JP5470555B2 - Method for producing arylborane compound - Google Patents
Method for producing arylborane compound Download PDFInfo
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- JP5470555B2 JP5470555B2 JP2009202706A JP2009202706A JP5470555B2 JP 5470555 B2 JP5470555 B2 JP 5470555B2 JP 2009202706 A JP2009202706 A JP 2009202706A JP 2009202706 A JP2009202706 A JP 2009202706A JP 5470555 B2 JP5470555 B2 JP 5470555B2
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- iridium
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- 150000001875 compounds Chemical class 0.000 title claims description 49
- 238000004519 manufacturing process Methods 0.000 title description 11
- -1 aryl compound Chemical class 0.000 claims description 60
- 125000000217 alkyl group Chemical group 0.000 claims description 38
- 239000003054 catalyst Substances 0.000 claims description 28
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 26
- 229910052741 iridium Inorganic materials 0.000 claims description 25
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 150000002504 iridium compounds Chemical class 0.000 claims description 13
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 claims description 5
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 5
- URYYVOIYTNXXBN-UHFFFAOYSA-N cyclooctene Chemical compound [CH]1[CH]CCCCCC1 URYYVOIYTNXXBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- LZPWAYBEOJRFAX-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2$l^{2}-dioxaborolane Chemical compound CC1(C)O[B]OC1(C)C LZPWAYBEOJRFAX-UHFFFAOYSA-N 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- ZDQWVKDDJDIVAL-UHFFFAOYSA-N catecholborane Chemical compound C1=CC=C2O[B]OC2=C1 ZDQWVKDDJDIVAL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004913 cyclooctene Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 50
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 42
- 239000007787 solid Substances 0.000 description 26
- 239000012299 nitrogen atmosphere Substances 0.000 description 17
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 16
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- FXPLCAKVOYHAJA-UHFFFAOYSA-N 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1 FXPLCAKVOYHAJA-UHFFFAOYSA-N 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- KKLCYBZPQDOFQK-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=CC=C1 KKLCYBZPQDOFQK-UHFFFAOYSA-N 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 10
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 8
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 125000006165 cyclic alkyl group Chemical group 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 5
- GGMXSSNJKVWXMD-UHFFFAOYSA-N 2-[3,5-bis(trifluoromethyl)phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 GGMXSSNJKVWXMD-UHFFFAOYSA-N 0.000 description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- PEFDHAOFDBNZEQ-UHFFFAOYSA-N 2,6-dichloro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC(Cl)=NC(Cl)=C1 PEFDHAOFDBNZEQ-UHFFFAOYSA-N 0.000 description 3
- FILKGCRCWDMBKA-UHFFFAOYSA-N 2,6-dichloropyridine Chemical compound ClC1=CC=CC(Cl)=N1 FILKGCRCWDMBKA-UHFFFAOYSA-N 0.000 description 3
- RQIATWFGYKTVCM-UHFFFAOYSA-N 2-(1-benzothiophen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC2=CC=CC=C2S1 RQIATWFGYKTVCM-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 3
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 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 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 125000004815 1,2-dimethylethylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([*:2])C([H])([H])[H] 0.000 description 2
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 2
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical group CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 2
- DTAZBCNEXKOLPE-UHFFFAOYSA-N 2-(3,4-dichlorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(Cl)C(Cl)=C1 DTAZBCNEXKOLPE-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- FRYSEKUUHUUJPX-UHFFFAOYSA-N 2-pyridin-2-ylpyridine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC(C=2N=CC=CC=2)=C1 FRYSEKUUHUUJPX-UHFFFAOYSA-N 0.000 description 2
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 2
- GCQADNWXVSTJQW-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-[4-(trifluoromethyl)phenyl]-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(C(F)(F)F)C=C1 GCQADNWXVSTJQW-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- POYRLWQLOUUKAY-UHFFFAOYSA-N 6,7,8,9-tetrahydro-5h-carbazol-3-amine Chemical compound C1CCCC2=C1NC1=CC=C(N)C=C12 POYRLWQLOUUKAY-UHFFFAOYSA-N 0.000 description 2
- KVQMUHHSWICEIH-UHFFFAOYSA-N 6-(5-carboxypyridin-2-yl)pyridine-3-carboxylic acid Chemical compound N1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=N1 KVQMUHHSWICEIH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 125000005036 alkoxyphenyl group Chemical group 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000000068 chlorophenyl group Chemical group 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- RQKGHIGGSFNVGW-UHFFFAOYSA-N ethyl 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate Chemical compound CCOC(=O)C1=CC=CC(B2OC(C)(C)C(C)(C)O2)=C1 RQKGHIGGSFNVGW-UHFFFAOYSA-N 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical compound CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- JBJGSVBGUBATNH-UHFFFAOYSA-N methyl 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate Chemical compound COC(=O)C1=CC=CC(B2OC(C)(C)C(C)(C)O2)=C1 JBJGSVBGUBATNH-UHFFFAOYSA-N 0.000 description 2
- REIZEQZILPXYKS-UHFFFAOYSA-N methyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate Chemical compound C1=CC(C(=O)OC)=CC=C1B1OC(C)(C)C(C)(C)O1 REIZEQZILPXYKS-UHFFFAOYSA-N 0.000 description 2
- 229940095102 methyl benzoate Drugs 0.000 description 2
- 125000006178 methyl benzyl group Chemical group 0.000 description 2
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 2
- 125000006501 nitrophenyl group Chemical group 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- XXZOEDQFGXTEAD-UHFFFAOYSA-N 1,2-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1C(F)(F)F XXZOEDQFGXTEAD-UHFFFAOYSA-N 0.000 description 1
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PDCBZHHORLHNCZ-UHFFFAOYSA-N 1,4-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(C(F)(F)F)C=C1 PDCBZHHORLHNCZ-UHFFFAOYSA-N 0.000 description 1
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- SRQOBNUBCLPPPH-UHFFFAOYSA-N 1-ethyl-4-phenylbenzene Chemical group C1=CC(CC)=CC=C1C1=CC=CC=C1 SRQOBNUBCLPPPH-UHFFFAOYSA-N 0.000 description 1
- 125000004776 1-fluoroethyl group Chemical group [H]C([H])([H])C([H])(F)* 0.000 description 1
- SLMHHOVQRSSRCV-UHFFFAOYSA-N 2,3-dibromopyridine Chemical compound BrC1=CC=CN=C1Br SLMHHOVQRSSRCV-UHFFFAOYSA-N 0.000 description 1
- PCMMSLVJMKQWMQ-UHFFFAOYSA-N 2,4-dibromopyridine Chemical compound BrC1=CC=NC(Br)=C1 PCMMSLVJMKQWMQ-UHFFFAOYSA-N 0.000 description 1
- GVWNFCUCNAWDNO-UHFFFAOYSA-N 2-(1-benzofuran-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC2=CC=CC=C2O1 GVWNFCUCNAWDNO-UHFFFAOYSA-N 0.000 description 1
- HKSNHZBPIBSVGI-UHFFFAOYSA-N 2-(3,5-dichlorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC(Cl)=CC(Cl)=C1 HKSNHZBPIBSVGI-UHFFFAOYSA-N 0.000 description 1
- AFHLHDNGQLTXFH-UHFFFAOYSA-N 2-(4-carboxypyridin-2-yl)pyridine-3-carboxylic acid Chemical compound N1=C(C(=CC=C1)C(=O)O)C1=NC=CC(=C1)C(=O)O AFHLHDNGQLTXFH-UHFFFAOYSA-N 0.000 description 1
- ATRQECRSCHYSNP-UHFFFAOYSA-N 2-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=CC=N1 ATRQECRSCHYSNP-UHFFFAOYSA-N 0.000 description 1
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 description 1
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 description 1
- OKDGRDCXVWSXDC-UHFFFAOYSA-N 2-chloropyridine Chemical compound ClC1=CC=CC=N1 OKDGRDCXVWSXDC-UHFFFAOYSA-N 0.000 description 1
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- ZFZWZGANFCWADD-UHFFFAOYSA-N 3,4-dibromopyridine Chemical compound BrC1=CC=NC=C1Br ZFZWZGANFCWADD-UHFFFAOYSA-N 0.000 description 1
- ZMPYQKNNUHPTLT-UHFFFAOYSA-N 3,4-dichloropyridine Chemical compound ClC1=CC=NC=C1Cl ZMPYQKNNUHPTLT-UHFFFAOYSA-N 0.000 description 1
- ARRJAONCYUAPJR-UHFFFAOYSA-N 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)quinoline Chemical compound O1C(C)(C)C(C)(C)OB1C1=CN=C(C=CC=C2)C2=C1 ARRJAONCYUAPJR-UHFFFAOYSA-N 0.000 description 1
- NYPYPOZNGOXYSU-UHFFFAOYSA-N 3-bromopyridine Chemical compound BrC1=CC=CN=C1 NYPYPOZNGOXYSU-UHFFFAOYSA-N 0.000 description 1
- PWRBCZZQRRPXAB-UHFFFAOYSA-N 3-chloropyridine Chemical compound ClC1=CC=CN=C1 PWRBCZZQRRPXAB-UHFFFAOYSA-N 0.000 description 1
