JP2008285454A - Method for producing imidazole compound - Google Patents
Method for producing imidazole compound Download PDFInfo
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- JP2008285454A JP2008285454A JP2007134098A JP2007134098A JP2008285454A JP 2008285454 A JP2008285454 A JP 2008285454A JP 2007134098 A JP2007134098 A JP 2007134098A JP 2007134098 A JP2007134098 A JP 2007134098A JP 2008285454 A JP2008285454 A JP 2008285454A
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- ligand
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- imidazole compound
- imidazoline
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 52
- -1 imidazole compound Chemical class 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000003446 ligand Substances 0.000 claims abstract description 65
- 239000012327 Ruthenium complex Substances 0.000 claims abstract description 18
- 230000007935 neutral effect Effects 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000129 anionic group Chemical group 0.000 claims abstract description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 150000002462 imidazolines Chemical class 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 239000007800 oxidant agent Substances 0.000 abstract description 11
- 125000001424 substituent group Chemical group 0.000 abstract description 9
- 125000001931 aliphatic group Chemical group 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 7
- VWSLLSXLURJCDF-UHFFFAOYSA-N 2-methyl-4,5-dihydro-1h-imidazole Chemical compound CC1=NCCN1 VWSLLSXLURJCDF-UHFFFAOYSA-N 0.000 description 7
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000006356 dehydrogenation reaction Methods 0.000 description 7
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 150000002460 imidazoles Chemical class 0.000 description 6
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 5
- DRGAZIDRYFYHIJ-UHFFFAOYSA-N 2,2':6',2''-terpyridine Chemical compound N1=CC=CC=C1C1=CC=CC(C=2N=CC=CC=2)=N1 DRGAZIDRYFYHIJ-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 3
- NBPGPQJFYXNFKN-UHFFFAOYSA-N 4-methyl-2-(4-methylpyridin-2-yl)pyridine Chemical compound CC1=CC=NC(C=2N=CC=C(C)C=2)=C1 NBPGPQJFYXNFKN-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
- 150000001412 amines Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 0 *C1=NCCN1 Chemical compound *C1=NCCN1 0.000 description 2
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 2
- WLDGDTPNAKWAIR-UHFFFAOYSA-N 1,4,7-trimethyl-1,4,7-triazonane Chemical compound CN1CCN(C)CCN(C)CC1 WLDGDTPNAKWAIR-UHFFFAOYSA-N 0.000 description 2
- ZXLQVVRBSAUVJB-UHFFFAOYSA-N 2-(3-pyridin-2-ylphenyl)pyridine Chemical compound N1=CC=CC=C1C1=CC=CC(C=2N=CC=CC=2)=C1 ZXLQVVRBSAUVJB-UHFFFAOYSA-N 0.000 description 2
- POIHGNUQPJHDTP-UHFFFAOYSA-N 2-phenyl-6-pyridin-2-ylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC(C=2N=CC=CC=2)=N1 POIHGNUQPJHDTP-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000005595 deprotonation Effects 0.000 description 2
- 238000010537 deprotonation reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- AHTPZXAPHHTTFU-UHFFFAOYSA-N 1-[3-(4,5-dihydroimidazol-1-yl)phenyl]-4,5-dihydroimidazole Chemical compound C1=NCCN1C1=CC=CC(N2C=NCC2)=C1 AHTPZXAPHHTTFU-UHFFFAOYSA-N 0.000 description 1
- OUWLQMIJGBZEME-UHFFFAOYSA-N 1-[3-[(dimethylamino)methyl]phenyl]-n,n-dimethylmethanamine Chemical compound CN(C)CC1=CC=CC(CN(C)C)=C1 OUWLQMIJGBZEME-UHFFFAOYSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 1
- HKMPIVAZXQFXPD-UHFFFAOYSA-N 2-[3-(1h-imidazol-2-yl)phenyl]-1h-imidazole Chemical compound C1=CNC(C=2C=C(C=CC=2)C=2NC=CN=2)=N1 HKMPIVAZXQFXPD-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- IYKBMPHOPLFHAQ-UHFFFAOYSA-N 2-phenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=C(C=CC=2C3=NC=CC=2)C3=N1 IYKBMPHOPLFHAQ-UHFFFAOYSA-N 0.000 description 1
- BKCCAYLNRIRKDJ-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1h-imidazole Chemical compound N1CCN=C1C1=CC=CC=C1 BKCCAYLNRIRKDJ-UHFFFAOYSA-N 0.000 description 1
- DFXNVSIALRDJHY-UHFFFAOYSA-N 2-pyrazin-2-ylpyrazine Chemical compound C1=NC=CN=C1C1=CN=CC=N1 DFXNVSIALRDJHY-UHFFFAOYSA-N 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- QLSOZHFOFHARBJ-UHFFFAOYSA-N [3-(diphenylphosphanylmethyl)phenyl]methyl-diphenylphosphane Chemical compound C=1C=CC(CP(C=2C=CC=CC=2)C=2C=CC=CC=2)=CC=1CP(C=1C=CC=CC=1)C1=CC=CC=C1 QLSOZHFOFHARBJ-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical group C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- VNLHPVUKSKTUPA-UHFFFAOYSA-N ditert-butyl-[[3-(ditert-butylphosphanylmethyl)phenyl]methyl]phosphane Chemical compound CC(C)(C)P(C(C)(C)C)CC1=CC=CC(CP(C(C)(C)C)C(C)(C)C)=C1 VNLHPVUKSKTUPA-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- JVZRCNQLWOELDU-UHFFFAOYSA-N gamma-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 description 1
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Abstract
【課題】特定の酸化剤を使用することなく、温和な反応条件下でイミダゾリン化合物を効率よく脱水素化してイミダゾール化合物の製造法を提供する。
【解決手段】２位に置換基としてアルキル基、芳香族脂肪族基、芳香族基で表されるイミダゾリン化合物から、上記置換基を有するイミダゾール化合物を製造する方法において、単座配位子がアニオン性や中性であり、中性の配位子がピリジン、ジメチルスルホキシド等からなる群から選択されるルテニウム錯体を使用する。
【選択図】なしProvided is a method for producing an imidazole compound by efficiently dehydrogenating an imidazoline compound under mild reaction conditions without using a specific oxidizing agent.
