]
<Synthesis of 4- (4-chlorophenyl) -2- (2,4-dichlorobenzyl) imidazole>
A suspension composed of 35.9 g (0.15 mol) of (2,4-dichlorophenyl) acetamidine hydrochloride, 52 g (0.38 mol) of potassium carbonate and 120 ml of N, N-dimethylformamide was stirred at 50 ° C. for 30 minutes. At the same temperature, a solution consisting of 35.0 g (0.15 mol) of 2-bromo-4′-chloroacetophenone, 50 ml of chloroform and 30 ml of N, N-dimethylformamide was added dropwise over 1 hour, and further at 60 ° C. Stir for 3 hours. Then, the reaction suspension was cooled and then partitioned into 800 ml of water and 200 ml of chloroform, and the chloroform layer was washed twice with water, and then chloroform was distilled off under reduced pressure to obtain a candy-like concentrate. The candy-like product was dissolved in acetone, oxalic acid was added until the system became weakly acidic, and the precipitated crystals were collected by filtration and washed with acetone to obtain the desired oxalate salt as gray crystals. Suspend the oxalate salt in methanol and add 28% sodium methoxide-methanol solution to alkalinity. After removing methanol under reduced pressure, wash the candy-like concentrate three times with hot water. Further, a crude product in the form of a tan powder was obtained by stirring with acetonitrile. The powder was recrystallized from acetonitrile to obtain 11.6 g (0.035 mol, yield 23%) of yellowish white crystals.
得られた結晶の融点、薄層クロマトグラフィーのＲｆ値、１Ｈ−ＮＭＲ及びマススペクトルデータは、以下のとおりであった。
・mp. 168−169℃
・TLC (シリカゲル，アセトン) ： Rf = 0.68
・1H-NMR(d6-DMSO) δ： 4.10(s, 2H), 7.29−7.71(m, 8H)
・MS m/z(%) ： 336(M+, 33),
301(100), 266(42), 231(5), 159(6), 133(5), 115(8), 102(4), 89(11).
これらのスペクトルデータから、得られた化合物は、化６で示される４−（４−クロロフェニル）−２−（２，４−ジクロロベンジル）イミダゾールであるものと同定した。
The melting point of the obtained crystal, the Rf value of thin layer chromatography, 1 H-NMR and mass spectral data were as follows.
・ Mp.168-169 ℃
・ TLC (silica gel, acetone): Rf = 0.68
・1 H-NMR (d 6 -DMSO) δ: 4.10 (s, 2H), 7.29-7.71 (m, 8H)
・ MS m / z (%): 336 (M + , 33),
301 (100), 266 (42), 231 (5), 159 (6), 133 (5), 115 (8), 102 (4), 89 (11).
From these spectral data, the obtained compound was identified as 4- (4-chlorophenyl) -2- (2,4-dichlorobenzyl) imidazole represented by Chemical formula 6.
〔実施例２〕
＜４−（４−ブロモフェニル）−２−（２，４−ジクロロベンジル）イミダゾールの合成＞
実施例１の２−ブロモ−４′−クロロアセトフェノンを２，４′−ジブロモアセトフェノンに代えて、実施例１の方法に準拠して合成試験を実施し、灰白色粉末状の結晶を得た。
[Example 2]
<Synthesis of 4- (4-bromophenyl) -2- (2,4-dichlorobenzyl) imidazole>
A synthesis test was carried out according to the method of Example 1 by replacing 2-bromo-4'-chloroacetophenone of Example 1 with 2,4'-dibromoacetophenone, and crystals of off-white powder were obtained.
得られた結晶の融点、薄層クロマトグラフィーのＲｆ値、１Ｈ−ＮＭＲ及びマススペクトルデータは、以下のとおりであった。
・mp. 186−187℃
・TLC (シリカゲル，アセトン) ： Rf = 0.73
・1H-NMR(d6-DMSO) δ： 4.12(s, 2H), 7.32−7.68(m, 8H)
・MS m/z(%) ： 382(M++2, 44),
380(M+, 28), 347(100), 310(28), 266(9), 231(9), 159(8), 133(9),
115(15), 102(6), 89(17).
これらのスペクトルデータから、得られた化合物は、化７で示される４−（４−ブロモフェニル）−２−（２，４−ジクロロベンジル）イミダゾールであるものと同定した。
The melting point of the obtained crystal, the Rf value of thin layer chromatography, 1 H-NMR and mass spectral data were as follows.
・ Mp. 186-187 ℃
・ TLC (silica gel, acetone): Rf = 0.73
・1 H-NMR (d 6 -DMSO) δ: 4.12 (s, 2H), 7.32-7.68 (m, 8H)
MS m / z (%): 382 (M + +2, 44),
380 (M + , 28), 347 (100), 310 (28), 266 (9), 231 (9), 159 (8), 133 (9),
115 (15), 102 (6), 89 (17).
