JP6444054B2 - Method for producing organoboron compound - Google Patents
Method for producing organoboron compound Download PDFInfo
- Publication number
- JP6444054B2 JP6444054B2 JP2014095207A JP2014095207A JP6444054B2 JP 6444054 B2 JP6444054 B2 JP 6444054B2 JP 2014095207 A JP2014095207 A JP 2014095207A JP 2014095207 A JP2014095207 A JP 2014095207A JP 6444054 B2 JP6444054 B2 JP 6444054B2
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- group
- carbon atoms
- bromide
- general formula
- ring
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 32
- -1 sodium alkoxide Chemical class 0.000 claims description 328
- 125000004432 carbon atom Chemical group C* 0.000 claims description 140
- 238000006243 chemical reaction Methods 0.000 claims description 62
- 125000001424 substituent group Chemical group 0.000 claims description 45
- 125000000217 alkyl group Chemical group 0.000 claims description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 31
- 125000003118 aryl group Chemical group 0.000 claims description 29
- 125000000623 heterocyclic group Chemical group 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 19
- 125000003342 alkenyl group Chemical group 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical group COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 15
- 125000003545 alkoxy group Chemical group 0.000 claims description 13
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 12
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 12
- 125000001153 fluoro group Chemical group F* 0.000 claims description 11
- 229910052740 iodine Chemical group 0.000 claims description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 10
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 8
- 150000002896 organic halogen compounds Chemical class 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 125000004434 sulfur atom Chemical group 0.000 claims description 8
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 7
- 125000005115 alkyl carbamoyl group Chemical group 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 125000003282 alkyl amino group Chemical group 0.000 claims description 5
- 125000002618 bicyclic heterocycle group Chemical group 0.000 claims description 5
- 125000002950 monocyclic group Chemical group 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 230000005494 condensation Effects 0.000 claims 2
- 238000009833 condensation Methods 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000000047 product Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 21
- 230000000704 physical effect Effects 0.000 description 21
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 238000004817 gas chromatography Methods 0.000 description 17
- 239000007858 starting material Substances 0.000 description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 14
- 125000005915 C6-C14 aryl group Chemical group 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 150000001502 aryl halides Chemical class 0.000 description 12
- 125000005842 heteroatom Chemical group 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 12
- VFIKPDSQDNROGM-UHFFFAOYSA-N 2-(4-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound C1=CC(OC)=CC=C1B1OC(C)(C)C(C)(C)O1 VFIKPDSQDNROGM-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 9
- 229910052796 boron Inorganic materials 0.000 description 9
- 125000004122 cyclic group Chemical group 0.000 description 9
- 229910052736 halogen Inorganic materials 0.000 description 9
- 150000002367 halogens Chemical class 0.000 description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 9
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 9
- 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 description 8
- 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 8
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 238000006467 substitution reaction Methods 0.000 description 8
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 7
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- 125000001624 naphthyl group Chemical group 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- 0 *N(C1C=C2)C=CC1C=C2Br Chemical compound *N(C1C=C2)C=CC1C=C2Br 0.000 description 6
- 125000006017 1-propenyl group Chemical group 0.000 description 6
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 6
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 125000006039 1-hexenyl group Chemical group 0.000 description 5
- 125000006023 1-pentenyl group Chemical group 0.000 description 5
- 125000006029 2-methyl-2-butenyl group Chemical group 0.000 description 5
- 125000006049 2-methyl-2-pentenyl group Chemical group 0.000 description 5
- 125000006024 2-pentenyl group Chemical group 0.000 description 5
- 125000006041 3-hexenyl group Chemical group 0.000 description 5
- 125000006043 5-hexenyl group Chemical group 0.000 description 5
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 5
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 5
- 125000005244 neohexyl group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 4
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 0.000 description 4
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 4
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 4
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000006040 2-hexenyl group Chemical group 0.000 description 4
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 4
- 125000005916 2-methylpentyl group Chemical group 0.000 description 4
- WMPPDTMATNBGJN-UHFFFAOYSA-N 2-phenylethylbromide Chemical compound BrCCC1=CC=CC=C1 WMPPDTMATNBGJN-UHFFFAOYSA-N 0.000 description 4
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 4
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 4
- 125000000474 3-butynyl group Chemical group [H]C#CC([H])([H])C([H])([H])* 0.000 description 4
- 125000003320 C2-C6 alkenyloxy group Chemical group 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 4
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- 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 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- 125000006035 1,2-dimethyl-2-propenyl group Chemical group 0.000 description 3
- AUIINENVMPWGQF-UHFFFAOYSA-N 1-(4-methoxyphenyl)-4-nitrobenzene Chemical group C1=CC(OC)=CC=C1C1=CC=C([N+]([O-])=O)C=C1 AUIINENVMPWGQF-UHFFFAOYSA-N 0.000 description 3
- SNGQJSWDDLYWSU-UHFFFAOYSA-N 2-(2-but-3-enylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OB(OC1(C)C)c1ccccc1CCC=C SNGQJSWDDLYWSU-UHFFFAOYSA-N 0.000 description 3
- XMZQWZJMTBCUFT-UHFFFAOYSA-N 3-bromopropylbenzene Chemical compound BrCCCC1=CC=CC=C1 XMZQWZJMTBCUFT-UHFFFAOYSA-N 0.000 description 3
- 125000005917 3-methylpentyl group Chemical group 0.000 description 3
- LVLQNRWCBBIVHR-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-(2-phenylethyl)-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1CCC1=CC=CC=C1 LVLQNRWCBBIVHR-UHFFFAOYSA-N 0.000 description 3
- 150000001347 alkyl bromides Chemical class 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 150000001499 aryl bromides Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 3
- ARMSAQNLTKGMGM-UHFFFAOYSA-N dimethyl-phenyl-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)silane Chemical compound O1C(C)(C)C(C)(C)OB1[Si](C)(C)C1=CC=CC=C1 ARMSAQNLTKGMGM-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000003387 indolinyl group Chemical group N1(CCC2=CC=CC=C12)* 0.000 description 3
- 125000001041 indolyl group Chemical group 0.000 description 3
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 3
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 3
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000005394 methallyl group Chemical group 0.000 description 3
- 125000002911 monocyclic heterocycle group Chemical group 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- RCOSUMRTSQULBK-UHFFFAOYSA-N sodium;propan-1-olate Chemical compound [Na+].CCC[O-] RCOSUMRTSQULBK-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 description 2
- SYSZENVIJHPFNL-UHFFFAOYSA-N (alpha-D-mannosyl)7-beta-D-mannosyl-diacetylchitobiosyl-L-asparagine, isoform B (protein) Chemical compound COC1=CC=C(I)C=C1 SYSZENVIJHPFNL-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- XMWJLKOCNKJERQ-UHFFFAOYSA-N 1-bromoanthracene Chemical compound C1=CC=C2C=C3C(Br)=CC=CC3=CC2=C1 XMWJLKOCNKJERQ-UHFFFAOYSA-N 0.000 description 2
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 2
- BKPFTDPOCSONMX-UHFFFAOYSA-N 1-iodopent-1-ene Chemical compound CCCC=CI BKPFTDPOCSONMX-UHFFFAOYSA-N 0.000 description 2
- URVWKTROBMKSAQ-UHFFFAOYSA-N 2-bromo-3-methylbut-1-ene Chemical compound CC(C)C(Br)=C URVWKTROBMKSAQ-UHFFFAOYSA-N 0.000 description 2
- WSFSJXBURLJOFD-UHFFFAOYSA-N 2-bromopropan-2-ylbenzene Chemical compound CC(C)(Br)C1=CC=CC=C1 WSFSJXBURLJOFD-UHFFFAOYSA-N 0.000 description 2
- NAMYKGVDVNBCFQ-UHFFFAOYSA-N 2-bromopropane Chemical compound CC(C)Br NAMYKGVDVNBCFQ-UHFFFAOYSA-N 0.000 description 2
- JUPBFIYJUCWJCT-UHFFFAOYSA-N 2-iodopentane Chemical compound CCCC(C)I JUPBFIYJUCWJCT-UHFFFAOYSA-N 0.000 description 2
- 125000006022 2-methyl-2-propenyl group Chemical group 0.000 description 2
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical group C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- 125000005336 allyloxy group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 2
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 2
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- ZPTVNYMJQHSSEA-UHFFFAOYSA-N Cc(cc1)ccc1[N+]([O-])=O Chemical compound Cc(cc1)ccc1[N+]([O-])=O ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 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 1
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- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=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
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- DXVOSTCYXXRQEW-UHFFFAOYSA-N iodocyclobutane Chemical compound IC1CCC1 DXVOSTCYXXRQEW-UHFFFAOYSA-N 0.000 description 1