In a method for producing an imidazole compound having the above substituent from an imidazoline compound represented by an alkyl group, an aromatic aliphatic group or an aromatic group as a substituent at the 2-position, the monodentate ligand is anionic. A ruthenium complex is used which is neutral and has a neutral ligand selected from the group consisting of pyridine, dimethyl sulfoxide and the like.
[Selection figure] None
Description
本発明は、イミダゾール化合物を製造する方法に関する。より詳しくは、本発明は、触媒としてルテニウム錯体を使用することで、特定の酸化剤を使用することなく、大気中の酸素を活用して温和な条件下で多様なイミダゾリン化合物を効率よく脱水素化してイミダゾール化合物を製造する方法に関する。 The present invention relates to a method for producing an imidazole compound. More specifically, the present invention uses a ruthenium complex as a catalyst, thereby efficiently dehydrogenating various imidazoline compounds under mild conditions using oxygen in the atmosphere without using a specific oxidant. The present invention relates to a method for producing an imidazole compound.
イミダゾール化合物類は、エポキシ樹脂の硬化剤や医農薬および染料の中間体、銅の防錆剤、電解質（イオン性液体）等様々な工業分野に広く利用されている（非特許文献１〜２）。一般に２−位に置換基を有するイミダゾール化合物は相当するイミダゾリン化合物を脱水素化することにより合成される（特許文献３〜８）。また、特開平９−２２７５２５号（特許文献１）および２０００−１７８２５６号（特許文献２）には遷移金属を触媒としてイミダゾリン化合物を脱水素化してイミダゾール化合物を製造する方法が開示されている。しかしながら、従来のイミダゾリン化合物の脱水素化によるイミダゾール化合物の製造には、厳しい反応条件や毒性・爆発性の高い重金属酸化剤の使用を必要とする。 Imidazole compounds are widely used in various industrial fields such as epoxy resin curing agents, medical and agricultural chemicals and dye intermediates, copper rust preventives, and electrolytes (ionic liquids) (Non-Patent Documents 1 and 2). . In general, an imidazole compound having a substituent at the 2-position is synthesized by dehydrogenating a corresponding imidazoline compound (Patent Documents 3 to 8). JP-A-9-227525 (Patent Document 1) and 2000-178256 (Patent Document 2) disclose a method for producing an imidazole compound by dehydrogenating an imidazoline compound using a transition metal as a catalyst. However, the production of imidazole compounds by dehydrogenation of conventional imidazoline compounds requires the use of harsh reaction conditions and heavy metal oxidants with high toxicity and explosive properties.
ルテニウム錯体はアルコールやオレフィンの水素移動型還元触媒として高い触媒活性を示すと同時に酸化触媒としても報告されている（非特許文献９）。また、遷移金属錯体に配位したアミン配位子はその水素原子の酸性度が大きくなり、酸化が促進される。特に、中心金属としてはルテニウムやオスミウムが有効であることが知られている（非特許文献１０〜１２；なお非特許文献１０および１２に関しては、それぞれの文献中で引用された文献も参照）。しかしながら、イミダゾリンがＮ−位で配位した金属錯体の例は少なく、配位したイミダゾリンが酸化された例は皆無である。 Ruthenium complexes have been reported as oxidation catalysts as well as high catalytic activity as hydrogen transfer reduction catalysts for alcohols and olefins (Non-patent Document 9). In addition, the amine ligand coordinated to the transition metal complex has a high acidity of the hydrogen atom and promotes oxidation. In particular, it is known that ruthenium and osmium are effective as the central metal (Non-Patent Documents 10 to 12; regarding Non-Patent Documents 10 and 12, refer to the documents cited in the respective documents). However, there are few examples of metal complexes in which imidazoline is coordinated at the N-position, and none of the coordinated imidazolines are oxidized.
上記のように、従来のイミダゾリン化合物の脱水素化によるイミダゾール化合物の製造には厳しい反応条件や毒性の高い重金属酸化剤の使用を必要とすることが多く、効率的で且つ安全性の高い合成法の開発が望まれている。特に、特定の酸化剤を使用せず、大気中の酸素を活用してイミダゾリン化合物を脱水素化できれば工業上非常に有意義である。 As mentioned above, the production of imidazole compounds by dehydrogenation of conventional imidazoline compounds often requires severe reaction conditions and the use of highly toxic heavy metal oxidants, and is an efficient and safe synthesis method. Development is desired. In particular, it is very significant industrially if a specific oxidant is not used and oxygen in the atmosphere can be utilized to dehydrogenate the imidazoline compound.
本発明の目的は、上記した従来技術の欠点を解消することができるイミダゾール化合物の製造法を提供することにある。 The objective of this invention is providing the manufacturing method of the imidazole compound which can eliminate the fault of the above-mentioned prior art.
本発明の他の目的は、特定の酸化剤を使用することなく、温和な反応条件下でイミダゾリン化合物を効率よく脱水素化することができるイミダゾール化合物の製造法を提供することにある。 Another object of the present invention is to provide a method for producing an imidazole compound that can efficiently dehydrogenate an imidazoline compound under mild reaction conditions without using a specific oxidizing agent.