- GJNOCGLTCQPYAC-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-[3-(trifluoromethyl)phenyl]-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=CC(C(F)(F)F)=C1 GJNOCGLTCQPYAC-UHFFFAOYSA-N 0.000 description 1
- BSDGZUDFPKIYQG-UHFFFAOYSA-N 4-bromopyridine Chemical compound BrC1=CC=NC=C1 BSDGZUDFPKIYQG-UHFFFAOYSA-N 0.000 description 1
- TXNLQUKVUJITMX-UHFFFAOYSA-N 4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine Chemical compound CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1 TXNLQUKVUJITMX-UHFFFAOYSA-N 0.000 description 1
- KNUSKSGBENWYRI-UHFFFAOYSA-N 6-(4-carboxypyridin-2-yl)pyridine-2-carboxylic acid Chemical compound OC(=O)C1=CC=NC(C=2N=C(C=CC=2)C(O)=O)=C1 KNUSKSGBENWYRI-UHFFFAOYSA-N 0.000 description 1
- HYDLFVISOOYNGJ-UHFFFAOYSA-N 6-(4-carboxypyridin-2-yl)pyridine-3-carboxylic acid Chemical compound N1=CC(C(=O)O)=CC=C1C1=CC(C(O)=O)=CC=N1 HYDLFVISOOYNGJ-UHFFFAOYSA-N 0.000 description 1
- DLLMWDJOFJHBEI-UHFFFAOYSA-N 6-(5-carboxypyridin-2-yl)pyridine-2-carboxylic acid Chemical compound N1=CC(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=N1 DLLMWDJOFJHBEI-UHFFFAOYSA-N 0.000 description 1
- DASAXWLMIWDYLQ-UHFFFAOYSA-N 6-(6-carboxypyridin-2-yl)pyridine-2-carboxylic acid Chemical compound OC(=O)C1=CC=CC(C=2N=C(C=CC=2)C(O)=O)=N1 DASAXWLMIWDYLQ-UHFFFAOYSA-N 0.000 description 1
- ZQTILGDVDYWICD-UHFFFAOYSA-N 6-pyridin-2-ylpyridine-2-carboxylic acid Chemical compound OC(=O)C1=CC=CC(C=2N=CC=CC=2)=N1 ZQTILGDVDYWICD-UHFFFAOYSA-N 0.000 description 1
- LWMHPOLRJIRLPN-UHFFFAOYSA-N 6-pyridin-2-ylpyridine-3-carboxylic acid Chemical compound N1=CC(C(=O)O)=CC=C1C1=CC=CC=N1 LWMHPOLRJIRLPN-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DEAKSZYMYJCKPC-UHFFFAOYSA-N ClC=1C(=NC=CC1)Cl.ClC1=CC=NC=C1 Chemical compound ClC=1C(=NC=CC1)Cl.ClC1=CC=NC=C1 DEAKSZYMYJCKPC-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- NMMIHXMBOZYNET-UHFFFAOYSA-N Methyl picolinate Chemical compound COC(=O)C1=CC=CC=N1 NMMIHXMBOZYNET-UHFFFAOYSA-N 0.000 description 1
- OACQMPCZCMHLOM-UHFFFAOYSA-N N1=C(C(=CC=C1)C(=O)O)C1=NC(=CC=C1)C(=O)O.N1=C(C(=CC=C1)C(=O)O)C1=NC=C(C=C1)C(=O)O Chemical compound N1=C(C(=CC=C1)C(=O)O)C1=NC(=CC=C1)C(=O)O.N1=C(C(=CC=C1)C(=O)O)C1=NC=C(C=C1)C(=O)O OACQMPCZCMHLOM-UHFFFAOYSA-N 0.000 description 1
- YINWDJVJLPUQBT-UHFFFAOYSA-N N1=C(C=C(C=C1)C(=O)O)C1=NC=CC(=C1)C(=O)O.[Na].[Na] Chemical compound N1=C(C=C(C=C1)C(=O)O)C1=NC=CC(=C1)C(=O)O.[Na].[Na] YINWDJVJLPUQBT-UHFFFAOYSA-N 0.000 description 1
- HGZPIABIZAYKAD-UHFFFAOYSA-L N1=C(C=C(C=C1)C(=O)[O-])C1=NC=CC(=C1)C(=O)[O-].[Ca+2] Chemical compound N1=C(C=C(C=C1)C(=O)[O-])C1=NC=CC(=C1)C(=O)[O-].[Ca+2] HGZPIABIZAYKAD-UHFFFAOYSA-L 0.000 description 1
- LYMIRAMTHDJMGF-UHFFFAOYSA-H [B+3].[B+3].C(CO)(=O)[O-].C(CO)(=O)[O-].C(CO)(=O)[O-].C(CO)(=O)[O-].C(CO)(=O)[O-].C(CO)(=O)[O-] Chemical compound [B+3].[B+3].C(CO)(=O)[O-].C(CO)(=O)[O-].C(CO)(=O)[O-].C(CO)(=O)[O-].C(CO)(=O)[O-].C(CO)(=O)[O-] LYMIRAMTHDJMGF-UHFFFAOYSA-H 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004802 cyanophenyl group Chemical group 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 125000004914 dipropylamino group Chemical group C(CC)N(CCC)* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000005935 hexyloxycarbonyl group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001148 pentyloxycarbonyl group Chemical group 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- USYCVFFWCMHPPG-UHFFFAOYSA-N tert-butyl 4-sulfanylpiperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCC(S)CC1 USYCVFFWCMHPPG-UHFFFAOYSA-N 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、アリールボラン化合物の製造方法に関する。 The present invention relates to a method for producing an arylborane compound.
アリールボラン化合物の製造方法としては、２，２’−ビピリジンもしくは４，４’−ジ−ｔｅｒｔ−ブチル−２，２’−ビピリジン、イリジウム化合物及びアルコキシボラン化合物から形成されるイリジウム錯体を触媒として用いて、アリール化合物とアルコキシボラン化合物とを反応させる方法が知られている（例えば、非特許文献１参照）。 As a method for producing an arylborane compound, an iridium complex formed from 2,2′-bipyridine or 4,4′-di-tert-butyl-2,2′-bipyridine, an iridium compound and an alkoxyborane compound is used as a catalyst. A method of reacting an aryl compound and an alkoxyborane compound is known (for example, see Non-Patent Document 1).
しかしながら、上記の方法では、触媒であるイリジウム錯体が、反応基質や反応生成物に溶解しやすいため、反応が均一系で行われることになる。その結果、反応後の反応混合物から直接的に錯体を回収することが容易ではなく、錯体を触媒として再使用することができない。 However, in the above method, the iridium complex as the catalyst is easily dissolved in the reaction substrate and the reaction product, so that the reaction is performed in a homogeneous system. As a result, it is not easy to recover the complex directly from the reaction mixture after the reaction, and the complex cannot be reused as a catalyst.
本発明は、前記の問題点に鑑みてなされたものであり、その目的はアリールボラン化合物の工業的に有利な製造方法を提供することにある。 The present invention has been made in view of the above-mentioned problems, and an object thereof is to provide an industrially advantageous method for producing an arylborane compound.
本発明者らは前記課題を解決するため、アリール化合物及びアルコキシボラン化合物を原料とするアリールボラン化合物の製造方法について鋭意検討した。その結果、式（１）で示されるビピリジン化合物、イリジウム化合物及びアルコキシボラン化合物から形成される錯体が、当該製造方法の触媒として用いることができ、しかも反応基質及び目的とする反応生成物に難溶な固体であるため、反応後の反応混合物を不活性ガス雰囲気下で濾過操作するだけで該錯体をろ残として容易に回収でき、そして回収した該錯体を当該製造方法の触媒として再利用できることを見出し、本発明を完成するに至った。 In order to solve the above-mentioned problems, the present inventors diligently studied a method for producing an arylborane compound using an aryl compound and an alkoxyborane compound as raw materials. As a result, the complex formed from the bipyridine compound, the iridium compound and the alkoxyborane compound represented by the formula (1) can be used as a catalyst for the production method and is hardly soluble in the reaction substrate and the target reaction product. The complex can be easily recovered as a filter residue by simply filtering the reaction mixture after the reaction under an inert gas atmosphere, and the recovered complex can be reused as a catalyst for the production method. The headline and the present invention were completed.
即ち本発明は、触媒の存在下にアリール化合物をアルコキシボラン化合物と反応させてアリールボラン化合物を製造する際に、イリジウム化合物、アルコキシボラン化合物及び式（１）で示されるビピリジン化合物から形成される錯体を触媒として用いることを特徴とするアリールボラン化合物の製造方法に関する。 That is, the present invention provides a complex formed from an iridium compound, an alkoxyborane compound and a bipyridine compound represented by the formula (1) when an arylborane compound is produced by reacting an aryl compound with an alkoxyborane compound in the presence of a catalyst. The present invention relates to a method for producing an arylborane compound, characterized in that is used as a catalyst.
式（１）： Formula (1):
（式中、Ｒ１及びＲ２は互いに同一又は異なってそれぞれ水素原子、アルキル基、アラルキル基又はアルキル基で置換されていてもよいアリール基を表す。Ｘ及びＹは互いに同一又は異なってそれぞれ水素原子又はアルカリ金属を表す。ｘ及びｙはそれぞれ０又は１であり、ｘ＋ｙは１又は２である。）
(Wherein R 1 and R 2 are the same or different and each represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group which may be substituted with an alkyl group. X and Y are the same or different from each other and each represents a hydrogen atom. Represents an atom or an alkali metal, x and y are 0 or 1, respectively, and x + y is 1 or 2.)
本発明によれば、触媒である錯体を反応後の反応混合物から不活性ガス雰囲気下での濾過操作により容易に回収でき、且つ回収されたものは触媒として再使用できることから、本発明はアリールボラン化合物の工業的に有利な製造方法である。 According to the present invention, since the complex as a catalyst can be easily recovered from the reaction mixture after the reaction by filtration under an inert gas atmosphere, and the recovered one can be reused as a catalyst. This is an industrially advantageous production method of the compound.
以下本発明を詳細に説明する。
ビピリジン化合物（１）において、式（１）中のＲ１及びＲ２で表されるアルキル基としては、直鎖状、分枝鎖状及び環状のいずれであってもよく、炭素数１〜６の直鎖状又は炭素数３〜６の分枝鎖状のアルキル基及び炭素数４〜６の環状のアルキル基が挙げられる。直鎖状又は分枝鎖状のアルキル基としては、具体的にはメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基等が挙げられ、環状のアルキル基としては、シクロブチル基、シクロヘキシル基、シクロペンチル基等が挙げられる。前記アルキル基のうち、好ましいものはメチル基、エチル基、プロピル基であり、より好ましいものはメチル基である。
The present invention will be described in detail below.
In the bipyridine compound (1), the alkyl group represented by R 1 and R 2 in the formula (1) may be linear, branched or cyclic, and has 1 to 6 carbon atoms. Linear or branched alkyl groups having 3 to 6 carbon atoms and cyclic alkyl groups having 4 to 6 carbon atoms. Specific examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, and a hexyl group. Examples of the cyclic alkyl group include a cyclobutyl group, a cyclohexyl group, and a cyclopentyl group. Of the alkyl groups, preferred are a methyl group, an ethyl group, and a propyl group, and more preferred is a methyl group.
Ｒ１及びＲ２で表されるアラルキル基としては、アリール基を置換基として有するアルキル基が挙げられ、具体的にはベンジル基、メチルベンジル基、フェネチル基、ナフチルメチル基、ジフェニルメチル基等が挙げられる。 Examples of the aralkyl group represented by R 1 and R 2 include an alkyl group having an aryl group as a substituent, and specifically include a benzyl group, a methylbenzyl group, a phenethyl group, a naphthylmethyl group, a diphenylmethyl group, and the like. Can be mentioned.