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- PCEBAZIVZVIQEO-UHFFFAOYSA-N iodocyclopentane Chemical compound IC1CCCC1 PCEBAZIVZVIQEO-UHFFFAOYSA-N 0.000 description 1
- VLODBNNWEWTQJX-UHFFFAOYSA-N iodocyclopropane Chemical compound IC1CC1 VLODBNNWEWTQJX-UHFFFAOYSA-N 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
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- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- XJTQJERLRPWUGL-UHFFFAOYSA-N iodomethylbenzene Chemical compound ICC1=CC=CC=C1 XJTQJERLRPWUGL-UHFFFAOYSA-N 0.000 description 1
- 125000005929 isobutyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])OC(*)=O 0.000 description 1
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- 125000005921 isopentoxy group Chemical group 0.000 description 1
- 125000005932 isopentyloxycarbonyl group Chemical group 0.000 description 1
- FMKOJHQHASLBPH-UHFFFAOYSA-N isopropyl iodide Chemical compound CC(C)I FMKOJHQHASLBPH-UHFFFAOYSA-N 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical group C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 125000003588 lysine group Chemical group [H]N([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(N([H])[H])C(*)=O 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000003136 n-heptyl 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])* 0.000 description 1
- 125000001298 n-hexoxy 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
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 1
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- 230000000269 nucleophilic effect Effects 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
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- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005327 perimidinyl group Chemical group N1C(=NC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- RDOWQLZANAYVLL-UHFFFAOYSA-N phenanthridine Chemical group C1=CC=C2C3=CC=CC=C3C=NC2=C1 RDOWQLZANAYVLL-UHFFFAOYSA-N 0.000 description 1
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- GJSGGHOYGKMUPT-UHFFFAOYSA-N phenoxathiine Chemical group C1=CC=C2OC3=CC=CC=C3SC2=C1 GJSGGHOYGKMUPT-UHFFFAOYSA-N 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical group C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
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- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 125000004585 polycyclic heterocycle group Chemical group 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- ZRLVQFQTCMUIRM-UHFFFAOYSA-N potassium;2-methylbutan-2-olate Chemical compound [K+].CCC(C)(C)[O-] ZRLVQFQTCMUIRM-UHFFFAOYSA-N 0.000 description 1
- CBMSDILKECEMOT-UHFFFAOYSA-N potassium;2-methylpropan-1-olate Chemical compound [K+].CC(C)C[O-] CBMSDILKECEMOT-UHFFFAOYSA-N 0.000 description 1
- ZUPDNLCLXSWMAE-UHFFFAOYSA-N potassium;butan-2-olate Chemical compound [K+].CCC(C)[O-] ZUPDNLCLXSWMAE-UHFFFAOYSA-N 0.000 description 1
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 1
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical group N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
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- 125000003072 pyrazolidinyl group Chemical group 0.000 description 1
- 125000002755 pyrazolinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
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- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
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- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- JYCDILBEUUCCQD-UHFFFAOYSA-N sodium;2-methylpropan-1-olate Chemical compound [Na+].CC(C)C[O-] JYCDILBEUUCCQD-UHFFFAOYSA-N 0.000 description 1
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- RKSOPLXZQNSWAS-UHFFFAOYSA-N tert-butyl bromide Chemical compound CC(C)(C)Br RKSOPLXZQNSWAS-UHFFFAOYSA-N 0.000 description 1
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- GVIJJXMXTUZIOD-UHFFFAOYSA-N thianthrene Chemical group C1=CC=C2SC3=CC=CC=C3SC2=C1 GVIJJXMXTUZIOD-UHFFFAOYSA-N 0.000 description 1
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- AIFRHYZBTHREPW-UHFFFAOYSA-N β-carboline Chemical group N1=CC=C2C3=CC=CC=C3NC2=C1 AIFRHYZBTHREPW-UHFFFAOYSA-N 0.000 description 1
Images
Description
本発明は、有機ハロゲン化合物のハロゲノ基をピナコールボリル基に由来するホウ素に置換して、有機ホウ素化合物を製造する方法に関する。 The present invention relates to a method for producing an organic boron compound by replacing a halogeno group of an organic halogen compound with boron derived from a pinacolboryl group.
ピナコール酸エステル等のアリールボロン酸エステルは、炭素-炭素結合反応、炭素-窒素結合反応、炭素-酸素結合反応等の合成反応における適用範囲が広く、また、水や空気に対する安定性が高く取り扱いが容易であるため、有機合成反応用試薬として非常に有用なものである。 Aryl boronic acid esters such as pinacolate have a wide range of applications in synthetic reactions such as carbon-carbon bond reactions, carbon-nitrogen bond reactions, and carbon-oxygen bond reactions, and are highly stable to water and air and can be handled easily. Since it is easy, it is very useful as a reagent for organic synthesis reaction.
従来、アリールボロン酸エステルを合成する一般的な方法として、アリールグリニャールやアリールリチウムを反応試薬としてトリアルキルボロン酸エステルと反応させる方法が知られているが(非特許文献1)、これらの反応試薬は強塩基性かつ強求核性のため、目的の基以外の置換基とも反応してしまい、適用できる基質の範囲が狭かった。また、アリールリチウムを用いる場合には、-78℃等の低温下で反応させる必要があり、簡便に使用できる方法ではなかった。 Conventionally, as a general method for synthesizing an aryl boronic acid ester, a method of reacting a trialkyl boronic acid ester with aryl Grignard or aryl lithium as a reaction reagent is known (Non-patent Document 1). Since it is strongly basic and strongly nucleophilic, it reacts with substituents other than the target group, and the range of applicable substrates is narrow. Further, when aryllithium is used, it is necessary to perform the reaction at a low temperature such as −78 ° C., which is not a method that can be used simply.
そこで、現在は、基質の適用性を広げるため、遷移金属を用いたアリールハライドのホウ素化法や芳香族C-H結合のホウ素化(C-B)法が広く研究されている(非特許文献2)。しかし、これらの方法は、遷移金属を用いる反応であるため、試薬が高額である、反応生成物に重金属が混入する等の問題があった。特に、重金属の混入は医薬品に適さないという問題があった。 Therefore, at present, in order to broaden the applicability of the substrate, a boronation method of an aryl halide using a transition metal and a boronation method (C-B) method of an aromatic C—H bond are widely studied (Non-patent Document 2). However, since these methods are reactions using transition metals, there are problems such as expensive reagents and contamination of reaction products with heavy metals. In particular, there is a problem that mixing of heavy metals is not suitable for pharmaceuticals.
そのため、上記問題を有さない、特に、重金属を用いることなく、適用基質の範囲が広いアリールボロン酸エステルの製造方法の開発が望まれていた。 Therefore, it has been desired to develop a method for producing an aryl boronic acid ester that does not have the above-described problems, and in particular, does not use heavy metals and has a wide range of applicable substrates.
本発明者らは、上記問題を解決するべく鋭意研究を行った結果、ナトリウムアルコキシドまたはカリウムアルコキシドの存在下でアリールハライドとシリルボロン酸エステルとを反応させると、重金属を用いることなくアリールボロン酸エステルが効率よく製造でき、且つ種々のアリールハライドと反応すること(適用基質の範囲が広いこと)を見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that when an aryl halide and a silyl boronic acid ester are reacted in the presence of sodium alkoxide or potassium alkoxide, the aryl boronic acid ester is obtained without using a heavy metal. It has been found that it can be efficiently produced and reacts with various aryl halides (a wide range of applicable substrates), and the present invention has been completed.
即ち、本発明は、「下記一般式(V)で示される有機ハロゲン化合物
(式中、Xは臭素原子又はヨウ素原子を表し、Rは、炭素数1〜20のアルキル基、炭素数2〜20のアルケニル基、炭素数2〜20のアルキニル基、炭素数6〜14のアリール基、或いは、窒素原子、酸素原子及び硫黄原子から選ばれる異性原子を1〜3個含む複素環基を表し、これらの基は、炭素数1〜6のアルキル基、炭素数2〜6のアルケニル基、炭素数1〜6のアルコキシ基、炭素数2〜7のアルコキシカルボニル基、炭素数2〜6のアルケニルオキシ基、炭素数2〜12のアルキルカルバモイル基、炭素数6〜14のアリール基、フルオロ基、クロロ基、又は炭素数2〜12のアルキルアミノ基を置換基として有していてもよい。)と、下記一般式(VI)で示される化合物
(式中、3個のR3はそれぞれ独立して、炭素数1〜6のアルキル基又は炭素数6〜10のアリール基を表し、4個のR4はそれぞれ独立して、炭素数1〜3のアルキル基を表す。)とを、ナトリウムアルコキシド又はカリウムアルコキシドの存在下で反応させることを特徴とする、下記一般式(VII)で示される化合物
(式中、R及びR4は、上記と同じ。)の製造方法」に関する。
That is, the present invention provides an “organic halogen compound represented by the following general formula (V):
(In the formula, X represents a bromine atom or an iodine atom, and R represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or 6 to 14 carbon atoms. Represents an aryl group or a heterocyclic group containing 1 to 3 isomeric atoms selected from a nitrogen atom, an oxygen atom and a sulfur atom, and these groups are an alkyl group having 1 to 6 carbon atoms and an alkyl group having 2 to 6 carbon atoms. An alkenyl group, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, an alkylcarbamoyl group having 2 to 12 carbon atoms, and an aryl group having 6 to 14 carbon atoms , A fluoro group, a chloro group, or an alkylamino group having 2 to 12 carbon atoms as a substituent.) And a compound represented by the following general formula (VI)
(In the formula, three R 3 s each independently represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and four R 4 s each independently represent one to 1 carbon atoms. And a compound represented by the following general formula (VII), wherein the compound is reacted in the presence of sodium alkoxide or potassium alkoxide:
(Wherein R and R 4 are the same as above).
本発明の製造方法は、従来のジオールホウ素化合物の製造方法(ホウ素置換反応法)のようにパラジウム等の重金属を用いる必要がないため、生成物への重金属の混入や生成物の着色が起こりにくく、医薬品の製造に好適な方法である。また、温和な条件で反応が進むため、100℃近い温度での加熱や0℃より低い温度の冷却等の必要がないため、操作が容易になる利点があり、スケールアップ合成に有用な新しい方法である。即ち、本発明の製造方法は、従来法の問題を解決した、簡便な方法である。 Since the production method of the present invention does not require the use of heavy metals such as palladium unlike the conventional method for producing diol boron compounds (boron substitution reaction method), it is difficult for the products to be mixed with heavy metals or to be colored. This is a suitable method for the production of pharmaceuticals. In addition, since the reaction proceeds under mild conditions, there is no need for heating at a temperature close to 100 ° C. or cooling at a temperature lower than 0 ° C., so there is an advantage that the operation is easy and a new method useful for scale-up synthesis. It is. That is, the production method of the present invention is a simple method that solves the problems of the conventional methods.