本発明者は鋭意研究の結果、従来におけるように特定の酸化剤を使用するのではなく、大気中の酸素を活用して、効率よくイミダゾリン化合物を脱水素化することが、上記目的の達成のために極めて効果的なことを見出した。 As a result of diligent research, the present inventor has achieved the above object by efficiently dehydrogenating an imidazoline compound by utilizing oxygen in the atmosphere instead of using a specific oxidizing agent as in the past. And found it extremely effective.
本発明のイミダゾール化合物の製造法は上記知見に基づくものであり、より詳しくは、下記式（１）、 The production method of the imidazole compound of the present invention is based on the above knowledge, and more specifically, the following formula (1),
で表されるイミダゾリン化合物から、下記式（２）、
From the imidazoline compound represented by the following formula (2),
で表されるイミダゾール化合物を製造する方法であって、且つ、下記式（３）で表されるルテニウム錯体を使用することを特徴とするものである。
And a ruthenium complex represented by the following formula (3) is used.
（式中、Ｘはイミダゾリンと置換が可能な単座配位子であり、Ｌ１は炭素で結合した配位子であり、Ｌ２、あるいはＬ２およびＬ３と連結した二座あるいは三座キレート配位子を形成し；またＬ４およびＬ５は配位子であり、それぞれ独立な単座配位子でも良く、お互いに連結した二座配位子でも良く、Ｌ３，Ｌ４，およびＬ５で連結した三座配位子でも良い）。 (Wherein, X is monodentate ligand capable substituted imidazoline, L 1 is a ligand bonded carbon, bidentate or tridentate chelating linked with L 2 or L 2 and L 3, L 4 and L 5 are ligands, each of which may be an independent monodentate ligand or a bidentate ligand linked to each other, L 3 , L 4 , and L Or a tridentate ligand linked by 5 ).
上記構成を有する本発明のイミダゾール化合物の製造法においては、遷移金属錯体に配位したアミン配位子はその水素原子の酸性度が大きくなり、酸化が促進される事実に注目し、遷移金属にイミダゾリン化合物を配位させることによって、イミダゾリン化合物の脱水素化が促進される。 In the method for producing an imidazole compound of the present invention having the above-described configuration, the amine ligand coordinated to the transition metal complex has a high acidity of the hydrogen atom, and attention is paid to the fact that oxidation is promoted. By coordinating the imidazoline compound, dehydrogenation of the imidazoline compound is promoted.
触媒として使用する遷移金属には、アミン配位子の酸化に有効であるルテニウムを使用し、且つ、メタラサイクル型配位子を用いてルテニウム錯体の適当な分子設計を行うことで、中心金属の酸化還元電位を適切に制御し、大気中の酸素を活用したイミダゾリン配位子の脱水素化反応が提供される。 As the transition metal used as a catalyst, ruthenium, which is effective for the oxidation of amine ligands, is used, and by designing an appropriate molecular design of the ruthenium complex using a metallacycle-type ligand, There is provided a dehydrogenation reaction of an imidazoline ligand by appropriately controlling the oxidation-reduction potential and utilizing oxygen in the atmosphere.
本発明により、ルテニウム錯体を触媒として使用することで、特定の酸化剤を使用せずに多様なイミダゾール化合物を高収率で生成できる製造法を提供できる。また、温和な条件下で大気中の酸素を活用した脱水素反応によってイミダゾール化合物を生成する製造法を提供できることから、工業上極めて有意義である。 According to the present invention, by using a ruthenium complex as a catalyst, it is possible to provide a production method capable of producing various imidazole compounds in high yield without using a specific oxidizing agent. Moreover, since it can provide the manufacturing method which produces | generates an imidazole compound by dehydrogenation reaction using the oxygen in air | atmosphere on mild conditions, it is very significant industrially.
以下、必要に応じて図面を参照しつつ本発明を更に具体的に説明する。以下の記載において量比を表す「部」および「％」は、特に断らない限り質量基準とする。 Hereinafter, the present invention will be described more specifically with reference to the drawings as necessary. In the following description, “parts” and “%” representing the quantity ratio are based on mass unless otherwise specified.
（イミダゾール化合物の製造法）
本発明のイミダゾール化合物の製造法は、下記式（１）で表されるイミダゾリン化合物から、下記式（２）で表されるイミダゾール化合物を製造する際に、ルテニウム錯体であって、下記式（３）で表されるものを使用する。
(Method for producing imidazole compound)
The production method of the imidazole compound of the present invention is a ruthenium complex when producing an imidazole compound represented by the following formula (2) from an imidazoline compound represented by the following formula (1), ) Is used.
（置換基Ｒ）
上記した置換基Ｒは、炭素数１〜１０のアルキル基、芳香脂肪族基、芳香族基から選択される。
(Substituent R)
The substituent R described above is selected from an alkyl group having 1 to 10 carbon atoms, an araliphatic group, and an aromatic group.
（置換基Ｒの例示）
上記した置換基Ｒの使用可能な例は、以下の通りである。
炭素数１〜１０のアルキル基：メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、イソプロピル、イソブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、イソアミル、ネオペンチル、２−メチルブチル
芳香族脂肪族基：ベンジル、フェネチル
芳香族基：フェニル、トリル、エチルフェニル、プロピルフェニル、ブチルフェニル、アニシル、エトキシフェニル、ピリジル、チエニル、ピロリル、イミダゾリジル、イミダゾリル、１−ナフチル、２−ナフチル
(Example of substituent R)
Examples of usable substituents R are as follows.