Ｒ１及びＲ２で表されるアリール基としては、フェニル基、クロロフェニル基などのハロゲノフェニル基、メチルフェニル基等のアルキルフェニル基、ビニルフェニル基等のアルケニルフェニル基、エチニルフェニル基等のアルキニルフェニル基、ビフェニル基等のアリールフェニル基、ベンジルフェニル基等のアラルキルフェニル基、メトキシフェニル基等のアルコキシフェニル基、トリフルオロメチルフェニル基等のフルオロアルキルフェニル基、アセチルフェニル基等のアシルフェニル基、シアノフェニル基及びニトロフェニル基が挙げられる。 Examples of the aryl group represented by R 1 and R 2 include a halogenophenyl group such as a phenyl group and a chlorophenyl group, an alkylphenyl group such as a methylphenyl group, an alkenylphenyl group such as a vinylphenyl group, and an alkynylphenyl such as an ethynylphenyl group. Group, arylphenyl group such as biphenyl group, aralkylphenyl group such as benzylphenyl group, alkoxyphenyl group such as methoxyphenyl group, fluoroalkylphenyl group such as trifluoromethylphenyl group, acylphenyl group such as acetylphenyl group, cyano A phenyl group and a nitrophenyl group are mentioned.
Ｘ及びＹで表されるアルカリ金属としては、リチウム、ナトリウム、カリウム等が挙げられ、ナトリウム及びカリウムが好ましく、ナトリウムがより好ましい。 Examples of the alkali metal represented by X and Y include lithium, sodium, potassium and the like. Sodium and potassium are preferable, and sodium is more preferable.
ビピリジン化合物（１）としては具体的には、例えば２，２’−ビピリジン−３−カルボン酸、２，２’−ビピリジン−４−カルボン酸、２，２’−ビピリジン−５−カルボン酸、２，２’−ビピリジン−６−カルボン酸、２，２’−ビピリジン−３，３’−ジカルボン酸、２，２’−ビピリジン−４，４’−ジカルボン酸、２，２’−ビピリジン−５，５’−ジカルボン酸、２，２’−ビピリジン−６，６’−ジカルボン酸、２，２’−ビピリジン−３，４’−ジカルボン酸、２，２’−ビピリジン−３，５’−ジカルボン酸、２，２’−ビピリジン−３，６’−ジカルボン酸、２，２’−ビピリジン−４，５’−ジカルボン酸、２，２’−ビピリジン−４，６’−ジカルボン酸、２，２’−ビピリジン−５，６’−ジカルボン酸及びそれらのアルカリ金属塩が挙げられ、２，２’−ビピリジン−４，４’−ジカルボン酸が好ましい。 Specific examples of the bipyridine compound (1) include 2,2′-bipyridine-3-carboxylic acid, 2,2′-bipyridine-4-carboxylic acid, 2,2′-bipyridine-5-carboxylic acid, and 2 2,2′-bipyridine-6-carboxylic acid, 2,2′-bipyridine-3,3′-dicarboxylic acid, 2,2′-bipyridine-4,4′-dicarboxylic acid, 2,2′-bipyridine-5, 5'-dicarboxylic acid, 2,2'-bipyridine-6,6'-dicarboxylic acid, 2,2'-bipyridine-3,4'-dicarboxylic acid, 2,2'-bipyridine-3,5'-dicarboxylic acid 2,2′-bipyridine-3,6′-dicarboxylic acid, 2,2′-bipyridine-4,5′-dicarboxylic acid, 2,2′-bipyridine-4,6′-dicarboxylic acid, 2,2 ′ -Bipyridine-5,6'-dicarboxylic acid and it It includes alkali metal salts of, 2,2'-bipyridine-4,4'-dicarboxylic acid.
アリール化合物としては具体的には、例えば式（２）： Specific examples of the aryl compound include, for example, formula (2):
Ｒ３及びＲ４で表されるハロゲン原子としては、塩素原子、臭素原子、沃素原子等が挙げられ、塩素原子が好ましい。 Examples of the halogen atom represented by R 3 and R 4 include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.
Ｒ３及びＲ４で表されるアルキル基としては、直鎖状、分枝鎖状及び環状のいずれであってもよく、炭素数１〜６の直鎖状又は炭素数３〜６の分枝鎖状のアルキル基及び炭素数４〜６の環状のアルキル基が挙げられる。直鎖状又は分枝鎖状のアルキル基としては、具体的にはメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基等が挙げられ、環状のアルキル基としては、シクロブチル基、シクロヘキシル基、シクロペンチル基等が挙げられる。前記アルキル基のうち、好ましいものはメチル基、エチル基、プロピル基であり、より好ましいものはメチル基である。 The alkyl group represented by R 3 and R 4 may be linear, branched, or cyclic, and is a straight chain having 1 to 6 carbon atoms or a branched chain having 3 to 6 carbon atoms. Examples thereof include a chain alkyl group and a cyclic alkyl group having 4 to 6 carbon atoms. Specific examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, and a hexyl group. Examples of the cyclic alkyl group include a cyclobutyl group, a cyclohexyl group, and a cyclopentyl group. Of the alkyl groups, preferred are a methyl group, an ethyl group, and a propyl group, and more preferred is a methyl group.
Ｒ３及びＲ４で表されるアリール基としては、具体的には、例えばフェニル基、ナフチル基、クロロフェニル基などのハロゲノフェニル基、メチルフェニル基等のアルキルフェニル基、ビニルフェニル基等のアルケニルフェニル基、エチニルフェニル基等のアルキニルフェニル基、ビフェニル基等のアリールフェニル基、ベンジルフェニル基等のアラルキルフェニル基、メトキシフェニル基等のアルコキシフェニル基、トリフルオロメチルフェニル基等のフルオロアルキルフェニル基、アセチルフェニル基等のアシルフェニル基、シアノフェニル基及びニトロフェニル基が挙げられる。 Specific examples of the aryl group represented by R 3 and R 4 include a halogenophenyl group such as a phenyl group, a naphthyl group, and a chlorophenyl group, an alkylphenyl group such as a methylphenyl group, and an alkenylphenyl such as a vinylphenyl group. Group, alkynylphenyl group such as ethynylphenyl group, arylphenyl group such as biphenyl group, aralkylphenyl group such as benzylphenyl group, alkoxyphenyl group such as methoxyphenyl group, fluoroalkylphenyl group such as trifluoromethylphenyl group, acetyl Examples thereof include an acylphenyl group such as a phenyl group, a cyanophenyl group, and a nitrophenyl group.
Ｒ３及びＲ４で表されるアラルキル基としては、アリール基を置換基として有するアルキル基が挙げられ、具体的には、ベンジル基、メチルベンジル基、フェネチル基、ナフチルメチル基、ジフェニルメチル基等が挙げられる。 Examples of the aralkyl group represented by R 3 and R 4 include an alkyl group having an aryl group as a substituent, and specifically include a benzyl group, a methylbenzyl group, a phenethyl group, a naphthylmethyl group, a diphenylmethyl group, and the like. Is mentioned.
Ｒ３及びＲ４で表されるアルコキシ基としては、アルキル基、アリール基、アラルキル基等の置換基が酸素原子に結合してなる有機基が挙げられる。好ましくは、当該置換基が炭素数１〜６の直鎖状又炭素数３〜６の分枝鎖状のアルキル基であるアルコキシ基であり、具体的には、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、ｔｅｒｔ−ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基等を例示でき、当該置換基が炭素数１〜４の直鎖又は炭素数３〜４分枝鎖状のアルキル基であるアルコキシ基が好ましい。 Examples of the alkoxy group represented by R 3 and R 4 include an organic group in which a substituent such as an alkyl group, an aryl group, or an aralkyl group is bonded to an oxygen atom. Preferably, the substituent is an alkoxy group which is a linear or branched alkyl group having 1 to 6 carbon atoms, specifically a methoxy group, an ethoxy group, or a propoxy group. , An isopropoxy group, a butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, and the like, and the substituent is a linear or branched chain alkyl group having 1 to 4 carbon atoms. An alkoxy group is preferred.
Ｒ３及びＲ４で表されるアルコキシカルボニル基としては、カルボキシル基の水酸基がアルコキシ基で置換されてなる有機基が挙げられる。好ましくは、アルコキシ基を構成する置換基が炭素数１〜６の直鎖状又炭素数３〜６の分枝鎖状のアルキル基であるアルコキシカルボニル基であり、具体的には、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、イソプロポキシカルボニル基、ブトキシカルボニル基、ｔｅｒｔ−ブトキシカルボニル基、ペンチルオキシカルボニル基、ヘキシルオキシカルボニル基等が挙げられる。特に好ましくは、アルコキシ基を構成する置換基が炭素数１〜４の直鎖又は炭素数３〜４分枝鎖状のアルキル基であるアルコキシカルボニル基である。 Examples of the alkoxycarbonyl group represented by R 3 and R 4 include an organic group in which a hydroxyl group of a carboxyl group is substituted with an alkoxy group. Preferably, the substituent constituting the alkoxy group is an alkoxycarbonyl group which is a linear or branched alkyl group having 1 to 6 carbon atoms, specifically, a methoxycarbonyl group. Ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, tert-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group and the like. Particularly preferred is an alkoxycarbonyl group in which the substituent constituting the alkoxy group is a linear or branched chain alkyl group having 1 to 4 carbon atoms.
Ｒ３及びＲ４で表されるフルオロアルキル基としては、直鎖又は分枝鎖状の脂肪族炭化水素の水素原子の少なくとも１個をフッ素原子に置換したものが挙げられる。好ましくは、メチル基又はエチル基が有する水素原子の１個〜全部をフッ素原子に置換したものであり、具体的には、モノフルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、１−フルオロエチル基、１，２−ジフルオロメチル基、１，１，２−トリフルオロエチル基、１，１，１，２−テトラフルオロエチル基、１，１，２，２−テトラフルオロエチル基、１，１，１，２，２−ペンタフルオロエチル基等が挙げられ、トリフルオロメチル基が好ましい。 Examples of the fluoroalkyl group represented by R 3 and R 4 include those in which at least one hydrogen atom of a linear or branched aliphatic hydrocarbon is substituted with a fluorine atom. Preferably, one to all of the hydrogen atoms of the methyl group or ethyl group are substituted with fluorine atoms, specifically, a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, 1-fluoroethyl Group, 1,2-difluoromethyl group, 1,1,2-trifluoroethyl group, 1,1,1,2-tetrafluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 1,1 1,2,2-pentafluoroethyl group and the like, and a trifluoromethyl group is preferable.