更に、本発明の製造方法は、臭素原子またはヨウ素原子以外の置換基との反応性が低いため、各種置換基を有する基質に適用することが可能な方法である。 Furthermore, since the production method of the present invention has low reactivity with substituents other than bromine atoms or iodine atoms, it can be applied to substrates having various substituents.
[一般式(V)で示される有機ハロゲン化合物]
一般式(V)におけるXは、臭素原子又はヨウ素原子を表し、臭素原子が好ましい。
一般式(V)におけるRの炭素数1〜20のアルキル基は、直鎖状、分枝状或いは環状の何れでもよいが、直鎖状又は分枝状が好ましい。炭素数は1〜10が好ましく、炭素数1〜6がより好ましく、炭素数1〜3が特に好ましい。具体的には、例えばメチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、イソペンチル基、sec-ペンチル基、tert-ペンチル基、ネオペンチル基、2-メチルブチル基、1-エチルプロピル基、n-ヘキシル基、イソヘキシル基、sec-ヘキシル基、tert-ヘキシル基、ネオヘキシル基、2-メチルペンチル基、3-メチルペンチル基、1,2-ジメチルブチル基、2,2-ジメチルブチル基、1-エチルブチル基、2-エチルブチル基、n-ヘプチル基、イソヘプチル基、sec-ヘプチル基、tert-ヘプチル基、ネオヘプチル基、2-メチルヘキシル基、3-メチルヘキシル基、2,2-ジメチルペンチル基、3-エチルペンチル基、2,4-ジメチルペンチル基、1-エチル-1-メチルブチル基、1,2,3-トリメチルブチル基、n-オクチル基、イソオクチル基、sec-オクチル基、tert-オクチル基、ネオオクチル基、n-ノニル基、イソノニル基、sec-ノニル基、tert-ノニル基、ネオノニル基、n-デシル基、イソデシル基、sec-デシル基、tert-デシル基、ネオデシル基、n-ウンデシル基、イソウンデシル基、sec-ウンデシル基、tert-ウンデシル基、ネオウンデシル基、n-ドデシル基、イソドデシル基、sec-ドデシル基、tert-ドデシル基、ネオドデシル基、n-トリデシル基、イソトリデシル基、sec-トリデシル基、tert-トリデシル基、ネオトリデシル基、n-テトラデシル基、イソテトラデシル基、sec-テトラデシル基、tert-テトラデシル基、ネオテトラデシル基、n-ペンタデシル基、イソペンタデシル基、sec-ペンタデシル基、tert-ペンタデシル基、ネオペンタデシル基、n-ヘキサデシル基、イソヘキサデシル基、sec-ヘキサデシル基、tert-ヘキサデシル基、ネオヘキサデシル基、n-ヘプタデシル基、イソヘプタデシル基、sec-ヘプタデシル基、tert-ヘプタデシル基、ネオヘプタデシル基、n-オクタデシル基、イソオクタデシル基、sec-オクタデシル基、tert-オクタデシル基、ネオオクタデシル基、n-ノナデシル基、イソノナデシル基、sec-ノナデシル基、tert-ノナデシル基、ネオデシル基、n-イコシル基、イソイコシル基、sec-イコシル基、tert-イコシル基、ネオイコシル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基、シクロウンデシル基、シクロドデシル基等が挙げられ、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、イソペンチル基、sec-ペンチル基、tert-ペンチル基、ネオペンチル基、2-メチルブチル基、1-エチルプロピル基、n-ヘキシル基、イソヘキシル基、sec-ヘキシル基、tert-ヘキシル基、ネオヘキシル基、2-メチルペンチル基、3-メチルペンチル基、1,2-ジメチルブチル基、2,2-ジメチルブチル基、1-エチルブチル基、2-エチルブチル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基が好ましく、メチル基、エチル基、n-プロピル基、イソプロピル基がより好ましい。
上記Rの炭素数1〜20のアルキル基は、炭素数1〜6のアルキル基、炭素数2〜6のアルケニル基、炭素数1〜6のアルコキシ基、炭素数2〜7のアルコキシカルボニル基、炭素数2〜6のアルケニルオキシ基、炭素数2〜12のアルキルカルバモイル基、炭素数6〜14のアリール基、フルオロ基、クロロ基、及び炭素数2〜12のアルキルアミノ基から選ばれる置換基を有していてもよいが、炭素数6〜14のアリール基を置換基として有するもの又は無置換のものが好ましい。
[Organic halogen compound represented by general formula (V)]
X in the general formula (V) represents a bromine atom or an iodine atom, and is preferably a bromine atom.
The alkyl group having 1 to 20 carbon atoms of R in the general formula (V) may be linear, branched or cyclic, but is preferably linear or branched. 1-10 are preferable, as for carbon number, 1-6 are more preferable, and carbon number 1-3 are especially preferable. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group Tert-pentyl group, neopentyl group, 2-methylbutyl group, 1-ethylpropyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2-methylpentyl group, 3-methyl Pentyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, n-heptyl group, isoheptyl group, sec-heptyl group, tert-heptyl group, neoheptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 3-ethylpentyl group, 2,4-dimethylpentyl group, 1-ethyl-1-methylbutyl group, 1,2,3-trimethyl Butyl group, n-octyl group, iso Octyl, sec-octyl, tert-octyl, neooctyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, neononyl, n-decyl, isodecyl, sec-decyl, tert-decyl group, neodecyl group, n-undecyl group, isoundecyl group, sec-undecyl group, tert-undecyl group, neoundecyl group, n-dodecyl group, isododecyl group, sec-dodecyl group, tert-dodecyl group, neododecyl group, n-tridecyl group, isotridecyl group, sec-tridecyl group, tert-tridecyl group, neotridecyl group, n-tetradecyl group, isotetradecyl group, sec-tetradecyl group, tert-tetradecyl group, neotetradecyl group, n-pentadecyl group , Isopentadecyl group, sec-pentadecyl group, tert-pentadecyl group, neopentadecyl group, n-hexadecyl group, isohexadecyl group, sec-he Xadecyl, tert-hexadecyl, neohexadecyl, n-heptadecyl, isoheptadecyl, sec-heptadecyl, tert-heptadecyl, neoheptadecyl, n-octadecyl, isooctadecyl, sec-octadecyl, tert- Octadecyl group, neooctadecyl group, n-nonadecyl group, isononadecyl group, sec-nonadecyl group, tert-nonadecyl group, neodecyl group, n-icosyl group, isoicosyl group, sec-icosyl group, tert-icosyl group, neoicosyl group, cyclo Propyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, and the like, such as methyl group, ethyl group, n-propyl group, Isopropyl group, n-butyl group, isobutyl group, sec- Tyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, 2-methylbutyl group, 1-ethylpropyl group, n-hexyl group, isohexyl group, sec- Hexyl, tert-hexyl, neohexyl, 2-methylpentyl, 3-methylpentyl, 1,2-dimethylbutyl, 2,2-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, cyclo A propyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group are preferable, and a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are more preferable.
The alkyl group having 1 to 20 carbon atoms of R is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, Substituent selected from C2-C6 alkenyloxy group, C2-C12 alkylcarbamoyl group, C6-C14 aryl group, fluoro group, chloro group, and C2-C12 alkylamino group However, those having an aryl group having 6 to 14 carbon atoms as a substituent or unsubstituted are preferable.
一般式(V)におけるRの炭素数2〜20のアルケニル基は、直鎖状、分枝状或いは環状の何れでもよいが、直鎖状が好ましい。炭素数は、2〜10が好ましく、炭素数2〜6がより好ましい。具体的には、例えばビニル基、アリル基、1-プロペニル基、イソプロペニル基、1-ブテニル基、2-ブテニル基、3-ブテニル基、2-メチル-2-プロペニル基、1-ペンテニル基、2-ペンテニル基、3-ペンテニル基、4-ペンテニル基、2-メチル-2-ブテニル基、1,2-ジメチル-2-プロペニル基、1-ヘキセニル基、2-ヘキセニル基、3-ヘキセニル基、4-ヘキセニル基、5-ヘキセニル基、2-メチル-2-ペンテニル基、1-ヘプテニル基、2-ヘプテニル基、3-ヘプテニル基、4-ヘプテニル基、5-ヘプテニル基、6-ヘプテニル基、1-オクテニル基、2-オクテニル基、1-ノネニル基、デセニル基、ウンデセニル基、ドデセニル基、トリデセニル基、テトラデセニル基、ペンタデセニル基、ヘキサデセニル基、ヘプタデセニル基、オクタデセニル基、ノナデセニル基、イコセニル基、1-シクロブテニル基、1-シクロペンテニル基、1-シクロヘキセニル基等が挙げられ、ビニル基、アリル基、1-プロペニル基、イソプロペニル基、1-ブテニル基、2-ブテニル基、3-ブテニル基、2-メチルアリル基、1-ペンテニル基、2-ペンテニル基、3-ペンテニル基、4-ペンテニル基、2-メチル-2-ブテニル基、1-ヘキセニル基、2-ヘキセニル基、3-ヘキセニル基、5-ヘキセニル基、2-メチル-2-ペンテニル基、1-シクロブテニル基、1-シクロペンテニル基、1-シクロヘキセニル基が好ましく、ビニル基、アリル基、1-プロペニル基、イソプロペニル基、1-ブテニル基、2-ブテニル基、3-ブテニル基、2-メチル-2-プロペニル基、1-ペンテニル基、2-ペンテニル基、3-ペンテニル基、4-ペンテニル基、2-メチル-2-ブテニル基、1,2-ジメチル-2-プロペニル基、1-ヘキセニル基、2-ヘキセニル基、3-ヘキセニル基、5-ヘキセニル基、2-メチル-2-ペンテニル基がより好ましく、ビニル基、アリル基、1,2-ジメチル-2-プロペニル基が更に好ましく、1,2-ジメチル-2-プロペニル基が特に好ましい。
上記Rの炭素数2〜20のアルケニル基は、炭素数1〜6のアルキル基、炭素数2〜6のアルケニル基、炭素数1〜6のアルコキシ基、炭素数2〜7のアルコキシカルボニル基、炭素数2〜6のアルケニルオキシ基、炭素数2〜12のアルキルカルバモイル基、炭素数6〜14のアリール基、フルオロ基、クロロ基、及び炭素数2〜12のアルキルアミノ基から選ばれる置換基を有していてもよいが、無置換のものが好ましい。
The alkenyl group having 2 to 20 carbon atoms of R in the general formula (V) may be linear, branched or cyclic, but is preferably linear. 2-10 are preferable and, as for carbon number, 2-6 are more preferable. Specifically, for example, vinyl group, allyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 2-methyl-2-butenyl group, 1,2-dimethyl-2-propenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 2-methyl-2-pentenyl group, 1-heptenyl group, 2-heptenyl group, 3-heptenyl group, 4-heptenyl group, 5-heptenyl group, 6-heptenyl group, 1 -Octenyl, 2-octenyl, 1-nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, icosenyl, 1-cycl Butenyl group, 1-cyclopentenyl group, 1-cyclohexenyl group and the like, vinyl group, allyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2 -Methylallyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 2-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 5- Hexenyl group, 2-methyl-2-pentenyl group, 1-cyclobutenyl group, 1-cyclopentenyl group, 1-cyclohexenyl group are preferable, vinyl group, allyl group, 1-propenyl group, isopropenyl group, 1-butenyl group 2-butenyl group, 3-butenyl group, 2-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 2-methyl-2-butenyl group, 1 , 2-dimethyl-2-propenyl group, 1-hexenyl group, 2-hexyl More preferred are senyl group, 3-hexenyl group, 5-hexenyl group and 2-methyl-2-pentenyl group, more preferred are vinyl group, allyl group and 1,2-dimethyl-2-propenyl group, and 1,2-dimethyl group. A 2-propenyl group is particularly preferred.