Alkyl group having 1 to 10 carbon atoms: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isoamyl, neopentyl, 2-methylbutyl aromatic Aliphatic groups: benzyl, phenethyl Aromatic groups: phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, anisyl, ethoxyphenyl, pyridyl, thienyl, pyrrolyl, imidazolidyl, imidazolyl, 1-naphthyl, 2-naphthyl
（好適な置換基Ｒの例示）
上記した置換基Ｒのうち、市販されており入手しやすさの点から好ましい例は、以下の通りである。
炭素数１〜１０のアルキル基：メチル
芳香族脂肪族基：ベンジル
芳香族基：フェニル、４−ピリジル
(Example of suitable substituent R)
Among the above-described substituents R, preferred examples from the viewpoint of availability and availability are as follows.
C1-C10 alkyl group: methyl aromatic aliphatic group: benzyl aromatic group: phenyl, 4-pyridyl
（配位子）
上記式中、Ｘはイミダゾリンと置換が可能な単座配位子、例えばＣｌ、Ｂｒ、Ｉ、アセテート等のアニオン配位子、ピリジン、ジメチルスルホキシド、Ｈ２Ｏ等の中性配位子が挙げられる。Ｌ１は炭素で結合した配位子であり、Ｌ２、あるいはＬ２およびＬ３と連結した二座あるいは三座キレート配位子を形成し；またＬ４およびＬ５は配位子であり、それぞれ独立な単座配位子でも良く、お互いに連結した二座配位子でも良く、Ｌ３，Ｌ４，およびＬ５で連結した三座配位子でも良い（以下これを「メタラサイクル型配位子」と呼称する）。
(Ligand)
In the above formula, X is a monodentate ligand capable of substituting with imidazoline, for example, anionic ligands such as Cl, Br, I and acetate, and neutral ligands such as pyridine, dimethyl sulfoxide and H 2 O. . L 1 is a ligand bonded carbon, L 2, or L 2 and L 3 and form a bidentate or tridentate chelating ligands linked; and L 4 and L 5 represents be ligand Independent monodentate ligands, bidentate ligands linked to each other, and tridentate ligands linked by L 3 , L 4 , and L 5 may be used (hereinafter referred to as “metallacycle type”). Referred to as a "ligand").
（配位子の例示）
配位子Ｌ１〜Ｌ２の例としては２−フェニルピリジン等が、Ｌ１〜Ｌ２−Ｌ３の例としては６’−フェニル−２，２’−ビピリジン、２，６−ビス（２−ピリジル）ベンゼン、２，６−ビス（２−イミダゾリル）ベンゼン、２，６−ビス（２−イミダゾリニル）ベンゼン等が挙げられる。上記以外の配位子は中性の配位子が望ましく、反応中に解離を起こさないことが望ましい。
(Examples of ligands)
Examples of the ligands L 1 to L 2 include 2-phenylpyridine and the like, and examples of L 1 to L 2 -L 3 include 6′-phenyl-2,2′-bipyridine, 2,6-bis (2 -Pyridyl) benzene, 2,6-bis (2-imidazolyl) benzene, 2,6-bis (2-imidazolinyl) benzene and the like. The ligands other than the above are desirably neutral ligands and desirably do not cause dissociation during the reaction.
Ｌ１を含む配位子が二座である場合（すなわち、Ｌ１〜Ｌ２）、Ｌ３−Ｌ４−Ｌ５の例としては、２，２’：６’，２”−ターピリジン、１，４，７−トリメチル−１，４，７−トリアザシクロノナン等が挙げられ、Ｌ１を含む配位子が三座である場合（すなわち、Ｌ１〜Ｌ２−Ｌ３）、Ｌ４−Ｌ５の例としては、２，２’−ビピリジン、４，４’−ジメチル−２，２’−ビピリジン等が挙げられる。）で表される化合物が触媒として好適に使用される。 When the ligand containing L 1 is bidentate (ie, L 1 -L 2 ), examples of L 3 -L 4 -L 5 include 2,2 ′: 6 ′, 2 ″ -terpyridine, , 4,7-trimethyl-1,4,7-triazacyclononane and the like, and when the ligand containing L 1 is tridentate (ie, L 1 -L 2 -L 3 ), L 4 Examples of -L 5 include 2,2′-bipyridine, 4,4′-dimethyl-2,2′-bipyridine, and the like.
（配位子Ｌ１〜Ｌ２の他の例）
上記した配位子Ｌ１〜Ｌ２（更にはＬ３、Ｌ４−Ｌ５）として使用可能な他の例は、以下の通りである。
２−イミダゾリルフェニル、４−イミダゾリルフェニル、ピラジルフェニル、２−ピリミリジルフェニル、４−ピリミリジルフェニル、
１，３−ビス（ジ−ｔｅｒｔ−ブチルホスフィノメチル）ベンゼン、１，３−ビス（ジフェニルホスフィノメチル）ベンゼン、１，３−ビス（ジメチルアミノメチル）ベンゼン、２−フェニル−１，１０−フェナントロリン
(Other examples of ligands L 1 to L 2 )
Other examples that can be used as the above-described ligands L 1 to L 2 (further, L 3 , L 4 -L 5 ) are as follows.