Ｒ３及びＲ４で表される窒素原子上に置換基を有するアミノ基としては具体的には、例えばジメチルアミノ基、ジエチルアミノ基、ジプロピルアミノ基、エチルメチルアミノ基、メチルプロピルアミノ基、アセチルアミノ基、ベンジルオキシカルボニルアミノ基、ｔ−ブトキシカルボニルアミノ基、トリメチルシリルアミノ基等が挙げられる。 Specific examples of the amino group having a substituent on the nitrogen atom represented by R 3 and R 4 include a dimethylamino group, a diethylamino group, a dipropylamino group, an ethylmethylamino group, a methylpropylamino group, and an acetyl group. Examples include an amino group, benzyloxycarbonylamino group, t-butoxycarbonylamino group, and trimethylsilylamino group.
また、Ｒ３とＲ４が末端で互いに結合している場合、アルキル基で置換されていてもよいアルキレン基もしくはｏ−フェニレン基を形成する。Ｒ５及びＲ６とが末端で結合してアルキル基で置換されていてもよいアルキレン基としては、炭素数２〜１０のアルキル基で置換されていてもアルキレン基が挙げられ、具体的には例えば、エチレン基、トリメチレン基、テトラメチレン基、１，２−ジメチルエチレン基、２，２―ジメチルトリメチレン基、１，１，２，２−テトラメチルエチレン基等が挙げられる。 Further, when R 3 and R 4 are bonded to each other at the terminal, an alkylene group or an o-phenylene group which may be substituted with an alkyl group is formed. Examples of the alkylene group which may be bonded to the end of R 5 and R 6 and substituted with an alkyl group include an alkylene group which may be substituted with an alkyl group having 2 to 10 carbon atoms. Specifically, For example, ethylene group, trimethylene group, tetramethylene group, 1,2-dimethylethylene group, 2,2-dimethyltrimethylene group, 1,1,2,2-tetramethylethylene group and the like can be mentioned.
アリール化合物（２）の具体例としては、例えばベンゼン、クロロベンゼン、１，２−ジクロロベンゼン、１，３−ジクロロベンゼン、１，４−ジクロロベンゼン、ブロモベンゼン、１，２−ジブロモベンゼン、１，３−ジブロモベンゼン、１，４−ジブロモベンゼン、メチルベンゼン、１，２−ジメチルベンゼン、１，３−ジメチルベンゼン、１，４−ジメチルベンゼン、１，２−ビス（トリフルオロメチル）ベンゼン、１，３−ビス（トリフルオロメチル）ベンゼン、１，４−ビス（トリフルオロメチル）ベンゼン、メトキシカルボニルベンゼン、メトキシジトリフルオロメチルベンゼン、アセチルベンゼン、ピリジン、２−クロロピリジン、３−クロロピリジン、４−クロロピリジン、２，３−ジクロロピリジン、２，４−ジクロロピリジン、３，４−ジクロロピリジン、２−ブロモピリジン、３−ブロモピリジン、４−ブロモピリジン、２，３−ジブロモピリジン、２，４−ジブロモピリジン、３，４−ジブロモピリジン、２−メチルピリジン、３−メチルピリジン、４−メチルピリジン、２−メトキシカルボニルピリジン、２−メトキシピリジン、２−トリフルオロメチルピリジン、２−アセチルピリジン、キノリン、インドール、ベンゾフラン、ベンゾチオフェンなどが挙げられ、ベンゼン、１，２−ジクロロベンゼン、１，３−ビス（トリフルオロメチル）ベンゼン、２，６−ジクロロピリジン、インドール、ベンゾフラン及びベンゾチオフェンが好ましい。 Specific examples of the aryl compound (2) include, for example, benzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, bromobenzene, 1,2-dibromobenzene, 1,3. -Dibromobenzene, 1,4-dibromobenzene, methylbenzene, 1,2-dimethylbenzene, 1,3-dimethylbenzene, 1,4-dimethylbenzene, 1,2-bis (trifluoromethyl) benzene, 1,3 -Bis (trifluoromethyl) benzene, 1,4-bis (trifluoromethyl) benzene, methoxycarbonylbenzene, methoxyditrifluoromethylbenzene, acetylbenzene, pyridine, 2-chloropyridine, 3-chloropyridine, 4-chloropyridine 2,3-dichloropyridine, 2,4-dichloropi Gin, 3,4-dichloropyridine, 2-bromopyridine, 3-bromopyridine, 4-bromopyridine, 2,3-dibromopyridine, 2,4-dibromopyridine, 3,4-dibromopyridine, 2-methylpyridine, Examples include 3-methylpyridine, 4-methylpyridine, 2-methoxycarbonylpyridine, 2-methoxypyridine, 2-trifluoromethylpyridine, 2-acetylpyridine, quinoline, indole, benzofuran, benzothiophene, and the like. 2-Dichlorobenzene, 1,3-bis (trifluoromethyl) benzene, 2,6-dichloropyridine, indole, benzofuran and benzothiophene are preferred.
イリジウム化合物としては具体的には、例えば式（３）：
［｛Ｉｒ（Ｅ）ｎ｝２（Ｚ）２］ （３）
（式中、Ｅはη４−１，５-シクロオクタジエン、η２−エテン又はη２−シクロオクテンを表す。Ｚはハロゲン原子又は式（４）：
ＲＯ− （４）
（式中、Ｒはアルキル基又はフェニル基を表す。）で示される有機基を示す。ｎは、１又は２であって、Ｅがη４−１，５-シクロオクタジエンであるとき、１を示し、Ｅがη２−エテン又はη２−シクロオクテンであるとき２を示す。）で示される化合物が挙げられる。
Specific examples of the iridium compound include, for example, formula (3):
[{Ir (E) n } 2 (Z) 2 ] (3)
(In the formula, E represents η 4 -1,5-cyclooctadiene, η 2 -ethene or η 2 -cyclooctene. Z represents a halogen atom or formula (4):
RO- (4)
(Wherein R represents an alkyl group or a phenyl group). n is 1 or 2, and represents 1 when E is η 4 -1,5-cyclooctadiene, and 2 when E is η 2 -ethene or η 2 -cyclooctene. ).
式（３）で表される化合物の具体例としては、ジ−μ−クロロ−ビス［（η４−１，５−シクロオクタジエン）イリジウム］、ジ−μ−メトキシ−ビス［（η４−１，５−シクロオクタジエン）イリジウム］、ジ−μ−エトキシ−ビス［（η４−１，５−シクロオクタジエン）イリジウム］、ジ−μ−フェノキシ−ビス［（η４−１，５−シクロオクタジエン）イリジウム］、ジ−μ−クロロ−ビス［ビス（η２−エテン）イリジウム］、ジ−μ−クロロ−ビス［ビス（η２−シクロオクテン）イリジウム］等が挙げられ、好ましくはジ−μ−クロロ−ビス［（η４−１，５−シクロオクタジエン）イリジウム］、ジ−μ−メトキシ−ビス［（η４−１，５−シクロオクタジエン）イリジウム］、ジ−μ−エトキシ−ビス［（η４−１，５−シクロオクタジエン）イリジウム］及びジ−μ−クロロ−ビス［ビス（η２−シクロオクテン）イリジウム］であり、より好ましくはジ−μ−クロロ−ビス［（η４−１，５−シクロオクタジエン）イリジウム］である。 Specific examples of the compound represented by the formula (3) include di-μ-chloro-bis [(η 4 -1,5-cyclooctadiene) iridium], di-μ-methoxy-bis [(η 4 − 1,5-cyclooctadiene) iridium], di-μ-ethoxy-bis [(η 4 -1,5-cyclooctadiene) iridium], di-μ-phenoxy-bis [(η 4 -1,5- Cyclooctadiene) iridium], di-μ-chloro-bis [bis (η 2 -ethene) iridium], di-μ-chloro-bis [bis (η 2 -cyclooctene) iridium], and the like, preferably Di-μ-chloro-bis [(η 4 -1,5-cyclooctadiene) iridium], di-μ-methoxy-bis [(η 4 -1,5-cyclooctadiene) iridium], di-μ- ethoxy - bis [(η 4 -1,5- Black cyclooctadiene) iridium] and di -μ- chloro - bis [bis (eta 2 - a cyclooctene) iridium], more preferably di -μ- chloro - bis [(eta 4-1,5-cyclooctadiene ) Iridium].
アルコキシボラン化合物としては具体的には、例えば式（５）： Specific examples of the alkoxyborane compound include, for example, formula (5):
（式中、Ｒ５及びＲ６は互いに同一又は異なってアルキル基を表すか、又はＲ５及びＲ６とが末端で結合してアルキル基で置換されていてもよいアルキレン基若しくはｏ−フェニレン基を形成する。）で示されるアルコキシボラン化合物（以下、アルコキシボラン化合物（５）という。）又は式（６）：
(In the formula, R 5 and R 6 are the same or different from each other and represent an alkyl group, or R 5 and R 6 are bonded to each other at the terminal and may be substituted with an alkyl group or an o-phenylene group. An alkoxyborane compound (hereinafter referred to as alkoxyborane compound (5)) or formula (6):
（式中、Ｒ５及びＲ６は前記に同じ。）で示されるアルコキシボラン化合物（以下、アルコキシボラン化合物（６）という。）が挙げられる。
(Wherein R 5 and R 6 are the same as above), and an alkoxyborane compound (hereinafter referred to as alkoxyborane compound (6)).
Ｒ５及びＲ６で表されるアルキル基としては、直鎖状、分枝鎖状及び環状のいずれであってもよく、炭素数１〜６の直鎖状又は炭素数３〜６の分枝鎖状のアルキル基及び炭素数４〜６の環状のアルキル基が挙げられる。直鎖状又は分枝鎖状のアルキル基としては、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基等を、環状のアルキル基としては、シクロブチル基、シクロヘキシル基、シクロペンチル基等が挙げられる。前記アルキル基のうち、好ましいものはメチル基、エチル基、プロピル基であり、より好ましいものはメチル基である。 The alkyl group represented by R 5 and R 6 may be linear, branched or cyclic, and is a straight chain having 1 to 6 carbon atoms or a branched chain having 3 to 6 carbon atoms. Examples thereof include a chain alkyl group and a cyclic alkyl group having 4 to 6 carbon atoms. Specific examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, and a hexyl group. Examples of the cyclic alkyl group include a cyclobutyl group, a cyclohexyl group, and a cyclopentyl group. Of the alkyl groups, preferred are a methyl group, an ethyl group, and a propyl group, and more preferred is a methyl group.