The alkenyl group having 2 to 20 carbon atoms of R is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, Substituent selected from C2-C6 alkenyloxy group, C2-C12 alkylcarbamoyl group, C6-C14 aryl group, fluoro group, chloro group, and C2-C12 alkylamino group However, an unsubstituted one is preferable.
一般式(V)におけるRの炭素数2〜20のアルキニル基は、直鎖状でも分枝状でもよいが、直鎖状が好ましい。炭素数は、2〜10が好ましく、2〜6がより好ましい。具体的には、例えばエチニル基、1-プロピニル基、2-プロピニル基、1-ブチニル基、2-ブチニル基、3-ブチニル基、1-メチル-2-プロピニル基、1-ペンチニル基、2-ペンチニル基、3-ペンチニル基、4-ペンチニル基、1-メチル-3-ブチニル基、1-ヘキシニル基、2-ヘキシニル基、3-ヘキシニル基、4-ヘキシニル基、5-ヘキシニル基、2-メチル-4-へプチニル基、1-へプチニル基、2-へプチニル基、3-へプチニル基、4-へプチニル基、5-へプチニル基、6-へプチニル基、1-オクチニル基、2-オクチニル基、3-オクチニル基、4-オクチニル基、5-オクチニル基、6-オクチニル基、7-オクチニル基、1-ノニニル基、2-ノニニル基、3-ノニニル基、4-ノニニル基、5-ノニニル基、6-ノニニル基、7-ノニニル基、8-ノニニル基、1-デシニル基、3-デシニル基、5-デシニル基、7-デシニル基、9-デシニル基、1-ウンデシニル基、3-ウンデシニル基、5-ウンデシニル基、7-ウンデシニル基、9-ウンデシニル基、1-ドデシニル基、3-ドデシニル基、5-ドデシニル基、7-ドデシニル基、9-ドデシニル基、11-ドデシニル基、トリデシニル基、テトラデシニル基、ペンタデシニル基、ヘキサデシニル基、ヘプタデシニル基、オクタデシニル基、ノナデシニル基、イコシニル基等が挙げられ、エチニル基、1-プロピニル基、2-プロピニル基、1-ブチニル基、2-ブチニル基、3-ブチニル基、1-メチル-2-プロピニル基、1-ペンチニル基、2-ペンチニル基、3-ペンチニル基、4-ペンチニル基、1-メチル-3-ブチニル基、1-ヘキシニル基、2-ヘキシニル基、3-ヘキシニル基、4-ヘキシニル基、5-ヘキシニル基、2-メチル-4-へプチニル基、1-へプチニル基、2-へプチニル基、3-へプチニル基、4-へプチニル基、5-へプチニル基、6-へプチニル基、1-オクチニル基、2-オクチニル基、3-オクチニル基、4-オクチニル基、5-オクチニル基、6-オクチニル基、7-オクチニル基、1-ノニニル基、2-ノニニル基、3-ノニニル基、4-ノニニル基、5-ノニニル基、6-ノニニル基、7-ノニニル基、8-ノニニル基、1-デシニル基、3-デシニル基、5-デシニル基、7-デシニル基、9-デシニル基が好ましく、エチニル基、1-プロピニル基、2-プロピニル基、1-ブチニル基、2-ブチニル基、3-ブチニル基、1-メチル-2-プロピニル基、1-ペンチニル基、2-ペンチニル基、3-ペンチニル基、4-ペンチニル基、1-メチル-3-ブチニル基、1-ヘキシニル基、2-ヘキシニル基、3-ヘキシニル基、4-ヘキシニル基、5-ヘキシニル基がより好ましい。
上記Rの炭素数2〜20のアルキニル基は、炭素数1〜6のアルキル基、炭素数2〜6のアルケニル基、炭素数1〜6のアルコキシ基、炭素数2〜7のアルコキシカルボニル基、炭素数2〜6のアルケニルオキシ基、炭素数2〜12のアルキルカルバモイル基、炭素数6〜14のアリール基、フルオロ基、クロロ基、及び炭素数2〜12のアルキルアミノ基から選ばれる置換基を有していてもよいが、無置換のものが好ましい。
The alkynyl group having 2 to 20 carbon atoms of R in the general formula (V) may be linear or branched, but is preferably linear. 2-10 are preferable and, as for carbon number, 2-6 are more preferable. Specifically, for example, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group, 1-pentynyl group, 2- Pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-methyl-3-butynyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexynyl group, 2-methyl -4-heptynyl group, 1-heptynyl group, 2-heptynyl group, 3-heptynyl group, 4-heptynyl group, 5-heptynyl group, 6-heptynyl group, 1-octynyl group, 2- Octynyl group, 3-octynyl group, 4-octynyl group, 5-octynyl group, 6-octynyl group, 7-octynyl group, 1-noninyl group, 2-noninyl group, 3-noninyl group, 4-noninyl group, 5- Noninyl group, 6-noninyl group, 7-noninyl group, 8-noninyl group, 1-decynyl group, 3-decynyl group, 5-decynyl group, 7-decynyl group, 9 -Decynyl group, 1-undecynyl group, 3-undecynyl group, 5-undecynyl group, 7-undecynyl group, 9-undecynyl group, 1-dodecynyl group, 3-dodecynyl group, 5-dodecynyl group, 7-dodecynyl group, 9 -Dodecynyl group, 11-dodecynyl group, tridecynyl group, tetradecynyl group, pentadecynyl group, hexadecynyl group, heptadecynyl group, octadecynyl group, nonadecynyl group, icosinyl group and the like, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-methyl-3- Butynyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexynyl group, 2-methyl-4-heptynyl group, 1-heptynyl group, 2-heptynyl group, 3-heptyl Nyl group, 4-heptynyl group, 5-heptynyl group, 6-heptynyl group, 1-octynyl group, 2-octynyl group, 3-octynyl group, 4-octynyl group, 5-octynyl group, 6-octynyl group 7-octynyl group, 1-noninyl group, 2-noninyl group, 3-noninyl group, 4-noninyl group, 5-noninyl group, 6-noninyl group, 7-noninyl group, 8-noninyl group, 1-decynyl group , 3-decynyl group, 5-decynyl group, 7-decynyl group and 9-decynyl group are preferred, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group and 3-butynyl group 1-methyl-2-propynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-methyl-3-butynyl group, 1-hexynyl group, 2-hexynyl group, 3 More preferred are -hexynyl group, 4-hexynyl group and 5-hexynyl group.
The alkynyl group having 2 to 20 carbon atoms of R is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, Substituent selected from C2-C6 alkenyloxy group, C2-C12 alkylcarbamoyl group, C6-C14 aryl group, fluoro group, chloro group, and C2-C12 alkylamino group However, an unsubstituted one is preferable.
一般式(V)におけるRの炭素数6〜14のアリール基としては、例えばフェニル基、ナフチル基、アントラセニル基が挙げられる。
上記Rの炭素数6〜14のアリール基は、炭素数1〜6のアルキル基、炭素数2〜6のアルケニル基、炭素数1〜6のアルコキシ基、炭素数2〜7のアルコキシカルボニル基、炭素数2〜6のアルケニルオキシ基、炭素数2〜12のアルキルカルバモイル基、炭素数6〜14のアリール基、フルオロ基、クロロ基、及び炭素数2〜12のアルキルアミノ基から選ばれる置換基を有していてもよいが、炭素数1〜6のアルキル基、炭素数2〜6のアルケニル基、炭素数1〜6のアルコキシ基、炭素数2〜7のアルコキシカルボニル基、炭素数2〜6のアルケニルオキシ基、炭素数2〜12のアルキルカルバモイル基、フルオロ基、クロロ基、及び炭素数2〜12のアルキルアミノ基から選ばれる置換基を有するもの或いは無置換のものが好ましい。
Examples of the aryl group having 6 to 14 carbon atoms of R in the general formula (V) include a phenyl group, a naphthyl group, and an anthracenyl group.