2-imidazolylphenyl, 4-imidazolylphenyl, pyrazylphenyl, 2-pyrimidylphenyl, 4-pyrimidylphenyl,
1,3-bis (di-tert-butylphosphinomethyl) benzene, 1,3-bis (diphenylphosphinomethyl) benzene, 1,3-bis (dimethylaminomethyl) benzene, 2-phenyl-1,10- Phenanthroline
（配位子Ｌ１〜Ｌ２の好ましい例）
上記した配位子Ｌ１〜Ｌ２（更にはＬ３、Ｌ４−Ｌ５）として、入手しやすさから、市販されているものもしくは合成の簡便性の点から好ましい例は、以下の通りである。
配位子Ｌ１−Ｌ２の例としては、２−フェニルピリジンが好ましい。
配位子Ｌ１−Ｌ２−Ｌ３の例としては、６’−フェニル−２，２’−ビピリジン、２，６−ビス（２−ピリジル）ベンゼンが好ましい。
(Preferred examples of ligands L 1 to L 2 )
Preferred examples of the above-described ligands L 1 to L 2 (further, L 3 and L 4 -L 5 ) from the viewpoint of availability and the point of simplicity of synthesis are as follows. It is.
As an example of the ligand L 1 -L 2 , 2-phenylpyridine is preferable.
As examples of the ligand L 1 -L 2 -L 3 , 6′-phenyl-2,2′-bipyridine and 2,6-bis (2-pyridyl) benzene are preferable.
（中性配位子の例）
上記した中性配位子として使用可能な例は、以下の通りである。
２，２’−ビピリジン、１，１０−フェナントロリン、２，２’−ビピラジン、４，４’−ジメチル−２，２’−ビピリジン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、２，２’−ビス（ジフェニルホスフィノ）−１，１’−ビナフチル、１，２−ビス（ジフェニルホスフィノ）エタン、１，３−ビス（ジフェニルホスフィノ）プロパン、１，１’−ビス（ジフェニルホスフィノ）フェロセン、
２，２’：６’，２”−ターピリジン、１，４，７−トリメチル−１，４，７−トリアザシクロノナン
(Example of neutral ligand)
Examples that can be used as the neutral ligand described above are as follows.
2,2′-bipyridine, 1,10-phenanthroline, 2,2′-bipyrazine, 4,4′-dimethyl-2,2′-bipyridine, N, N, N ′, N′-tetramethylethylenediamine, 2, 2'-bis (diphenylphosphino) -1,1'-binaphthyl, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,1'-bis (diphenylphos Fino) ferrocene,
2,2 ′: 6 ′, 2 ″ -terpyridine, 1,4,7-trimethyl-1,4,7-triazacyclononane
（中性配位子の好ましい例）
上記した中性配位子として、入手しやすさから、市販されているものもしくは合成の簡便性の点から好ましい例は、以下の通りである。
Ｌ３−Ｌ４−Ｌ５としては、２，２’：６’，２”−ターピリジン、１，４，７−トリメチル−１，４，７−トリアザシクロノナンが好ましい。
Ｌ４−Ｌ５としては、２，２’−ビピリジン、４，４’−ジメチル−２，２’−ビピリジンが好ましい。
(Preferred examples of neutral ligands)
Preferred examples of the above-described neutral ligands are those that are commercially available or that are easy to synthesize from the viewpoint of availability.
As L 3 -L 4 -L 5 , 2,2 ′: 6 ′, 2 ″ -terpyridine and 1,4,7-trimethyl-1,4,7-triazacyclononane are preferable.
L 4 -L 5 is preferably 2,2′-bipyridine or 4,4′-dimethyl-2,2′-bipyridine.
上記したように、本発明においては、式（３）のルテニウム錯体を触媒として使用することにより、特定の酸化剤を添加せず、大気中の酸素で効率よくイミダゾリン化合物を脱水素化してイミダゾールを生成する。 As described above, in the present invention, by using the ruthenium complex of the formula (3) as a catalyst, an imidazoline compound can be efficiently dehydrogenated with oxygen in the atmosphere without adding a specific oxidant and imidazole can be obtained. Generate.
本発明においては、触媒として使用するルテニウム錯体がメタラサイクル型配位子を有する式（３）で表される有機金属化合物であることが好ましい。 In the present invention, the ruthenium complex used as the catalyst is preferably an organometallic compound represented by the formula (3) having a metallacycle-type ligand.
（塩基の添加）
本発明においては、塩基を添加することにより反応が促進することが好ましい。この場合、塩基性の度合いと反応溶媒への溶解性の点からは、塩基の好適な添加量は、イミダゾリン基準（１００質量部）として、１〜１０００質量部が好ましく、更には５０〜１００質量部が好ましい。
(Addition of base)
In the present invention, the reaction is preferably accelerated by adding a base. In this case, from the viewpoint of the degree of basicity and the solubility in the reaction solvent, the preferred addition amount of the base is preferably 1 to 1000 parts by mass, more preferably 50 to 100 parts by mass, based on the imidazoline standard (100 parts by mass). Part is preferred.
（塩基の例示）
本発明において使用可能な塩基の例は、以下の通りである。
ｔｅｒｔ−ブトキシカリウム、ｔｅｒｔ−ブトキシナトリウム、ｔｅｒｔ−ブトキシリチウム、メトキシカリウム、メトキシナトリウム、メトキシリチウム、エトキシカリウム、エトキシナトリウム、エトキシリチウム、水酸化カリウム、水酸化ナトリウム、炭酸セシウム
(Example of base)
Examples of bases that can be used in the present invention are as follows.
tert-butoxy potassium, tert-butoxy sodium, tert-butoxy lithium, methoxy potassium, methoxy sodium, methoxy lithium, ethoxy potassium, ethoxy sodium, ethoxy lithium, potassium hydroxide, sodium hydroxide, cesium carbonate
（好適な塩基の例示）
本発明において、塩基性の度合いと市販されており入手しやすさの点から好適な塩基の例は、以下の通りである。
ｔｅｒｔ−ブトキシカリウム、ｔｅｒｔ−ブトキシナトリウム
(Example of suitable base)
In the present invention, examples of suitable bases from the standpoint of basicity and commercial availability are as follows.