Ｒ５及びＲ６とが末端で結合してアルキル基で置換されていてもよいアルキレン基としては、炭素数２〜１０のアルキル基で置換されていてもアルキレン基が挙げられ、具体的には例えば、エチレン基、トリメチレン基、テトラメチレン基、１，２−ジメチルエチレン基、２，２―ジメチルトリメチレン基、１，１，２，２−テトラメチルエチレン基等が挙げられる。 Examples of the alkylene group which may be bonded to the end of R 5 and R 6 and substituted with an alkyl group include an alkylene group which may be substituted with an alkyl group having 2 to 10 carbon atoms. Specifically, For example, ethylene group, trimethylene group, tetramethylene group, 1,2-dimethylethylene group, 2,2-dimethyltrimethylene group, 1,1,2,2-tetramethylethylene group and the like can be mentioned.
アルコキシボラン化合物（５）の具体例としては例えば、式（８）： Specific examples of the alkoxyborane compound (5) include, for example, the formula (8):
アルコキシボラン化合物（６）の具体例としては、例えば式（１０）： Specific examples of the alkoxyborane compound (6) include, for example, the formula (10):
ビピリジン化合物（１）、アリール化合物、イリジウム化合物及びアルコキシボラン化合物は、市販されているものを用いてもよいし、公知の方法に準じて製造したものを用いてもよい。 As the bipyridine compound (1), the aryl compound, the iridium compound, and the alkoxyborane compound, commercially available products may be used, or those prepared according to known methods may be used.
本発明の触媒は、例えば不活性ガス雰囲気下、反応器にビピリジン化合物（１）、アルコキシボラン化合物、イリジウム化合物及び溶媒を所定量仕込み、通常５０〜１５０℃、好ましくは７５〜１００℃で攪拌して錯体を形成して調製する。このようにして形成された錯体は、その分子構造が十分に明らかとなっていないが、ＩＣＰ発光分析よりイリジウム原子に対してビピリジン化合物（１）及びアルコキシボラン化合物が結合しているものと推察される。 The catalyst of the present invention is charged with a predetermined amount of a bipyridine compound (1), an alkoxyborane compound, an iridium compound, and a solvent in an inert gas atmosphere, for example, and usually stirred at 50 to 150 ° C, preferably 75 to 100 ° C. To form a complex. Although the molecular structure of the complex thus formed is not sufficiently clear, it is presumed from the ICP emission analysis that the bipyridine compound (1) and the alkoxyborane compound are bonded to the iridium atom. The
本発明の製造方法の反応を実施するには、触媒を予め調製した後に反応する方法及び反応系内で触媒を調製しながら反応する方法が挙げられる。触媒を予め調製した後に反応する方法としては、例えば反応器にビピリジン化合物（１）、アルコキシボラン化合物、イリジウム化合物及び溶媒を所定量仕込み、攪拌下、通常５０〜１５０℃、好ましくは７５〜１００℃で触媒を調製した後、触媒を含む溶液にアルコキシボラン化合物とアリール化合物（なお、触媒調製時にアルコキシボラン化合物を過剰量用いたときには、アリール化合物だけを加えてもいい。以下同様）とを使用する量の全量を一括して加えるか連続的もしくは断続的に供給しながら、或いはアルコキシボラン化合物とアリール化合物との混合物に触媒を含む溶液を加えて同温度で１〜２０時間反応させる方法が挙げられる。反応系内で触媒を調製しながら反応する方法としては、例えば反応器にビピリジン化合物（１）、アリール化合物、アルコキシボラン化合物、イリジウム化合物及び溶媒を所定量仕込み、攪拌下、通常５０〜１５０℃、好ましくは７５〜１００℃で１〜２０時間反応させる方法が挙げられる。 In order to carry out the reaction of the production method of the present invention, there are a method of reacting after preparing a catalyst in advance and a method of reacting while preparing the catalyst in a reaction system. As a method for reacting after preparing the catalyst in advance, for example, a predetermined amount of bipyridine compound (1), alkoxyborane compound, iridium compound and solvent are charged into the reactor, and usually 50 to 150 ° C., preferably 75 to 100 ° C. with stirring. After preparing the catalyst in step 1, use an alkoxyborane compound and an aryl compound in a solution containing the catalyst (in the case where an excessive amount of the alkoxyborane compound is used during the preparation of the catalyst, only the aryl compound may be added. The same applies hereinafter). Examples include a method in which the total amount is added all at once or continuously or intermittently, or a solution containing a catalyst is added to a mixture of an alkoxyborane compound and an aryl compound and reacted at the same temperature for 1 to 20 hours. . As a method of reacting while preparing a catalyst in the reaction system, for example, a predetermined amount of a bipyridine compound (1), an aryl compound, an alkoxyborane compound, an iridium compound, and a solvent are charged into a reactor, and usually 50 to 150 ° C. with stirring. A method of reacting at 75 to 100 ° C. for 1 to 20 hours is preferable.
触媒調製におけるビピリジン化合物（１）の使用量は、イリジウム化合物中のイリジウム原子１．０モルに対し通常０．１〜１０モルであり、１．０〜２．０モルが好ましい。 The usage-amount of the bipyridine compound (1) in catalyst preparation is 0.1-10 mol normally with respect to 1.0 mol of iridium atoms in an iridium compound, and 1.0-2.0 mol is preferable.
触媒調製におけるイリジウム化合物の使用量は、アルコキシボラン化合物１モルに対して通常０．３３モル以下、好ましくは０．３３〜０．０１モルである。 The amount of the iridium compound used in the catalyst preparation is usually 0.33 mol or less, preferably 0.33 to 0.01 mol, relative to 1 mol of the alkoxyborane compound.
本発明の反応におけるアリール化合物とアルコキシボラン化合物との使用割合は限定されないが、アリール化合物をアルコキシボラン化合物１モルに対して通常０．５〜１００モル、好ましくは０．５〜６０モル使用するのがよい。 The proportion of the aryl compound and alkoxyborane compound used in the reaction of the present invention is not limited, but the aryl compound is usually used in an amount of 0.5 to 100 mol, preferably 0.5 to 60 mol, relative to 1 mol of the alkoxyborane compound. Is good.
本発明の反応及び触媒調製には、溶媒を使用することができる。使用される溶媒としては、例えば、エーテル類、ケトン類及び脂肪族炭化水素類等が挙げられ、これらを１種単独又は２種以上混合して使用できる。 A solvent can be used in the reaction and catalyst preparation of the present invention. Examples of the solvent used include ethers, ketones and aliphatic hydrocarbons, and these can be used singly or in combination of two or more.
エーテル類としては、例えばジメトキシエタン、テトラヒドロフラン、１，４−ジオキ
サン、ジエチルエーテル等が、ケトン類としては、例えば、アセトン、エチルメチルケト
ン等が、脂肪族炭化水素としては、例えばヘキサン、メチルシクロヘキサン、ヘプタン、オクタン、ノナン、デカン等が挙げられる。
Examples of ethers include dimethoxyethane, tetrahydrofuran, 1,4-dioxane, and diethyl ether. Examples of ketones include acetone and ethyl methyl ketone. Examples of aliphatic hydrocarbons include hexane, methylcyclohexane, Examples include heptane, octane, nonane and decane.
溶媒の使用量は特に限定されないが、アリール化合物１重量部に対して、通常０．１〜１００重量部、好ましくは１〜１００重量部である。 Although the usage-amount of a solvent is not specifically limited, It is 0.1-100 weight part normally with respect to 1 weight part of aryl compounds, Preferably it is 1-100 weight part.
触媒である錯体が反応基質及び目的とする反応生成物に難溶な固体であるため、反応終了後の反応混合物は、固体の錯体と液体である反応生成物等とに分離している。そのため、錯体を遠心濾過、加圧濾過、減圧濾過等により容易に反応混合物から回収することができ、不活性ガス雰囲気下で上記操作により回収した錯体はそのまま又は不活性ガス雰囲気下での溶媒による洗浄後、反応に使用することができる。 Since the complex as a catalyst is a solid that is hardly soluble in the reaction substrate and the target reaction product, the reaction mixture after the reaction is separated into a solid complex and a liquid reaction product. Therefore, the complex can be easily recovered from the reaction mixture by centrifugal filtration, pressure filtration, reduced pressure filtration, etc., and the complex recovered by the above operation in an inert gas atmosphere is used as it is or by a solvent in an inert gas atmosphere. After washing, it can be used for the reaction.
触媒である錯体がこのように難溶な固体であるので、反応器内に予め存在させた触媒に、アリール化合物とアルコキシボラン化合物を連続的又は断続的に供給しながら反応を行うと同時に、反応によって生成するアリールボラン化合物を反応器から連続的又は断続的に抜き出す方法で、本発明の製造方法を実施することができる。 Since the complex which is a catalyst is a hardly soluble solid, the reaction is performed while supplying the aryl compound and the alkoxyborane compound continuously or intermittently to the catalyst previously present in the reactor. The production method of the present invention can be carried out by a method of continuously or intermittently extracting the arylborane compound produced by the above process from the reactor.
このようにして得られるアリールボラン化合物は、アリール化合物（２）の芳香環の水素原子がアルコキシボリル基で置換された化合物である。アリールボラン化合物としては具体的には、例えば式（７）： The arylborane compound thus obtained is a compound in which the hydrogen atom of the aromatic ring of the aryl compound (2) is substituted with an alkoxyboryl group. Specific examples of the arylborane compound include, for example, formula (7):
（式中、Ａ、環Ｃ、Ｒ３〜Ｒ６は前記に同じ。ｚは１又は２である。但し、ｚが２の場合は、ＡはＮＨ、酸素原子又は硫黄原子を表し、環Ｃは５員環の芳香環を表し、Ｒ３及びＲ４は水素原子を表す。）で示される化合物（以下、アリールボラン化合物（７）という。）である。
(In the formula, A, ring C and R 3 to R 6 are the same as described above. Z is 1 or 2. However, when z is 2, A represents NH, an oxygen atom or a sulfur atom, and ring C Represents a 5-membered aromatic ring, and R 3 and R 4 represent a hydrogen atom.) (Hereinafter referred to as arylborane compound (7)).
アリールボラン化合物（７）の具体例としては、例えば（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼン、１，２−ジクロロ−４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼン、１，３−ビス（トリフルオロメチル）−５−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼン、２，６−ジクロロ−４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ピリジン、３−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）キノリン、２−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）インドール、２−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゾフラン、２−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゾチオフェンが挙げられる。 Specific examples of the arylborane compound (7) include (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene, 1,2-dichloro-4- (4, 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene, 1,3-bis (trifluoromethyl) -5- (4,4,5,5-tetramethyl-1, 3,2-dioxaborolan-2-yl) benzene, 2,6-dichloro-4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine, 3- (4 , 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) quinoline, 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) Indole, 2- (4,4,5,5-tetrame Le 1,3,2-dioxaborolan-2-yl) benzofuran, 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo thiophene.