The aryl group having 6 to 14 carbon atoms of R is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, Substituent selected from C2-C6 alkenyloxy group, C2-C12 alkylcarbamoyl group, C6-C14 aryl group, fluoro group, chloro group, and C2-C12 alkylamino group The alkyl group having 1 to 6 carbon atoms, the alkenyl group having 2 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms, the alkoxycarbonyl group having 2 to 7 carbon atoms, and 2 to 2 carbon atoms. Preferred are those having a substituent selected from an alkenyloxy group having 6 carbon atoms, an alkylcarbamoyl group having 2 to 12 carbon atoms, a fluoro group, a chloro group, and an alkylamino group having 2 to 12 carbon atoms, or unsubstituted. .
一般式(V)におけるRの、窒素原子、酸素原子及び硫黄原子から選ばれる異性原子を1〜3個含む複素環基としては、芳香族性を有していてもよい、通常3〜20員、好ましくは3〜14員、より好ましくは5〜10員の単環式複素環又は多環式複素環由来の基が挙げられる。単環式複素環由来の基の場合には5〜6員のものが好ましく、多環式複素環由来の基の場合には、9〜10員、特に9員のものが好ましく、中でも、多環式複素環由来の基が好ましい。これらは鎖状、分枝状或いは環状に環が縮合して、それらが平面構造をとっていても或いは立体構造をとっていてもよい。 As the heterocyclic group containing 1 to 3 isomeric atoms selected from a nitrogen atom, an oxygen atom and a sulfur atom of R in the general formula (V), it may have aromaticity, usually 3 to 20 members. And preferably a group derived from a 3 to 14-membered, more preferably 5 to 10-membered monocyclic heterocyclic ring or polycyclic heterocyclic ring. In the case of a group derived from a monocyclic heterocyclic ring, those having 5 to 6 members are preferable, and in the case of a group derived from a polycyclic heterocyclic ring, those having 9 to 10 members, particularly 9 members are preferable. Groups derived from cyclic heterocycles are preferred. These may be condensed in a chain, branched or cyclic form, and they may have a planar structure or a three-dimensional structure.
上記複素環由来の基は、窒素原子、酸素原子又は硫黄原子を通常1〜3個、好ましくは1〜2個、より好ましくは1個有し、これらの中でも窒素原子を有するものが好ましい。 The group derived from the heterocyclic ring generally has 1 to 3, preferably 1 to 2, more preferably 1 nitrogen atom, oxygen atom or sulfur atom, and among these, those having a nitrogen atom are preferable.
上記単環式複素環としては、例えばオキシラン環、アジリジン環等のヘテロ原子1つを有する3員複素環、例えばフラン環,チオフェン環,ピロール環,2H−ピロール環,ピロリン環,2−ピロリン環,ピロリジン環等のヘテロ原子を1つ有する5員複素環、例えば1,3−ジオキソラン環,オキサゾール環,イソオキサゾール環,チアゾール環,イソチアゾール環,イミダゾール環,イミダゾリン環,2−イミダゾリン環,イミダゾリジン環,ピラゾール環,ピラゾリン環,3−ピラゾリン環,ピラゾリジン環等のヘテロ原子を2つ有する5員複素環、例えばフラザン環,トリアゾール環,チアジアゾール環,オキサジアゾール環等のヘテロ原子を3つ有する5員複素環、例えばピラン環,2H−ピラン環,ピリジン環,ピペリジン環等のヘテロ原子を1つ有する6員複素環、例えばチオピラン環,ピリダジン環,ピリミジン環,ピラジン環,ピペラジン環,モルホリン環等のヘテロ原子を2つ有する6員複素環、1,2,4−トリアジン環等のヘテロ原子を3つ有する6員複素環等が挙げられる。 Examples of the monocyclic heterocycle include 3-membered heterocycles having one heteroatom such as an oxirane ring and an aziridine ring, such as a furan ring, a thiophene ring, a pyrrole ring, a 2H-pyrrole ring, a pyrroline ring, and a 2-pyrroline ring. , 5-membered heterocycle having one heteroatom such as pyrrolidine ring, such as 1,3-dioxolane ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, 2-imidazoline ring, imidazole 5-membered heterocycle having two heteroatoms such as lysine ring, pyrazole ring, pyrazoline ring, 3-pyrazolin ring and pyrazolidine ring, for example, three heteroatoms such as furazane ring, triazole ring, thiadiazole ring and oxadiazole ring 5-membered heterocyclic ring having, for example, pyran ring, 2H-pyran ring, pyridine ring, piperidine ring, etc. 6-membered heterocycle having 1 heteroatom, for example, 6-membered heterocycle having 2 heteroatoms such as thiopyran ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring, morpholine ring, 1,2,4-triazine ring 6-membered heterocycle having 3 heteroatoms such as
上記多環式複素環としては、2〜3個の単環式複素環同士が縮合したもの或いは単環式複素環と例えばベンゼン環,ナフタレン環等の芳香族環1〜2個が縮合して成る、二環系複素環、三環系複素環等が挙げられる。 Examples of the polycyclic heterocycle include those obtained by condensing 2 to 3 monocyclic heterocycles or monocyclic heterocycles and 1 to 2 aromatic rings such as benzene ring and naphthalene ring. And bicyclic heterocycles, tricyclic heterocycles, and the like.
該二環系複素環としては、例えばベンゾフラン環,イソベンゾフラン環,1−ベンゾチオフェン環,2−ベンゾチオフェン環,インドール環,3−インドール環,イソインドール環,インドリジン環,インドリン環,イソインドリン環,2H−クロメン環,クロマン環,イソクロマン環,1H−2−ベンゾピラン環,キノリン環,イソキノリン環,4H−キノリジン環等のヘテロ原子を1つ有する複素環、例えばベンゾイミダゾール環,ベンゾチアゾール環,1H−インダゾール環,1,8−ナフチリジン環,キノキサリン環,キナゾリン環,キナゾリジン環,シンノリン環,フタラジン環等のヘテロ原子を2つ有する複素環、例えばプリン環,プテリジン環等のヘテロ原子を4つ有する複素環等が挙げられる。 Examples of the bicyclic heterocyclic ring include benzofuran ring, isobenzofuran ring, 1-benzothiophene ring, 2-benzothiophene ring, indole ring, 3-indole ring, isoindole ring, indolizine ring, indoline ring, isoindoline. Heterocycles having one heteroatom such as a ring, 2H-chromene ring, chroman ring, isochroman ring, 1H-2-benzopyran ring, quinoline ring, isoquinoline ring, 4H-quinolidine ring, such as benzoimidazole ring, benzothiazole ring, Heterocycles having two heteroatoms such as 1H-indazole ring, 1,8-naphthyridine ring, quinoxaline ring, quinazoline ring, quinazolidine ring, cinnoline ring, phthalazine ring, for example, four heteroatoms such as purine ring and pteridine ring The heterocyclic ring etc. which have are mentioned.
該三環系複素環としては、例えばカルバゾール環,4aH−カルバゾール環,キサンテン環,フェナントリジン環,アクリジン環等のヘテロ原子を1つ有する複素環、例えばβ−カルボリン環,ペリミジン環,1,7−フェナントロリン環,1,10−フェナントロリン環,チアントレン環,フェノキサチイン環,フェノキサジン環,フェノチアジン環,フェナジン環等のヘテロ原子を2つ有する複素環等が挙げられる。 Examples of the tricyclic heterocycle include heterocycles having one heteroatom such as carbazole ring, 4aH-carbazole ring, xanthene ring, phenanthridine ring, acridine ring, such as β-carboline ring, perimidine ring, 1, Examples include 7-phenanthroline ring, 1,10-phenanthroline ring, thianthrene ring, phenoxathiin ring, phenoxazine ring, phenothiazine ring, and heterocycle having two heteroatoms such as phenazine ring.
一般式(V)におけるRの、窒素原子、酸素原子及び硫黄原子から選ばれる異性原子を1〜3個含む複素環基の好ましい例としては、上記単環式複素環由来の基、上記二環系複素環由来の基等が挙げられるが、中でも、インドール環,イソインドール環,インドリン環,イソインドリン環,キノリン環,イソキノリン環,4H−キノリジン環等が好ましい。
上記Rの窒素原子、酸素原子及び硫黄原子から選ばれる異性原子を1〜3個含む複素環基は、炭素数1〜6のアルキル基、炭素数2〜6のアルケニル基、炭素数1〜6のアルコキシ基、炭素数2〜7のアルコキシカルボニル基、炭素数2〜6のアルケニルオキシ基、炭素数2〜12のアルキルカルバモイル基、炭素数6〜14のアリール基、フルオロ基、クロロ基、及び炭素数2〜12のアルキルアミノ基から選ばれる置換基を有していてもよいが、炭素数1〜6のアルキル基を置換基として有するもの又は無置換のものが好ましい。
Preferred examples of the heterocyclic group containing 1 to 3 isomeric atoms selected from a nitrogen atom, an oxygen atom and a sulfur atom of R in the general formula (V) include a group derived from the above monocyclic heterocyclic ring and the above bicyclic ring. Examples thereof include a group derived from a system heterocycle, among which an indole ring, isoindole ring, indoline ring, isoindoline ring, quinoline ring, isoquinoline ring, 4H-quinolidine ring and the like are preferable.
The heterocyclic group containing 1 to 3 isomeric atoms selected from the nitrogen atom, oxygen atom and sulfur atom of R is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and 1 to 6 carbon atoms. An alkoxy group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, an alkylcarbamoyl group having 2 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, a fluoro group, a chloro group, and Although it may have a substituent selected from an alkylamino group having 2 to 12 carbon atoms, one having an alkyl group having 1 to 6 carbon atoms as a substituent or an unsubstituted one is preferable.