tert-Butoxy potassium, tert-Butoxy sodium
（反応の推定メカニズム）
本発明者は、上記の目的が式（３）で表されるルテニウム錯体を触媒として用い、式（１）で表されるイミダゾリン化合物を大気中の酸素を活用して効率よく酸化させることによって式（２）で表されるイミダゾール化合物を生成できることを見出し、本発明に到達した。
(Estimation mechanism of reaction)
The inventor of the present invention uses the ruthenium complex represented by the formula (3) as a catalyst and efficiently oxidizes the imidazoline compound represented by the formula (1) by utilizing oxygen in the atmosphere. It discovered that the imidazole compound represented by (2) was generable, and reached | attained this invention.
本発明によれば、ルテニウム錯体の中心金属にイミダゾリン化合物が配位して１〜位の水素原子の脱プロトン化が促進されることによって、特定の酸化剤を添加せずに温和な条件下でもイミダゾリン化合物の脱水素化が可能となりイミダゾール化合物が製造できる。そして、塩基を添加することによりその脱プロトン化が更に促進され、イミダゾリン化合物の脱水素化をより速く進行させることができる。更に、ルテニウム錯体にメタラサイクル型配位子を導入し、ルテニウムの酸化還元電位を適正に制御することによって、初めて大気中の酸素による脱水素化反応が効率よく進行するイミダゾール化合物の製造法を提供することができる。 According to the present invention, the imidazoline compound is coordinated to the central metal of the ruthenium complex and the deprotonation of the hydrogen atom at the 1-position is promoted, so even under mild conditions without adding a specific oxidizing agent. The imidazoline compound can be dehydrogenated to produce an imidazole compound. By adding a base, the deprotonation is further promoted, and the dehydrogenation of the imidazoline compound can be advanced more rapidly. In addition, by introducing a metallacycle-type ligand into a ruthenium complex and appropriately controlling the oxidation-reduction potential of ruthenium, we provide for the first time a method for producing an imidazole compound in which the dehydrogenation reaction with oxygen in the air proceeds efficiently. can do.
本発明によれば、式（３）で表されるルテニウム錯体を触媒として用いることによって、特定の酸化剤を使用せずに式（２）で表される多様なイミダゾール化合物を生成できる。 According to the present invention, by using the ruthenium complex represented by the formula (3) as a catalyst, various imidazole compounds represented by the formula (2) can be generated without using a specific oxidizing agent.
（ルテニウム錯体）
上記の製造法において、ルテニウム錯体には、反応直前に反応系で合成したものをそのまま用いるか、または予め合成単離したものを用いることもできる。かかるルテニウム錯体はメタラサイクル型配位子と中性配位子存在下での還元反応および配位子交換反応なる方法によって生成される錯体であり、そのメタラサイクル型配位子としては、２−フェニルピリジン等をその中性配位子としては、ターピリジン等を例示することができる。
(Ruthenium complex)
In the above production method, as the ruthenium complex, one synthesized in the reaction system immediately before the reaction can be used as it is, or one synthesized in advance can be used. Such a ruthenium complex is a complex produced by a method of reduction reaction and ligand exchange reaction in the presence of a metallacycle-type ligand and a neutral ligand. As the metallacycle-type ligand, 2- Examples of the neutral ligand of phenylpyridine and the like include terpyridine and the like.
（ルテニウム錯体の使用量）
本発明において、実質的に反応が進行する限り、ルテニウム錯体の使用量は特に制限されない。反応効率と経済的な観点から、ルテニウム触媒の使用量は、イミダゾリンを基準（１００質量部）として、０．１〜５０質量部が好ましく、更には１〜１０質量部が好ましい。
(Usage of ruthenium complex)
In the present invention, the amount of ruthenium complex used is not particularly limited as long as the reaction proceeds substantially. From the reaction efficiency and economical viewpoint, the use amount of the ruthenium catalyst is preferably 0.1 to 50 parts by mass, more preferably 1 to 10 parts by mass based on imidazoline (100 parts by mass).
（酸素の圧力）
本発明においては、実質的に反応が進行する限り、酸素の圧力は特に制限されない。反応効率と経済的な観点から、酸素分圧は５０００Ｐａ以上（更には１００００Ｐａ以上）であることが好ましい。本発明の方法は、例えば、下記式（４）に示すように、大気圧下で（すなわち、大気圧の空気中に含まれる酸素分圧下において）好適に行うことができる。
(Oxygen pressure)
In the present invention, the pressure of oxygen is not particularly limited as long as the reaction proceeds substantially. From the viewpoint of reaction efficiency and economy, the oxygen partial pressure is preferably 5000 Pa or more (further 10,000 Pa or more). The method of the present invention can be suitably carried out under atmospheric pressure (that is, under the partial pressure of oxygen contained in atmospheric air) as shown in the following formula (4), for example.
（反応条件）
本発明において、好適な反応条件は、以下の通りである。
反応温度：２０〜１００℃
反応時間：１〜７２時間
(Reaction conditions)
In the present invention, suitable reaction conditions are as follows.
Reaction temperature: 20-100 ° C
Reaction time: 1 to 72 hours
（収率）
本発明において、好適な収率としては、好適な収率はイミダゾリンを基準として、３０％以上が好ましく、更には８０％以上が好ましい。
(yield)
In the present invention, the preferred yield is preferably 30% or more, more preferably 80% or more, based on imidazoline.
以下、実施例により本発明を更に具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to examples.