From these spectral data, the obtained compound was identified as 4- (4-bromophenyl) -2- (2,4-dichlorobenzyl) imidazole represented by Chemical formula 7.
〔実施例３〕
実施例１および２において合成したイミダゾール化合物と、これらとは別に２−フェニルイミダゾールを有効成分とする表面処理液を各々調製し、該処理液に銅を接触させることにより銅の表面に化成皮膜を形成させ、銅に対する溶融半田の濡れ時間を測定して、各々のイミダゾール化合物が作用する銅表面への酸化防止性能を評価した。この場合、濡れ時間が短い程、イミダゾール化合物の酸化防止性能が優れているものと判定される。
評価試験の詳細は、次のとおりである。
（１）表面処理液の調整
イミダゾール化合物、酸、金属塩およびハロゲン化合物を、表１記載の組成となるようにイオン交換水に溶解させた後、アンモニア水でｐＨを調整して表面処理液を調製した。
（２）表面処理方法
材質が金属銅の試験片（５ｍｍ×５０ｍｍ×０．３ｍｍの銅板）を脱脂し、次いでソフトエッチングを行い、所定温度の表面処理液に所定時間浸漬して、銅の表面に化成皮膜を形成させた後、水洗して乾燥した。
（３）濡れ時間の測定
表面処理を行った試験片を、ポストフラックス〔商品名「ＪＳ−６４ＭＳＳ」（株）弘輝製〕に浸漬して、半田濡れ性試験器（ＳＡＴ−２０００、（株）レスカ製）を使用して半田濡れ時間（秒）を測定した。使用した半田は錫−鉛系共晶半田（商品名：Ｈ６３Ａ、千住金属工業製）であり、測定条件は半田温度２４０℃，浸漬深さ２ｍｍ，浸漬スピード１６ｍｍ／秒とした。
なお、半田濡れ時間を測定した試験片は、（Ａ）表面処理直後のものと、（Ｂ）温度４０℃、湿度９０％ＲＨの恒温恒湿器に入れて９６時間放置したものと、（Ｃ）さらに（Ｂ）を２００℃で１０分間加熱したものである。
得られた試験結果は、表１に示したとおりであった。
Example 3
A surface treatment liquid containing 2-phenylimidazole as an active ingredient is prepared separately from the imidazole compound synthesized in Examples 1 and 2, and a chemical conversion film is formed on the copper surface by bringing the treatment liquid into contact with copper. It was formed, and the wetting time of the molten solder with respect to copper was measured, and the antioxidant performance on the copper surface on which each imidazole compound acts was evaluated. In this case, it is determined that the shorter the wetting time, the better the antioxidant performance of the imidazole compound.
The details of the evaluation test are as follows.
(1) Preparation of surface treatment solution After dissolving an imidazole compound, an acid, a metal salt, and a halogen compound in ion-exchanged water so as to have the composition shown in Table 1, the pH is adjusted with ammonia water to adjust the surface treatment solution Prepared.
(2) Surface treatment method A test piece (5 mm x 50 mm x 0.3 mm copper plate) made of metallic copper is degreased, then soft-etched, and immersed in a surface treatment solution at a predetermined temperature for a predetermined time to obtain a copper surface. After the chemical conversion film was formed on, it was washed with water and dried.
(3) Wetting time measurement The surface-treated test piece was immersed in a post-flux [trade name “JS-64MSS” manufactured by Hiroki Co., Ltd.] and solder wettability tester (SAT-2000, Inc.). Solder wetting time (seconds) was measured using Resca. The solder used was tin-lead eutectic solder (trade name: H63A, manufactured by Senju Metal Industry), and the measurement conditions were a solder temperature of 240 ° C., an immersion depth of 2 mm, and an immersion speed of 16 mm / second.
In addition, the test piece which measured the solder wetting time includes (A) a sample immediately after the surface treatment, (B) a sample left in a constant temperature and humidity chamber at a temperature of 40 ° C. and a humidity of 90% RH for 96 hours, and (C ) Further, (B) is heated at 200 ° C. for 10 minutes.
The test results obtained were as shown in Table 1.
表１に示した試験結果によれば、本願発明の２−（２，４−ジクロロベンジル）−４−（ハロゲン化フェニル）イミダゾール化合物を有効成分として含有する表面処理液は、銅の表面に耐湿性および耐熱性に優れた化成皮膜を形成させることができるので、銅表面の酸化防止に有用である。
According to the test results shown in Table 1, the surface treatment solution containing the 2- (2,4-dichlorobenzyl) -4- (halogenated phenyl) imidazole compound of the present invention as an active ingredient is resistant to moisture on the surface of copper. Therefore, it is useful for preventing the oxidation of the copper surface.
Claims (1)
A 2- (2,4-dichlorobenzyl) -4- (halogenated phenyl) imidazole compound represented by the chemical formula (I) of Chemical Formula 1.
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