反応終了後の反応混合物からは、公知の単離精製手段、例えば濾過、抽出、濃縮、蒸留、再結晶、カラムクロマトグラフィー等の単離操作を組み合わせて目的とするアリールボラン化合物（７）を単離することができる。 From the reaction mixture after completion of the reaction, the desired arylborane compound (7) is obtained by combining known isolation and purification means, for example, isolation operations such as filtration, extraction, concentration, distillation, recrystallization, column chromatography and the like. Can be separated.
以下、実施例により本発明をさらに具体的に説明するが、本発明はそれらの実施例に限定されるものではない。なお、下記の実施例におけるガスクロマトグラフィー（以下、ＧＣという。）分析の条件は次の通りであり、収率はホウ素原子を基準として算出した。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, the conditions of the gas chromatography (henceforth GC) analysis in the following Example are as follows, The yield was computed on the basis of the boron atom.
［ＧＣ分析条件］
カラム；ＤＢ−１７（０．２５μｍ）０．２５ｍｍφ×３０ｍ（Ｊ＆Ｗサイエンティフィック社製）
キャリアガス；ヘリウム １００ｋＰａ
カラム温度；１００℃→（１０℃／分）→２５０℃（５分）
検出器；ＦＩＤ
検出器温度；２５０℃
注入口温度；２５０℃
内部標準物質；４−エチルビフェニル
[GC analysis conditions]
Column: DB-17 (0.25 μm) 0.25 mmφ × 30 m (manufactured by J & W Scientific)
Carrier gas; helium 100 kPa
Column temperature: 100 ° C. → (10 ° C./min)→250° C. (5 min)
Detector; FID
Detector temperature: 250 ° C
Inlet temperature: 250 ° C
Internal standard substance; 4-ethylbiphenyl
実施例１
窒素雰囲気下、ビスピナコレートジボロン２５４ｍｇ（１．０ミリモル）、ジ−μ−クロロ−ビス［（η４−１，５−シクロオクタジエン）イリジウム］１０．１ｍｇ（０．０１５ミリモル）、２，２’−ビピリジン−４，４’−ジカルボン酸７．３ｍｇ（０．０３ミリモル）及びベンゼン５．３５ｍｌ（６０ミリモル）を混合し、８０℃で１２時間加熱撹拌した。反応終了後、反応混合物を窒素雰囲気下で濾過し、ろ残を窒素雰囲気下でベンゼン２０ｍｌ及びヘキサン２０ｍｌで洗浄することにより、ろ残である黒色固体の錯体１０５ｍｇ及びろ洗液を得た。得られたろ洗液をＧＣで定量分析した結果、（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼンが、３４９ｍｇ（収率８６％）含まれていることを確認した。
Example 1
Under a nitrogen atmosphere, 254 mg (1.0 mmol) of bispinacolate diboron, 10.1 mg (0.015 mmol) of di-μ-chloro-bis [(η 4 -1,5-cyclooctadiene) iridium], 2 , 2′-bipyridine-4,4′-dicarboxylic acid (7.3 mg, 0.03 mmol) and benzene (5.35 ml, 60 mmol) were mixed and heated and stirred at 80 ° C. for 12 hours. After completion of the reaction, the reaction mixture was filtered under a nitrogen atmosphere, and the filter residue was washed with 20 ml of benzene and 20 ml of hexane under a nitrogen atmosphere to obtain 105 mg of a black solid complex as a filter residue and a filter wash. As a result of quantitative analysis of the obtained washing solution by GC, 349 mg (yield 86%) of (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene was contained. I confirmed.
実施例２〜７
窒素雰囲気下、ビスピナコレートジボロン７６２ｍｇ（３．０ミリモル）、実施例１において回収した錯体１０５ｍｇ、ベンゼン１６．１ｍｌ（１８０ミリモル）を混合し、８０℃で１２時間加熱撹拌した。反応終了後、反応混合物を窒素雰囲気下で濾過し、ろ残を窒素雰囲気下でベンゼン２０ｍｌ及びヘキサン２０ｍｌで洗浄することにより、黒色固体の錯体及びろ洗液を得た。得られたろ洗液を実施例１と同様にＧＣで定量分析した。同様の操作を６回繰り返して行った結果を以下の表１にまとめて示す。
Examples 2-7
Under a nitrogen atmosphere, 762 mg (3.0 mmol) of bispinacolate diboron, 105 mg of the complex recovered in Example 1 and 16.1 ml (180 mmol) of benzene were mixed and stirred with heating at 80 ° C. for 12 hours. After completion of the reaction, the reaction mixture was filtered under a nitrogen atmosphere, and the residue was washed with 20 ml of benzene and 20 ml of hexane under a nitrogen atmosphere to obtain a black solid complex and a filtrate. The obtained filtrate was quantitatively analyzed by GC as in Example 1. The results obtained by repeating the same operation 6 times are summarized in Table 1 below.
実施例８
実施例１のビスピナコレートジボロン２５４ｍｇ（１．０ミリモル）をピナコールボラン２５６ｍｇ（２．０ミリモル）に代えた以外は実施例１と同様にして反応を実施した結果、黒色固体の錯体をろ残として得た。また（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼンの収率は７８％であった。
Example 8
The reaction was carried out in the same manner as in Example 1 except that 254 mg (1.0 mmol) of bispinacolate diboron in Example 1 was replaced with 256 mg (2.0 mmol) of pinacol borane. Got as the rest. The yield of (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene was 78%.
実施例９
実施例１のジ−μ−クロロ−ビス［（η４−１，５−シクロオクタジエン）イリジウム］１０．１ｍｇ（０．０１５ミリモル）をジ−μ−メトキシ−ビス［（η４−１，５−シクロオクタジエン）イリジウム］９．９ｍｇ（０．０１５ミリモル）に代えた以外は実施例１と同様にして反応を実施した結果、黒色固体の錯体をろ残として得た。また（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼンの収率は７６％であった。
Example 9
10.1 mg (0.015 mmol) of di-μ-chloro-bis [(η 4 -1,5-cyclooctadiene) iridium] of Example 1 was added to di-μ-methoxy-bis [(η 4 -1, 5-Cyclooctadiene) iridium] The reaction was carried out in the same manner as in Example 1 except that 9.9 mg (0.015 mmol) was used. As a result, a black solid complex was obtained as a filter residue. The yield of (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene was 76%.
実施例１０
実施例１の２，２’−ビピリジン−４，４’−ジカルボン酸７．３ｍｇ（０．０３ミリモル）を２，２’−ビピリジン−５，５’−ジカルボン酸７．３ｍｇ（０．０３ミリモル）に代えた以外は実施例１と同様にして反応を実施した結果、黒色固体の錯体をろ残として得た。また（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼンの収率は７８％であった。
Example 10
7.3 mg (0.03 mmol) of 2,2′-bipyridine-4,4′-dicarboxylic acid of Example 1 was converted to 7.3 mg (0.03 mmol) of 2,2′-bipyridine-5,5′-dicarboxylic acid. As a result of carrying out the reaction in the same manner as in Example 1 except that it was changed to), a black solid complex was obtained as a filter residue. The yield of (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene was 78%.
実施例１１
実施例１の２，２’−ビピリジン−４，４’−ジカルボン酸７．３ｍｇ（０．０３ミリモル）を２，２’−ビピリジン−３，３’−ジカルボン酸７．３ｍｇ（０．０３ミリモル）に代えた以外は実施例１と同様にして反応を実施した結果、黒色固体の錯体をろ残として得た。また（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼンの収率は７７％であった。
Example 11
7.3 mg (0.03 mmol) of 2,2′-bipyridine-4,4′-dicarboxylic acid of Example 1 was converted to 7.3 mg (0.03 mmol) of 2,2′-bipyridine-3,3′-dicarboxylic acid. As a result of carrying out the reaction in the same manner as in Example 1 except that it was changed to), a black solid complex was obtained as a filter residue. The yield of (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene was 77%.
実施例１２
窒素雰囲気下、ビスピナコレートジボロン２５４ｍｇ（１．０ミリモル）、ジ−μ−クロロ−ビス［（η４−１，５−シクロオクタジエン）イリジウム］１０．１ｍｇ（０．０１５ミリモル）及び２，２’−ビピリジンー４，４’−ジカルボン酸７．３ｍｇ（０．０３ミリモル）、１，２−ジクロロベンゼン５８８ｍｇ（２．０ミリモル）、メチルシクロヘキサン２ｍｌを混合し、８０℃で１２時間加熱撹拌した。反応後、反応液を窒素雰囲気下で濾過し、ろ残を窒素雰囲気下でメチルシクロヘキサン２０ｍｌで洗浄し、得られたろ洗液を実施例１と同様に分析した結果、１，２−ジクロロ−４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼンが３８８ｍｇ（収率７１％）含まれていることを確認した。上記ろ残は黒色固体の錯体であった。
Example 12
Under a nitrogen atmosphere, 254 mg (1.0 mmol) of bispinacolate diboron, 10.1 mg (0.015 mmol) of di-μ-chloro-bis [(η 4 -1,5-cyclooctadiene) iridium] and 2 , 2′-bipyridine-4,4′-dicarboxylic acid (7.3 mg, 0.03 mmol), 1,2-dichlorobenzene (588 mg, 2.0 mmol) and methylcyclohexane (2 ml) are mixed, and heated and stirred at 80 ° C. for 12 hours. did. After the reaction, the reaction solution was filtered under a nitrogen atmosphere, the residue was washed with 20 ml of methylcyclohexane under a nitrogen atmosphere, and the obtained filtrate was analyzed in the same manner as in Example 1. As a result, 1,2-dichloro-4 It was confirmed that 388 mg (yield 71%) of-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene was contained. The filter residue was a black solid complex.
実施例１３
実施例１２の１，２−ジクロロベンゼン５８８ｍｇ（２．０ミリモル）を１，３−ビス（トリフルオロメチル）ベンゼン４２８ｍｇ（２．０ミリモル）に代えた以外は実施例１２と同様にして反応を実施した結果、黒色固体の錯体をろ残として得た。また１，３−ビス（トリフルオロメチル）−５−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼンの収率は７８％であった。
Example 13
The reaction was conducted in the same manner as in Example 12 except that 588 mg (2.0 mmol) of 1,2-dichlorobenzene of Example 12 was replaced with 428 mg (2.0 mmol) of 1,3-bis (trifluoromethyl) benzene. As a result, a black solid complex was obtained as a filter residue. The yield of 1,3-bis (trifluoromethyl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene was 78%.