実施例１：
［ＲｕＣｌ（ｐｐｙ）（ｔｐｙ）］ＰＦ６（ｔｐｙ＝２，２’：６’，２”−terpyridine，ｐｐｙ＝２−phenylpyridine）の合成
１００ｍｌナス型フラスコに［ＲｕＣｌ３（ｔｐｙ）］（２００ｍｇ，０．４５４ｍｍｏｌ）とヘキサフルオロリン酸銀（２５３ｍｇ，１．００ｍｍｏｌ）をはかりとり、２−メトキシエタノール４０ｍｌを加え７０℃で２時間攪拌した。生成した塩化銀をセライトろ過により取り除き、ろ液に２−phenylpyridine（４４．０μｌ，０．４５４ｍｍｏｌ）を加え７０℃で１２時間攪拌した。得られた緑色溶液を約１ｍｌまで濃縮し、飽和ヘキサフルオロリン酸アンモニウム水溶液を加え、析出した紫色固体をろ取、乾燥させた。収量：３０３．５ｍｇ，収率：１００％。
Example 1 :
Synthesis of [RuCl (ppy) (tpy)] PF 6 (tpy = 2,2 ′: 6 ′, 2 ″ -terpyridine, ppy = 2-phenylpyridine) [RuCl 3 (tpy)] (200 mg, 200 mg, 0.454 mmol) and silver hexafluorophosphate (253 mg, 1.00 mmol) were added, 40 ml of 2-methoxyethanol was added, and the mixture was stirred for 2 hours at 70 ° C. The formed silver chloride was removed by Celite filtration, and 2% was added to the filtrate. -Phenylpyridine (44.0 μl, 0.454 mmol) was added and stirred for 12 hours at 70 ° C. The obtained green solution was concentrated to about 1 ml, saturated aqueous ammonium hexafluorophosphate solution was added, and the precipitated purple solid was collected by filtration. Yield: 303.5 mg, yield: 100%.
実施例２
（触媒反応：２−メチルイミダゾールの合成−１）
ＮＭＲ管に［ＲｕＣｌ（ｐｐｙ）（ｔｐｙ）］ＰＦ６（４．０ｍｇ，０．００６ｍｍｏｌ）と２−メチルイミダゾリン（５．０ｍｇ，０．０６ｍｍｏｌ）をはかりとり、重メタノール１ｍｌを加え５５℃で加熱した。反応の様子を１Ｈ−ＮＭＲにより追跡した。８４時間後、２５％の２−メチルイミダゾールが生成した。
Example 2
(Catalytic reaction: Synthesis of 2-methylimidazole-1)
Weigh [RuCl (ppy) (tpy)] PF 6 (4.0 mg, 0.006 mmol) and 2-methylimidazoline (5.0 mg, 0.06 mmol) in an NMR tube, add 1 ml of deuterated methanol and heat at 55 ° C. did. The state of the reaction was followed by 1 H-NMR. After 84 hours, 25% of 2-methylimidazole was formed.
実施例３
（２−メチルイミダゾールの合成−２）
ＮＭＲ管に［ＲｕＣｌ（ｐｐｙ）（ｔｐｙ）］ＰＦ６（４．０ｍｇ，０．００６ｍｍｏｌ）と２−メチルイミダゾリン（５．０ｍｇ，０．０６ｍｍｏｌ）、カリウムｔｅｒｔ−ブトキシド（７．３ｍｇ，０．０６ｍｍｏｌ）をはかりとり、重メタノール１ｍｌを加え５５℃で加熱した。反応の様子を１Ｈ−ＮＭＲにより追跡した。４８時間後、６０％の２−メチルイミダゾールが、２８８時間後では、９７％の２−メチルイミダゾールが生成した。
Example 3
(Synthesis of 2-methylimidazole-2)
[RuCl (ppy) (tpy)] PF 6 (4.0 mg, 0.006 mmol), 2-methylimidazoline (5.0 mg, 0.06 mmol), potassium tert-butoxide (7.3 mg, 0.06 mmol) in an NMR tube. ), 1 ml of heavy methanol was added, and the mixture was heated at 55 ° C. The state of the reaction was followed by 1 H-NMR. After 48 hours, 60% of 2-methylimidazole was produced, and after 288 hours, 97% of 2-methylimidazole was produced.
比較例１
（シクロメタル化した錯体の必要性）
ＮＭＲ管に［ＲｕＣｌ（ｂｐｙ）（ｔｐｙ）］ＰＦ６］（ｂｐｙ＝２，２’−ｂｉｐｙｒｉｄｉｎｅ）（４．０ｍｇ，０．００６ｍｍｏｌ）、２−メチルイミダゾリン（５．０ｍｇ，０．０６ｍｍｏｌ）、およびカリウムｔｅｒｔ−ブトキシド（７．３ｍｇ，０．０６ｍｍｏｌ）をはかりとり、重メタノール１ｍｌを加え５５℃で加熱した結果、４８時間後、２−メチルイミダゾールの生成は全く確認されず、１ヶ月経過しても２−メチルイミダゾリンの酸化反応は観測されなかった。
Comparative Example 1
(Necessity of cyclometalated complex)
[RuCl (bpy) (tpy)] PF 6 ] (bpy = 2,2′-bipyridine) (4.0 mg, 0.006 mmol), 2-methylimidazoline (5.0 mg, 0.06 mmol), and NMR tube Potassium tert-butoxide (7.3 mg, 0.06 mmol) was weighed, 1 ml of deuterated methanol was added, and the mixture was heated at 55 ° C. As a result, no formation of 2-methylimidazole was confirmed after 48 hours, and one month passed. No oxidation reaction of 2-methylimidazoline was observed.