一般式(V)におけるRの置換基である炭素数1〜6のアルキル基は、直鎖状、分枝状或いは環状の何れでもよく、炭素数1〜4のものが好ましい。具体的には、例えばメチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、イソペンチル基、sec-ペンチル基、tert-ペンチル基、ネオペンチル基、n-ヘキシル基、イソヘキシル基、sec-ヘキシル基、tert-ヘキシル基、ネオヘキシル基等が挙げられ、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基等が好ましい。 The alkyl group having 1 to 6 carbon atoms, which is a substituent of R in the general formula (V), may be linear, branched or cyclic, and preferably has 1 to 4 carbon atoms. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group Tert-pentyl group, neopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, etc., including methyl group, ethyl group, n-propyl group, isopropyl group, n- A butyl group, isobutyl group, sec-butyl group, tert-butyl group and the like are preferable.
一般式(V)におけるRの置換基である炭素数2〜6のアルケニル基は、直鎖状、分枝状或いは環状の何れでも良く、炭素数2〜4のものが好ましい。具体的には例えばビニル基、アリル基、1-プロペニル基、イソプロペニル基、1-ブテニル基、2-ブテニル基、3-ブテニル基、2-メチルアリル基、1-ペンテニル基、2-ペンテニル基、3-ペンテニル基、4-ペンテニル基、2-メチル-2-ブテニル基、1-ヘキセニル基、2-ヘキセニル基、3-ヘキセニル基、5-ヘキセニル基、2-メチル-2-ペンテニル基、1-シクロブテニル基、1-シクロペンテニル基、1-シクロヘキセニル基等が挙げられ、ビニル基、アリル基、1-プロペニル基、イソプロペニル基、1-ブテニル基、2-ブテニル基、3-ブテニル基、2-メチルアリル基等が好ましい。 The alkenyl group having 2 to 6 carbon atoms which is a substituent of R in the general formula (V) may be linear, branched or cyclic, and preferably has 2 to 4 carbon atoms. Specifically, for example, vinyl group, allyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methylallyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 2-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 5-hexenyl group, 2-methyl-2-pentenyl group, 1- And cyclobutenyl group, 1-cyclopentenyl group, 1-cyclohexenyl group, etc., vinyl group, allyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2 -A methyl allyl group etc. are preferable.
一般式(V)におけるRの置換基である炭素数1〜6のアルコキシ基は、直鎖状、分枝状或いは環状の何れでもよく、炭素数1〜4のものが好ましい。具体的には、例えばメトキシ基、エトキシ基、n-プロポキシ基、イソプロポキシ基、n-ブトキシ基、イソブトキシ基、sec-ブトキシ基、tert-ブトキシ基、n-ペンチルオキシ基、イソペンチルオキシ基、sec-ペンチルオキシ基、tert-ペンチルオキシ基、ネオペンチルオキシ基、n-ヘキシルオキシ基、イソヘキシルオキシ基、sec-ヘキシルオキシ基、tert-ヘキシルオキシ基、ネオヘキシルオキシ基等が挙げられ、メトキシ基、エトキシ基、n-プロポキシ基、イソプロポキシ基、n-ブトキシ基、イソブトキシ基、sec-ブトキシ基、tert-ブトキシ基等が好ましい。 The alkoxy group having 1 to 6 carbon atoms which is a substituent of R in the general formula (V) may be linear, branched or cyclic, and preferably has 1 to 4 carbon atoms. Specifically, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, neopentyloxy group, n-hexyloxy group, isohexyloxy group, sec-hexyloxy group, tert-hexyloxy group, neohexyloxy group, etc. Group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group and the like are preferable.
一般式(V)におけるRの置換基である炭素数2〜7のアルコキシカルボニル基は、
直鎖状、分枝状或いは環状の何れでもよく、炭素数2〜5のものが好ましい。具体的には、例えばメトキシカルボニル基、エトキシカルボニル基、n-プロポキシカルボニル基、イソプロポキシカルボニル基、n-ブトキシカルボニル基、イソブトキシカルボニル基、sec-ブトキシカルボニル基、tert-ブトキシカルボニル基、n-ペンチルオキシカルボニル基、イソペンチルオキシカルボニル基、sec-ペンチルオキシカルボニル基、tert-ペンチルオキシカルボニル基、ネオペンチルオキシカルボニル基、n-ヘキシルオキシカルボニル基、イソヘキシルオキシカルボニル基、sec-ヘキシルオキシカルボニル基、tert-ヘキシルオキシカルボニル基、ネオヘキシルオキシカルボニル基等が挙げられ、メトキシカルボニル基、エトキシカルボニル基、n-プロポキシカルボニル基、イソプロポキシカルボニル基、n-ブトキシカルボニル基、イソブトキシカルボニル基、sec-ブトキシカルボニル基、tert-ブトキシカルボニル基等が好ましい。
The alkoxycarbonyl group having 2 to 7 carbon atoms, which is a substituent of R in the general formula (V),
It may be linear, branched or cyclic, and preferably has 2 to 5 carbon atoms. Specifically, for example, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n- Pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, neopentyloxycarbonyl group, n-hexyloxycarbonyl group, isohexyloxycarbonyl group, sec-hexyloxycarbonyl group Tert-hexyloxycarbonyl group, neohexyloxycarbonyl group, etc., methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxy Aryloxycarbonyl group, sec- butoxycarbonyl group, etc. tert- butoxycarbonyl group are preferred.
一般式(V)におけるRの置換基である炭素数2〜6のアルケニルオキシ基は、直鎖状、分枝状或いは環状の何れでもよく、炭素数2〜4のものが好ましい。具体的には、例えばビニルオキシ基、アリルオキシ基、1-プロペニルオキシ基、イソプロペニルオキシ基、1-ブテニルオキシ基、2-ブテニルオキシ基、3-ブテニルオキシ基、2-メチルアリルオキシ基、1-ペンテニルオキシ基、2-ペンテニルオキシ基、3-ペンテニルオキシ基、4-ペンテニルオキシ基、2-メチル-2-ブテニルオキシ基、1-ヘキセニルオキシ基、2-ヘキセニルオキシ基、3-ヘキセニルオキシ基、5-ヘキセニルオキシ基、2-メチル-2-ペンテニルオキシ基、1-シクロブテニルオキシ基、1-シクロペンテニルオキシ基、1-シクロヘキセニルオキシ基等が挙げられ、ビニルオキシ基、アリルオキシ基、1-プロペニルオキシ基、イソプロペニルオキシ基、1-ブテニルオキシ基、2-ブテニルオキシ基、3-ブテニルオキシ基、2-メチルアリルオキシ基等が好ましい。 The alkenyloxy group having 2 to 6 carbon atoms which is a substituent of R in the general formula (V) may be linear, branched or cyclic, and preferably has 2 to 4 carbon atoms. Specifically, for example, vinyloxy group, allyloxy group, 1-propenyloxy group, isopropenyloxy group, 1-butenyloxy group, 2-butenyloxy group, 3-butenyloxy group, 2-methylallyloxy group, 1-pentenyloxy group 2-pentenyloxy group, 3-pentenyloxy group, 4-pentenyloxy group, 2-methyl-2-butenyloxy group, 1-hexenyloxy group, 2-hexenyloxy group, 3-hexenyloxy group, 5-hexenyloxy group Group, 2-methyl-2-pentenyloxy group, 1-cyclobutenyloxy group, 1-cyclopentenyloxy group, 1-cyclohexenyloxy group and the like, vinyloxy group, allyloxy group, 1-propenyloxy group, An isopropenyloxy group, a 1-butenyloxy group, a 2-butenyloxy group, a 3-butenyloxy group, a 2-methylallyloxy group, and the like are preferable.
一般式(V)におけるRの置換基である炭素数2〜12のアルキルカルバモイル基としては、カルバモイル(−CONH2)基の水素原子2個が炭素数1〜6、好ましくは炭素数1〜3のアルキル基で置換されたものが挙げられ、具体的には、例えばN,N-メチルエチルカルバモイル基、N,N-n-メチルプロピルカルバモイル基、N,N-メチルイソプロピルカルバモイル基、N,N-メチル-n-ブチルカルバモイル基、N,N-メチル-tert-ブチルカルバモイル基、N,N-メチル-n-ヘキシルカルバモイル基、N,N-メチルシクロヘキシルカルバモイル基、N,N-ジメチルカルバモイル基、N,N-ジエチルカルバモイル基、N,N-ジシクロヘキシルカルバモイル基等が挙げられる。 As the alkyl carbamoyl group having 2 to 12 carbon atoms which is a substituent of R in the general formula (V), two hydrogen atoms of the carbamoyl (—CONH 2 ) group have 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Specific examples include N, N-methylethylcarbamoyl group, N, Nn-methylpropylcarbamoyl group, N, N-methylisopropylcarbamoyl group, N, N-methyl, and the like. -n-butylcarbamoyl group, N, N-methyl-tert-butylcarbamoyl group, N, N-methyl-n-hexylcarbamoyl group, N, N-methylcyclohexylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-diethylcarbamoyl group, N, N-dicyclohexylcarbamoyl group and the like can be mentioned.
一般式(V)におけるRの置換基である炭素数6〜14のアリール基としては、例えばフェニル基、ナフチル基、アントラセニル基等が挙げられる。 As a C6-C14 aryl group which is a substituent of R in General formula (V), a phenyl group, a naphthyl group, an anthracenyl group etc. are mentioned, for example.