実施例１４
実施例１２の１，２−ジクロロベンゼン５８８ｍｇ（２．０ミリモル）を２，６−ジクロロピリジン５９２ｍｇ（２．０ミリモル）に代えた以外は実施例１２と同様にして反応を実施した結果、黒色固体の錯体をろ残として得た。また２，６−ジクロロ−４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ピリジンの収率は７２％であった。
Example 14
The reaction was carried out in the same manner as in Example 12 except that 588 mg (2.0 mmol) of 1,2-dichlorobenzene of Example 12 was replaced with 592 mg (2.0 mmol) of 2,6-dichloropyridine. A solid complex was obtained as a filter residue. The yield of 2,6-dichloro-4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine was 72%.
実施例１５
実施例１２の１，２−ジクロロベンゼン５８８ｍｇ（２．０ミリモル）をベンゾフラン２３６ｍｇ（２．０ミリモル）に代えた以外は実施例１２と同様にして反応を実施した結果、黒色固体の錯体をろ残として得た。また２−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゾフランの収率は６９％であった。
Example 15
As a result of carrying out the reaction in the same manner as in Example 12 except that 588 mg (2.0 mmol) of 1,2-dichlorobenzene of Example 12 was replaced with 236 mg (2.0 mmol) of benzofuran, a black solid complex was filtered. Got as the rest. The yield of 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzofuran was 69%.
実施例１６
実施例１２の１，２−ジクロロベンゼン５８８ｍｇ（２．０ミリモル）をベンゾチオフェン２３６ｍｇ（２．０ミリモル）に代えた以外は実施例１２と同様にして反応を実施した結果、黒色固体の錯体をろ残として得た。また２−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゾチオフェンの収率は６８％であった。
Example 16
As a result of carrying out the reaction in the same manner as in Example 12 except that 588 mg (2.0 mmol) of 1,2-dichlorobenzene of Example 12 was replaced with 236 mg (2.0 mmol) of benzothiophene, a black solid complex was obtained. Obtained as a filter residue. The yield of 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzothiophene was 68%.
実施例１７
実施例１の２，２’−ビピリジン−４，４’−ジカルボン酸７．３ｍｇ（０．０３ミリモル）を２，２’−ビピリジン−４，４’−ジカルボン酸ジナトリウム８．７ｍｇ（０．０３ミリモル）に代えた以外は実施例１と同様にして反応を実施した結果、黒色固体の錯体をろ残として得た。また（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼンの収率は７９％であった。
Example 17
7.3 mg (0.03 mmol) of 2,2′-bipyridine-4,4′-dicarboxylic acid of Example 1 was converted to 8.7 mg (0.03 mmol) of disodium 2,2′-bipyridine-4,4′-dicarboxylic acid. The reaction was carried out in the same manner as in Example 1 except that the amount was changed to 03 mmol). As a result, a black solid complex was obtained as a filter residue. The yield of (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene was 79%.
実施例１８
実施例１２の１，２−ジクロロベンゼン５８８ｍｇ（２．０ミリモル）を安息香酸メチル２７２ｍｇ（２．０ミリモル）に代えた以外は実施例１２と同様に反応を実施した結果、黒色固体の錯体をろ残として得た。また、３−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）安息香酸メチルと４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）安息香酸メチルとの混合物の収率は６２％であり、３−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）安息香酸メチルと４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）安息香酸メチルのモル比は５０：５０（１Ｈ−ＮＭＲによる積分比より算出）であった。
Example 18
As a result of carrying out the reaction in the same manner as in Example 12 except that 588 mg (2.0 mmol) of 1,2-dichlorobenzene of Example 12 was replaced with 272 mg (2.0 mmol) of methyl benzoate, a black solid complex was obtained. Obtained as a filter residue. In addition, methyl 3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate and 4- (4,4,5,5-tetramethyl-1,3, The yield of the mixture with methyl 2-dioxaborolan-2-yl) benzoate is 62% and 3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate The molar ratio of methyl acetate to methyl 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate is 50:50 (calculated from the integral ratio by 1 H-NMR) Met.
実施例１９
実施例１２の１，２−ジクロロベンゼン５８８ｍｇ（２．０ミリモル）をトリフルオロメチルベンゼン２９２ｍｇ（２．０ミリモル）に代えた以外は実施例１２と同様に反応を実施した結果、黒色固体の錯体をろ残として得た。また、１−トリフルオロメチル−３−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼンと１−トリフルオロメチル−４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼンとの混合物の収率６８％であり、１−トリフルオロメチル−３−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼンと１−トリフルオロメチル−４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼンのモル比は６５：３５（１Ｈ−ＮＭＲによる積分比より算出）であった。
Example 19
As a result of carrying out the reaction in the same manner as in Example 12 except that 588 mg (2.0 mmol) of 1,2-dichlorobenzene of Example 12 was replaced with 292 mg (2.0 mmol) of trifluoromethylbenzene, a black solid complex was obtained. Was obtained as a residue. Also, 1-trifluoromethyl-3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene and 1-trifluoromethyl-4- (4,4,5 , 5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene with a yield of 68%, 1-trifluoromethyl-3- (4,4,5,5-tetramethyl- Molar ratio of 1,3,2-dioxaborolan-2-yl) benzene to 1-trifluoromethyl-4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene Was 65:35 (calculated from the integration ratio by 1 H-NMR).
実施例２０
実施例１の２，２’−ビピリジン−４，４’−ジカルボン酸７．３ｍｇ（０．０３ミリモル）を２，２’−ビピリジン−４−カルボン酸６．０ｍｇ（０．０３ミリモル）に代えた以外は、実施例１と同様に反応を実施した結果、黒色固体の錯体をろ残として得た。また、（４，４，５，５，―テトラメチル―１，３，２―ジオキサボロラン―２−イル）ベンゼンの収率は８０％であった。
Example 20
The 7.3 mg (0.03 mmol) of 2,2′-bipyridine-4,4′-dicarboxylic acid in Example 1 was replaced with 6.0 mg (0.03 mmol) of 2,2′-bipyridine-4-carboxylic acid. Except for the above, the reaction was carried out in the same manner as in Example 1, and as a result, a black solid complex was obtained as a filter residue. The yield of (4,4,5,5, -tetramethyl-1,3,2-dioxaborolan-2-yl) benzene was 80%.
実施例２１
反応温度を１５０℃に変更した以外は、実施例１と同様に反応を実施した結果、黒色の錯体固体をろ残として得た。（４，４，５，５，―テトラメチル―１，３，２―ジオキサボロラン―２−イル）ベンゼンの収率は８３％であった。
Example 21
As a result of carrying out the reaction in the same manner as in Example 1 except that the reaction temperature was changed to 150 ° C., a black complex solid was obtained as a filter residue. The yield of (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene was 83%.
実施例２２
窒素雰囲気下、ビスピナコレートジボロン３０５ｍｇ（１．２ミリモル）、ジ−μ−クロロ−ビス［（η４−１，５−シクロオクタジエン）イリジウム］１０．１ｍｇ（０．０１５ミリモル）及び２，２’−ビピリジンー４，４’−ジカルボン酸７．３ｍｇ（０．０３ミリモル）、メチルシクロヘキサン１ｍｌを混合し８０℃で５分間加熱撹拌した。さらに１，２−ジクロロベンゼン５８８ｍｇ（２．０ミリモル）及びメチルシクロヘキサン２ｍｌを加え、８０℃で１２時間加熱撹拌した。反応後、反応液を窒素雰囲気下で濾過し、ろ残をメチルシクロヘキサン２０ｍｌで洗浄し、得られたろ洗液を実施例１と同様に分析した結果、１，２−ジクロロ−４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼンが４４３ｍｇ（収率８１％）含まれていることを確認した。上記ろ残は黒色固体の錯体であった。
Example 22
Under a nitrogen atmosphere, 305 mg (1.2 mmol) of bispinacolate diboron, 10.1 mg (0.015 mmol) of di-μ-chloro-bis [(η 4 -1,5-cyclooctadiene) iridium] and 2 , 2′-bipyridine-4,4′-dicarboxylic acid (7.3 mg, 0.03 mmol) and methylcyclohexane (1 ml) were mixed and stirred at 80 ° C. for 5 minutes. Further, 588 mg (2.0 mmol) of 1,2-dichlorobenzene and 2 ml of methylcyclohexane were added, and the mixture was heated and stirred at 80 ° C. for 12 hours. After the reaction, the reaction solution was filtered under a nitrogen atmosphere, the residue was washed with 20 ml of methylcyclohexane, and the obtained filtrate was analyzed in the same manner as in Example 1. As a result, 1,2-dichloro-4- (4, It was confirmed that 443 mg (yield 81%) of 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene was contained. The filter residue was a black solid complex.
実施例２３
実施例２２の１，２−ジクロロベンゼン５８８ｍｇ（２．０ミリモル）を安息香酸メチル２７２ｍｇ（２．０ミリモル）に代えた以外は実施例２２と同様に反応を実施した結果、黒色固体の錯体をろ残として得た。また、３−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）安息香酸メチルと４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）安息香酸メチルとの混合物の収率は７６％であり、３−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）安息香酸メチルと４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）安息香酸メチルのモル比は５０：５０（１Ｈ−ＮＭＲによる積分比より算出）であった。
Example 23
As a result of carrying out the reaction in the same manner as in Example 22 except that 588 mg (2.0 mmol) of 1,2-dichlorobenzene of Example 22 was replaced with 272 mg (2.0 mmol) of methyl benzoate, a black solid complex was obtained. Obtained as a filter residue. In addition, methyl 3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate and 4- (4,4,5,5-tetramethyl-1,3, The yield of the mixture with methyl 2-dioxaborolan-2-yl) benzoate is 76% and 3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate The molar ratio of methyl acetate to methyl 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate is 50:50 (calculated from the integral ratio by 1 H-NMR) Met.
実施例２４
実施例２２の１，２−ジクロロベンゼン５８８ｍｇ（２．０ミリモル）を１，３−ビス（トリフルオロメチル）ベンゼン４２８ｍｇ（２．０ミリモル）に代えた以外は実施例２２と同様にして反応を実施した結果、黒色固体の錯体をろ残として得た。また１，３−ビス（トリフルオロメチル）−５−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼンの収率は９５％であった。
Example 24
The reaction was conducted in the same manner as in Example 22 except that 588 mg (2.0 mmol) of 1,2-dichlorobenzene of Example 22 was replaced with 428 mg (2.0 mmol) of 1,3-bis (trifluoromethyl) benzene. As a result, a black solid complex was obtained as a filter residue. The yield of 1,3-bis (trifluoromethyl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene was 95%.