比較例２
（配位座が空いている必要性）
ＮＭＲ管に［Ｒｕ（ｐｐｙ）（ｂｐｙ）２］（ＰＦ６）（３．４ｍｇ，０．００６ｍｍｏｌ）、２−メチルイミダゾリン（５．０ｍｇ，０．０６ｍｍｏｌ）、およびカリウムｔｅｒｔ−ブトキシド（７．３ｍｇ，０．０６ｍｍｏｌ）をはかりとり、重メタノール１ｍｌを加え５５℃で加熱した結果、４８時間後、２−メチルイミダゾールの生成は全く確認されず、２週間経過しても２−メチルイミダゾリンの酸化反応は観測されなかった。
Comparative Example 2
(Necessity for vacant coordination seat)
[Ru (ppy) (bpy) 2 ] (PF 6 ) (3.4 mg, 0.006 mmol), 2-methylimidazoline (5.0 mg, 0.06 mmol), and potassium tert-butoxide (7.3 mg) in an NMR tube. , 0.06 mmol), and after adding 1 ml of deuterated methanol and heating at 55 ° C., no formation of 2-methylimidazole was confirmed after 48 hours, and the oxidation reaction of 2-methylimidazoline after 2 weeks. Was not observed.
比較例３
（空気の必要性）
窒素雰囲気下、ＮＭＲ管に［ＲｕＣｌ（ｐｐｙ）（ｔｐｙ）］ＰＦ６（４．０ｍｇ，０．００６ｍｍｏｌ）と２−メチルイミダゾリン（５．０ｍｇ，０．０６ｍｍｏｌ）、カリウムｔｅｒｔ−ブトキシド（７．３ｍｇ，０．０６ｍｍｏｌ）をはかりとり、重メタノール１ｍｌを加え５５℃で加熱した結果、４８時間後、４％の２−メチルイミダゾールが、３日後では６％、と２−メチルイミダゾールの生成が低収率で確認されたのみであった。
Comparative Example 3
(Need for air)
Under a nitrogen atmosphere, [RuCl (ppy) (tpy)] PF 6 (4.0 mg, 0.006 mmol), 2-methylimidazoline (5.0 mg, 0.06 mmol), potassium tert-butoxide (7.3 mg) was added to the NMR tube. , 0.06 mmol), and 1 ml of deuterated methanol was added and heated at 55 ° C. As a result, after 48 hours, 4% of 2-methylimidazole yielded 6% and the yield of 2-methylimidazole was low after 3 days. It was only confirmed by rate.
実施例４
（２−フェニルイミダゾールの合成）
ＮＭＲ管に［ＲｕＣｌ（ｐｐｙ）（ｔｐｙ）］ＰＦ６（４．０ｍｇ，０．００６ｍｍｏｌ）、２−フェニルイミダゾリン（８．８ｍｇ，０．０６ｍｍｏｌ）、カリウムｔｅｒｔ−ブトキシド（７．３ｍｇ，０．０６ｍｍｏｌ）をはかりとり、重メタノール１ｍｌを加え５５℃で加熱した。反応の様子を１Ｈ−ＮＭＲにより追跡した。４８時間後、５５％の２−フェニルイミダゾールが、４０８時間後では、９０％の２−フェニルイミダゾールが生成した。
Example 4
(Synthesis of 2-phenylimidazole)
In the NMR tube, [RuCl (ppy) (tpy)] PF 6 (4.0 mg, 0.006 mmol), 2-phenylimidazoline (8.8 mg, 0.06 mmol), potassium tert-butoxide (7.3 mg, 0.06 mmol). ), 1 ml of heavy methanol was added, and the mixture was heated at 55 ° C. The state of the reaction was followed by 1 H-NMR. After 48 hours, 55% of 2-phenylimidazole was produced, and after 408 hours, 90% of 2-phenylimidazole was produced.
Claims (5)
で表されるイミダゾリン化合物から、下記式（２）、
で表されるイミダゾール化合物を製造する方法であって、且つ、下記式（３）で表されるルテニウム錯体を使用することを特徴とするイミダゾール化合物の製造法。
From the imidazoline compound represented by the following formula (2),
A method for producing an imidazole compound represented by formula (3), wherein a ruthenium complex represented by the following formula (3) is used.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9045381B2 (en) | 2010-10-19 | 2015-06-02 | Yeda Research And Development Co. Ltd. | Ruthenium complexes and their uses in processes for formation and/or hydrogenation of esters, amides and derivatives thereof |
| US10533028B2 (en) | 2014-09-04 | 2020-01-14 | Yeda Research And Development Co. Ltd. | Ruthenium complexes and their uses as catalysts in processes for formation and/or hydrogenation of esters, amides and related reactions |
| US10562767B2 (en) | 2014-09-04 | 2020-02-18 | Yeda Research And Development Co. Ltd. | Liquid-organic hydrogen carrier systems based on catalytic peptide formation and hydrogenation |
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2007
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9045381B2 (en) | 2010-10-19 | 2015-06-02 | Yeda Research And Development Co. Ltd. | Ruthenium complexes and their uses in processes for formation and/or hydrogenation of esters, amides and derivatives thereof |
| US10533028B2 (en) | 2014-09-04 | 2020-01-14 | Yeda Research And Development Co. Ltd. | Ruthenium complexes and their uses as catalysts in processes for formation and/or hydrogenation of esters, amides and related reactions |
| US10562767B2 (en) | 2014-09-04 | 2020-02-18 | Yeda Research And Development Co. Ltd. | Liquid-organic hydrogen carrier systems based on catalytic peptide formation and hydrogenation |
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