一般式(V)におけるRの置換基である炭素数2〜12のアルキルアミノ基としては、アミノ基(−NH2)の水素原子2個が炭素数1〜6、好ましくは炭素数1〜3のアルキル基で置換されたものが挙げられ、具体的には、例えばN,N-メチルエチルアミノ基、N,N-メチル-n-プロピルアミノ基、N,N-メチルイソプロピルアミノ基、N,N-メチル-n-ブチルアミノ基、N,N-メチル-tert-ブチルアミノ基、N,N-メチル-n-ヘキシルアミノ基、N,N-メチルシクロヘキシルアミノ基、N,N-メチルエチルアミノ基、N,N-ジシクロアミノ基、N,N-ジメチルアミノ基等が挙げられる。 As a C2-C12 alkylamino group which is a substituent of R in General formula (V), two hydrogen atoms of an amino group (-NH2) are C1-C6, Preferably C1-C3 Specifically, for example, N, N-methylethylamino group, N, N-methyl-n-propylamino group, N, N-methylisopropylamino group, N, N-methyl-n-butylamino group, N, N-methyl-tert-butylamino group, N, N-methyl-n-hexylamino group, N, N-methylcyclohexylamino group, N, N-methylethylamino Group, N, N-dicycloamino group, N, N-dimethylamino group and the like.
一般式(V)におけるRは、炭素数6〜14のアリール基を置換基として有してもよい炭素数1〜20のアルキル基;炭素数2〜20のアルケニル基;炭素数2〜20のアルキニル基;炭素数1〜6のアルキル基、炭素数2〜6のアルケニル基、炭素数1〜6のアルコキシ基、炭素数2〜7のアルコキシカルボニル基、炭素数2〜6のアルケニルオキシ基、炭素数2〜12のアルキルカルバモイル基、炭素数6〜14のアリール基、フルオロ基、クロロ基、又は炭素数2〜12のアルキルアミノ基を置換基として有していてもよい炭素数6〜14のアリール基;或いは、窒素原子、酸素原子及び硫黄原子から選ばれる異性原子を1〜3個含む、炭素数1〜6のアルキル基を置換基として有していてもよい複素環基が好ましい。これらの好ましい具体例としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、イソペンチル基、sec-ペンチル基、tert-ペンチル基、ネオペンチル基、2-メチルブチル基、1-エチルプロピル基、n-ヘキシル基、イソヘキシル基、sec-ヘキシル基、tert-ヘキシル基、ネオヘキシル基、2-メチルペンチル基、3-メチルペンチル基、1,2-ジメチルブチル基、2,2-ジメチルブチル基、1-エチルブチル基、2-エチルブチル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、フェニルメチル基、フェニルエチル基、フェニル-n-プロピル基、フェニル-n-ブチル基、フェニル-n-ペンチル基、フェニル-n-ヘキシル基、ビニル基、アリル基、1-プロペニル基、イソプロペニル基、1-ブテニル基、2-ブテニル基、3-ブテニル基、2-メチルアリル基、1-ペンテニル基、2-ペンテニル基、3-ペンテニル基、4-ペンテニル基、2-メチル-2-ブテニル基、1-ヘキセニル基、2-ヘキセニル基、3-ヘキセニル基、5-ヘキセニル基、2-メチル-2-ペンテニル基、エチニル基、1-プロピニル基、2-プロピニル基、1-ブチニル基、2-ブチニル基、3-ブチニル基、1-メチル-2-プロピニル基、1-ペンチニル基、2-ペンチニル基、3-ペンチニル基、4-ペンチニル基、1-メチル-3-ブチニル基、1-ヘキシニル基、2-ヘキシニル基、3-ヘキシニル基、4-ヘキシニル基、5-ヘキシニル基、フェニル基、ナフチル基、アントラセニル基、インドール環由来の基,イソインドール環由来の基,インドリン環由来の基,イソインドリン環由来の基,キノリン環由来の基,イソキノリン環由来の基,4H−キノリジン環由来の基、N-メチルインドール環由来の基、N-エチルインドール環由来の基、N-n-プロピルインドール環由来の基、N-メチルイソインドール環由来の基、N-エチルイソインドール環由来の基、N-n-プロピルイソインドール環由来の基、メチルフェニル基、ジメチルフェニル基、トリメチルフェニル基、エチルフェニル基、プロピルフェニル基、トリプロピルフェニル基、トリイソプロピルフェニル基、アリルフェニル基、1-プロペニルフェニル基、メトキシフェニル基、エトキシフェニル基、プロポキシフェニル基、メトキシカルボニルフェニル基、エトキシカルボニルフェニル基、プロポキシカルボニルフェニル基、ブトキシカルボニルフェニル基、アリルオキシフェニル基、1-プロペニルオキシフェニル基、ジメチルカルバモイルフェニル基、ジエチルカルバモイルフェニル基、ジプロピルカルバモイルフェニル基、フルオロフェニル基、クロロフェニル基、ジメチルアミノフェニル基、ジエチルアミノフェニル基、ジプロピルアミノフェニル基等が挙げられる。 R in the general formula (V) may have an aryl group having 6 to 14 carbon atoms as a substituent, an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; An alkynyl group; an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, C6-C14 which may have a C2-C12 alkylcarbamoyl group, a C6-C14 aryl group, a fluoro group, a chloro group, or a C2-C12 alkylamino group as a substituent. Or a heterocyclic group optionally having as a substituent an alkyl group having 1 to 6 carbon atoms containing 1 to 3 isomeric atoms selected from a nitrogen atom, an oxygen atom and a sulfur atom. Specific examples of these include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec- Pentyl group, tert-pentyl group, neopentyl group, 2-methylbutyl group, 1-ethylpropyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2-methylpentyl group, 3 -Methylpentyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, phenylmethyl group, phenylethyl Group, phenyl-n-propyl group, phenyl-n-butyl group, phenyl-n-pentyl group, phenyl-n-hexyl group, vinyl group, allyl group, 1-propenyl group, iso Lopenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylallyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 2-methyl-2-butenyl Group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 5-hexenyl group, 2-methyl-2-pentenyl group, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2 -Butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 1-hexynyl Group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexynyl group, phenyl group, naphthyl group, anthracenyl group, group derived from indole ring, group derived from isoindole ring, group derived from indoline ring, Group derived from isoindoline ring, group derived from quinoline ring, iso Norin ring-derived group, 4H-quinolidine ring-derived group, N-methylindole ring-derived group, N-ethylindole ring-derived group, Nn-propylindole ring-derived group, N-methylisoindole ring-derived group , Group derived from N-ethylisoindole ring, group derived from Nn-propylisoindole ring, methylphenyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, tripropylphenyl group, triisopropylphenyl group Allylphenyl group, 1-propenylphenyl group, methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, propoxycarbonylphenyl group, butoxycarbonylphenyl group, allyloxyphenyl group, 1- Propenyloxyphenyl , Dimethylcarbamoyl phenyl group, diethylcarbamoyl phenyl group, dipropylcarbamoylphenyl group, fluorophenyl group, chlorophenyl group, dimethylaminophenyl group, diethylaminophenyl group, dipropylamino and a phenyl group.
一般式(V)で示される有機ハロゲン化合物としては、下記一般式(I)で示される化合物
(式中、Xは臭素原子又はヨウ素原子を表し、p1は0〜5の整数を表し、p1個のR1は、それぞれ独立して炭素数1〜6のアルキル基、炭素数2〜6のアルケニル基、炭素数1〜6のアルコキシ基、炭素数2〜7のアルコキシカルボニル基、炭素数2〜6のアルケニルオキシ基、炭素数2〜12のアルキルカルバモイル基、炭素数6〜14のアリール基、フルオロ基、クロロ基、又は炭素数2〜12のアルキルアミノ基を表す。)、下記一般式(II)で示される化合物
(式中、X及びR1は上記と同じ。p2は0〜7の整数を表す。)、下記一般式(III)で示される化合物
(式中、X及びR1は上記と同じ。p3は0〜9の整数を表す。)、下記一般式(IV)で示される化合物
(式中、Xは上記と同じ。R2は炭素数1〜6のアルキル基を表す。)、炭素数6〜14のアリール基を置換基として有する又は無置換の炭素数1〜20のアルキルブロマイド、炭素数6〜14のアリール基を置換基として有する又は無置換の炭素数1〜20のアルキルヨード、炭素数2〜20のアルケニルブロマイド、炭素数2〜20のアルケニルヨード、炭素数2〜20のアルキニルブロマイド、或いは、炭素数2〜20のアルキニルヨード等が挙げられる。これらの中でも、一般式(I)で示される化合物、一般式(III)で示される化合物、一般式(IV)で示される化合物、炭素数6〜14のアリール基を置換基として有する又は無置換の炭素数1〜20のアルキルブロマイド、炭素数2〜20のアルケニルブロマイドが好ましく、一般式(I)で示される化合物が特に好ましい。
As the organic halogen compound represented by the general formula (V), a compound represented by the following general formula (I)
(In the formula, X represents a bromine atom or an iodine atom, p 1 represents an integer of 0 to 5, and p 1 R 1 s are each independently an alkyl group having 1 to 6 carbon atoms or 2 to 2 carbon atoms. 6 alkenyl groups, alkoxy groups having 1 to 6 carbon atoms, alkoxycarbonyl groups having 2 to 7 carbon atoms, alkenyloxy groups having 2 to 6 carbon atoms, alkylcarbamoyl groups having 2 to 12 carbon atoms, and 6 to 14 carbon atoms An aryl group, a fluoro group, a chloro group, or an alkylamino group having 2 to 12 carbon atoms), a compound represented by the following general formula (II)
(Wherein X and R 1 are the same as described above; p 2 represents an integer of 0 to 7), a compound represented by the following general formula (III)
(Wherein X and R 1 are the same as described above; p 3 represents an integer of 0 to 9), a compound represented by the following general formula (IV)
(In the formula, X is the same as above. R 2 represents an alkyl group having 1 to 6 carbon atoms.), An aryl group having 6 to 14 carbon atoms as a substituent or an unsubstituted alkyl group having 1 to 20 carbon atoms. Bromide, C6-C14 aryl group as a substituent or unsubstituted alkyl iodo having 1 to 20 carbon atoms, C2-C20 alkenyl bromide, C2-C20 alkenyl iodide, C2-C2 Examples thereof include 20 alkynyl bromides or alkynyl iodides having 2 to 20 carbon atoms. Among these, the compound represented by the general formula (I), the compound represented by the general formula (III), the compound represented by the general formula (IV), an aryl group having 6 to 14 carbon atoms as a substituent or unsubstituted 1 to 20 alkyl bromide and
一般式(I)におけるp1は0〜5の整数であり、0〜3が好ましく、0又は1がより好ましい。 P < 1 > in general formula (I) is an integer of 0-5, 0-3 are preferable and 0 or 1 is more preferable.