実施例２５
実施例２２の１，２−ジクロロベンゼン５８８ｍｇ（２．０ミリモル）を２，６−ジクロロピリジン５９２ｍｇ（２．０ミリモル）に代えた以外は実施例２２と同様にして反応を実施した結果、黒色固体の錯体をろ残として得た。また２，６−ジクロロ−４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ピリジンの収率は８４％であった。
Example 25
The reaction was carried out in the same manner as in Example 22 except that 588 mg (2.0 mmol) of 1,2-dichlorobenzene of Example 22 was replaced with 592 mg (2.0 mmol) of 2,6-dichloropyridine. A solid complex was obtained as a filter residue. The yield of 2,6-dichloro-4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine was 84%.
実施例２６
実施例２２の１，２−ジクロロベンゼン５８８ｍｇ（２．０ミリモル）をベンゾチオフェン２３６ｍｇ（２．０ミリモル）に代えた以外は実施例２２と同様にして反応を実施した結果、黒色固体の錯体をろ残として得た。また２−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゾチオフェンの収率は８６％であった。
Example 26
The reaction was carried out in the same manner as in Example 22 except that 588 mg (2.0 mmol) of 1,2-dichlorobenzene in Example 22 was replaced with 236 mg (2.0 mmol) of benzothiophene. Obtained as a filter residue. The yield of 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzothiophene was 86%.
実施例２７
窒素雰囲気下、ビスピナコレートジボロン１．０２ｇ（４．０ミリモル）、ジ−μ−クロロ−ビス［（η４−１，５−シクロオクタジエン）イリジウム］６．７ｍｇ（０．０１ミリモル）、２，２’−ビピリジン−４，４’−ジカルボン酸４．９ｍｇ（０．０２ミリモル）及びベンゼン２１．４ｍｌ（２４０ミリモル）を混合し、８０℃で１２時間加熱撹拌した。反応終了後、反応混合物を窒素雰囲気下で濾過し、ろ残を窒素雰囲気下でベンゼン２０ｍｌで洗浄した。得られたろ洗液をＧＣで定量分析した結果、（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼンが、１．４８ｇ（収率９１％）含まれていることを確認した。上記ろ残は黒色固体の錯体であった。
Example 27
Under a nitrogen atmosphere, 1.02 g (4.0 mmol) of bispinacolate diboron, 6.7 mg (0.01 mmol) of di-μ-chloro-bis [(η 4 -1,5-cyclooctadiene) iridium] , 2,2′-bipyridine-4,4′-dicarboxylic acid (4.9 mg, 0.02 mmol) and benzene (21.4 ml, 240 mmol) were mixed and stirred with heating at 80 ° C. for 12 hours. After completion of the reaction, the reaction mixture was filtered under a nitrogen atmosphere, and the residue was washed with 20 ml of benzene under a nitrogen atmosphere. As a result of quantitative analysis of the obtained filter washing by GC, 1.48 g (yield 91%) of (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene was contained. It was confirmed that The filter residue was a black solid complex.
実施例２８
窒素雰囲気下、ビスピナコレートジボロン２．０３ｇ（８．０ミリモル）、ジ−μ−クロロ−ビス［（η４−１，５−シクロオクタジエン）イリジウム］８０６ｍｇ（１．２ミリモル）、２，２’−ビピリジン−４，４’−ジカルボン酸５８６ｍｇ（２．４ミリモル）及びベンゼン２１．４ｍｌを混合し、８０℃で４時間加熱撹拌した。反応終了後、反応混合物を窒素雰囲気下で濾過し、ろ残を窒素雰囲気下でベンゼン２０ｍｌ及びヘキサン１０ｍｌで洗浄した。得られたろ残を減圧下で乾燥して、黒色固体である錯体１．５８ｇを得た。
Example 28
Under a nitrogen atmosphere, 2.03 g (8.0 mmol) of bispinacolate diboron, 806 mg (1.2 mmol) of di-μ-chloro-bis [(η 4 -1,5-cyclooctadiene) iridium], 2 , 2′-bipyridine-4,4′-dicarboxylic acid (586 mg, 2.4 mmol) and benzene (21.4 ml) were mixed and heated and stirred at 80 ° C. for 4 hours. After completion of the reaction, the reaction mixture was filtered under a nitrogen atmosphere, and the residue was washed with 20 ml of benzene and 10 ml of hexane under a nitrogen atmosphere. The obtained filter residue was dried under reduced pressure to obtain 1.58 g of a black solid complex.
実施例２９
ビスピナコレートジボロン２５４ｍｇ（１．０ミリモル）をベンゼン５ｍｌに溶解させシリンジに仕込み、シリンジポンプを用いて０．２ミリモル／ｈｒの速度で、実施例２８で得られた黒色固体の錯体１７０ｍｇを充填した金属製カラムに８０℃で流通させた。流通後にベンゼン約６ｍｌを用いて１．０ｍｌ／ｈｒの速度で金属製カラムを洗浄し、流出液をガスクロマトグラフィーで分析した。その結果、（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼンの収率は８７％であった。
Example 29
Dissolve 254 mg (1.0 mmol) of bispinacholate diboron in 5 ml of benzene, charge into a syringe, and use 170 ml of the black solid complex obtained in Example 28 at a rate of 0.2 mmol / hr using a syringe pump. It was made to distribute | circulate at 80 degreeC to the metal column with which it filled. After circulation, about 6 ml of benzene was used to wash the metal column at a rate of 1.0 ml / hr, and the effluent was analyzed by gas chromatography. As a result, the yield of (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene was 87%.
実施例３０
ビスピナコレートジボロン２５４ｍｇ（１．０ミリモル）と１，２−ジクロロベンゼン２９４ｍｇ（２．０ミリモル）をメチルシクロヘキサン５ｍｌに溶解させシリンジに仕込み、シリンジポンプを用いて０．１ミリモル／ｈｒの速度で、実施例２８で得られた黒色固体の錯体１７０ｍｇを充填した金属製カラムに８０℃で流通させた。流通後にメチルシクロヘキサン約６ｍｌを用いて１．０ｍｌ／ｈｒの速度で金属製カラムを洗浄し、流出液をガスクロマトグラフィーで分析した。その結果、１，２−ジクロロ−４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼンの収率は８２％であった。
Example 30
Bispinacolate diboron (254 mg, 1.0 mmol) and 1,2-dichlorobenzene (294 mg, 2.0 mmol) were dissolved in 5 ml of methylcyclohexane and charged into a syringe. The rate was 0.1 mmol / hr using a syringe pump. Then, it was circulated at 80 ° C. through a metal column packed with 170 mg of the black solid complex obtained in Example 28. After distribution, the metal column was washed with about 6 ml of methylcyclohexane at a rate of 1.0 ml / hr, and the effluent was analyzed by gas chromatography. As a result, the yield of 1,2-dichloro-4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene was 82%.
実施例３１
１，２−ジクロロベンゼン２９４ｍｇ（２．０ミリモル）を１，３−ジクロロベンゼン２９４ｍｇ（２．０ミリモル）に、流速０．１ミリモル／ｈｒを０．２ミリモル／ｈｒに変えた以外は実施例３０と同様に実施した。１，３−ジクロロ−５−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼンの収率は６６％であった。
Example 31
Example except that 294 mg (2.0 mmol) of 1,2-dichlorobenzene was changed to 294 mg (2.0 mmol) of 1,3-dichlorobenzene and the flow rate of 0.1 mmol / hr was changed to 0.2 mmol / hr. It carried out like 30. The yield of 1,3-dichloro-5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene was 66%.
実施例３２
１，２−ジクロロベンゼン２９４ｍｇ（２．０ミリモル）を１，３−ビストリフルオロメチルベンゼン４２８ｍｇ（２．０ミリモル）に、流速０．１ミリモル／ｈｒを０．２ミリモル／ｈｒに変えた以外は実施例３０と同様に実施した。１，３−ビストリフルオロメチル−５−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼンの収率は９３％であった。
Example 32
294 mg (2.0 mmol) of 1,2-dichlorobenzene was changed to 428 mg (2.0 mmol) of 1,3-bistrifluoromethylbenzene, and the flow rate was changed from 0.1 mmol / hr to 0.2 mmol / hr. The same operation as in Example 30 was performed. The yield of 1,3-bistrifluoromethyl-5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene was 93%.
比較例１
実施例１の２，２’−ビピリジン−４，４’−ジカルボン酸７．３ｍｇ（０．０３ミリモル）を２，２’−ビピリジン−４，４’−ジカルボン酸カルシウム８．５ｍｇ（０．０３ミリモル）に代えた以外は実施例１と同様にして反応を実施した結果、黒色の錯体をろ残として得た。また（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼンの収率は１％以下であった。
Comparative Example 1
7.3 mg (0.03 mmol) of 2,2′-bipyridine-4,4′-dicarboxylic acid of Example 1 was converted to 8.5 mg (0.03 mmol) of calcium 2,2′-bipyridine-4,4′-dicarboxylate. As a result of carrying out the reaction in the same manner as in Example 1 except that it was changed to (mmol), a black complex was obtained as a filter residue. The yield of (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene was 1% or less.
Claims (4)
式（１）：
Formula (1):
［｛Ｉｒ（Ｅ）ｎ｝２（Ｚ）２］ （３）
（式中、Ｅはη４−１，５-シクロオクタジエン、η２−エテン又はη２−シクロオクテンを示す。Ｚはハロゲン原子又は式（４）：
ＲＯ− （４）
（式中、Ｒはアルキル基又はフェニル基を示す。）で表される有機基を示す。ｎは、１又は２であって、Ｅがη４−１，５-シクロオクタジエンであるとき、１を示し、Ｅがη２−エテン又はη２−シクロオクテンであるとき２を示す。）で示される化合物であり、アリール化合物と反応させるアルコキシボラン化合物及び触媒調製に用いられるアルコキシボラン化合物が、式（５）：
[{Ir (E) n } 2 (Z) 2 ] (3)
(Wherein, E is eta 4-1,5-cyclooctadiene, eta 2 - ethene or eta 2 - .Z showing a cyclooctene halogen atom or the formula (4):
RO- (4)
(In the formula, R represents an alkyl group or a phenyl group). n is 1 or 2, and represents 1 when E is η 4 -1,5-cyclooctadiene, and 2 when E is η 2 -ethene or η 2 -cyclooctene. And an alkoxyborane compound to be reacted with an aryl compound and an alkoxyborane compound used for catalyst preparation are represented by the formula (5):
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