一般式(I)におけるR1の、炭素数1〜6のアルキル基、炭素数2〜6のアルケニル基、炭素数1〜6のアルコキシ基、炭素数2〜7のアルコキシカルボニル基、炭素数2〜6のアルケニルオキシ基、炭素数2〜12のアルキルカルバモイル基、炭素数6〜14のアリール基、及び炭素数2〜12のアルキルアミノ基の具体例及び好ましいものは、一般式(V)におけるRの置換基として記載したものと同じものが挙げられる。 R 1 in the general formula (I), an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, 2 carbon atoms Specific examples and preferred examples of -6 alkenyloxy groups, C2-C12 alkylcarbamoyl groups, C6-C14 aryl groups, and C2-C12 alkylamino groups are given in general formula (V): The same thing as what was described as a substituent of R is mentioned.
一般式(I)で示される化合物としては、具体的には例えば以下のものが挙げられるが、中でも臭化化合物が好ましい。
Specific examples of the compound represented by the general formula (I) include the following compounds, among which bromide compounds are preferable.
一般式(II)におけるp2は0〜7の整数であり、0〜3が好ましく、0がより好ましい。 P < 2 > in general formula (II) is an integer of 0-7, 0-3 are preferable and 0 is more preferable.
一般式(II)におけるR1の具体例及び好ましいものは、一般式(I)におけるR1のそれらと同じである。 Specific examples and preferred examples of R 1 in formula (II) are the same as those for R 1 in formula (I).
一般式(II)で示される化合物の好ましいものとしては、一般式Iにおけるフェニレン基がナフチレン基に置換されたものが挙げられるが、中でもブロモナフチレン又はヨードナフチレンが好ましく、ブロモナフチレンが特に好ましい。 Preferred examples of the compound represented by the general formula (II) include those in which the phenylene group in the general formula I is substituted with a naphthylene group, among which bromonaphthylene or iodonaphthylene is preferable, and bromonaphthylene is particularly preferable.
一般式(III)におけるp3は0〜9の整数であり、0〜3が好ましく、0がより好ましい。 P < 3 > in general formula (III) is an integer of 0-9, 0-3 are preferable and 0 is more preferable.
一般式(III)におけるR1の具体例及び好ましいものは、一般式(I)におけるR1のそれらと同じである。 Specific examples and preferred examples of R 1 in the general formula (III) are the same as those for R 1 in the general formula (I).
一般式(III)で示される化合物の好ましいものとしては、一般式Iにおけるフェニレン基がアントラセニレン基に置換されたものが挙げられるが、中でもブロモアントラセン又はヨードアントラセンが好ましく、ブロモアントラセンが特に好ましい。 Preferred examples of the compound represented by the general formula (III) include those in which the phenylene group in the general formula I is substituted with an anthracenylene group. Among them, bromoanthracene or iodoanthracene is preferable, and bromoanthracene is particularly preferable.
一般式(IV)におけるR2の炭素数1〜6のアルキル基としては、一般式(V)におけるRの置換基である炭素数1〜6のアルキル基と同じものが挙げられ、具体例及び好ましいものも同じである。 Examples of the alkyl group having 1 to 6 carbon atoms of R 2 in the general formula (IV) include the same as the alkyl group having 1 to 6 carbon atoms which is the substituent of R in the general formula (V). The preferred ones are the same.
一般式(IV)で示される化合物の好ましいものとしては、例えば以下のものが挙げられ、中でも臭化化合物が好ましい。 Preferable examples of the compound represented by the general formula (IV) include the following, among which bromide compounds are preferable.
炭素数6〜14のアリール基を置換基として有する又は無置換の炭素数1〜20のアルキルブロマイドとしては、炭素数6〜14のアリール基を置換基として有する又は無置換の炭素数1〜10のアルキルブロマイドが好ましく、炭素数6〜14のアリール基を置換基として有する又は無置換の炭素数1〜6のアルキルブロマイドがより好ましい。上記置換基としてのアリール基としては、例えばフェニル基、ナフチル基、アントラセニル基等が挙げられ、フェニル基が好ましい。 As a C1-C14 aryl group which has a C6-C14 aryl group as a substituent, or an unsubstituted C1-C20 alkyl bromide, it has a C6-C14 aryl group as a substituent, or is unsubstituted C1-C10 Alkyl bromide is preferable, and an aryl bromide having 6 to 14 carbon atoms as a substituent or an unsubstituted alkyl bromide having 1 to 6 carbon atoms is more preferable. Examples of the aryl group as the substituent include a phenyl group, a naphthyl group, and an anthracenyl group, and a phenyl group is preferable.
炭素数6〜14のアリール基を置換基として有する又は無置換の炭素数1〜20のアルキルブロマイドの好ましい具体例としては、例えばメチルブロマイド、エチルブロマイド、n-プロピルブロマイド、イソプロピルブロマイド、n-ブチルブロマイド、イソブチルブロマイド、sec-ブチルブロマイド、tert-ブチルブロマイド、n-ペンチルブロマイド、イソペンチルブロマイド、sec-ペンチルブロマイド、tert-ペンチルブロマイド、ネオペンチルブロマイド、2-メチルブチルブロマイド、1-エチルプロピルブロマイド、n-ヘキシルブロマイド、イソヘキシルブロマイド、sec-ヘキシルブロマイド、tert-ヘキシルブロマイド、ネオヘキシルブロマイド、2-メチルペンチルブロマイド、3-メチルペンチルブロマイド、1,2-ジメチルブチルブロマイド、2,2-ジメチルブチルブロマイド、1-エチルブチルブロマイド、2-エチルブチルブロマイド、シクロプロピルブロマイド、シクロブチルブロマイド、シクロペンチルブロマイド、シクロヘキシルブロマイド、フェニルメチルブロマイド、フェニルエチルブロマイド、フェニル-n-プロピルブロマイド、フェニルイソプロピルブロマイド、フェニル-n-ブチルブロマイド、フェニルイソブチルブロマイド、フェニル-sec-ブチルブロマイド、フェニル-tert-ブチルブロマイド、フェニル-n-ペンチルブロマイド、フェニルイソペンチルブロマイド、フェニル-sec-ペンチルブロマイド、フェニル-tert-ペンチルブロマイド、フェニルネオペンチルブロマイド、4-フェニル-2-メチルブチルブロマイド、3-フェニル-1-エチルプロピルブロマイド、フェニル-n-ヘキシルブロマイド、フェニルイソヘキシルブロマイド、フェニル-sec-ヘキシルブロマイド、フェニル-tert-ヘキシルブロマイド、フェニルネオヘキシルブロマイド、5-フェニル-2-メチルペンチルブロマイド、5-フェニル-3-メチルペンチルブロマイド、4-フェニル-1,2-ジメチルブチルブロマイド、4-フェニル-2,2-ジメチルブチルブロマイド、4-フェニル-1-エチルブチルブロマイド、4-フェニル-2-エチルブチルブロマイド、フェニルシクロプロピルブロマイド、フェニルシクロブチルブロマイド、フェニルシクロペンチルブロマイド、フェニルシクロヘキシルブロマイド等が挙げられ、メチルブロマイド、エチルブロマイド、n-プロピルブロマイド、イソプロピルブロマイド、フェニルメチルブロマイド、フェニルエチルブロマイド、フェニル-n-プロピルブロマイド、フェニルイソプロピルブロマイド等が好ましく、フェニルメチルブロマイド、フェニルエチルブロマイド、フェニル-n-プロピルブロマイド、フェニルイソプロピルブロマイド等が好ましい。 Preferable specific examples of the alkyl bromide having an aryl group having 6 to 14 carbon atoms as a substituent or an unsubstituted alkyl group having 1 to 20 carbon atoms include, for example, methyl bromide, ethyl bromide, n-propyl bromide, isopropyl bromide, and n-butyl. Bromide, isobutyl bromide, sec-butyl bromide, tert-butyl bromide, n-pentyl bromide, isopentyl bromide, sec-pentyl bromide, tert-pentyl bromide, neopentyl bromide, 2-methylbutyl bromide, 1-ethylpropyl bromide, n-hexyl bromide, isohexyl bromide, sec-hexyl bromide, tert-hexyl bromide, neohexyl bromide, 2-methylpentyl bromide, 3-methylpentyl bromide, 1,2-dimethylbutyl bromide, 2,2-dimethyl Tyl bromide, 1-ethylbutyl bromide, 2-ethylbutyl bromide, cyclopropyl bromide, cyclobutyl bromide, cyclopentyl bromide, cyclohexyl bromide, phenylmethyl bromide, phenylethyl bromide, phenyl-n-propyl bromide, phenylisopropyl bromide, phenyl- n-butyl bromide, phenyl isobutyl bromide, phenyl-sec-butyl bromide, phenyl-tert-butyl bromide, phenyl-n-pentyl bromide, phenyl isopentyl bromide, phenyl-sec-pentyl bromide, phenyl-tert-pentyl bromide, phenyl Neopentyl bromide, 4-phenyl-2-methylbutyl bromide, 3-phenyl-1-ethylpropyl bromide, phenyl-n-hexyl bromide, phen Ruisohexyl bromide, phenyl-sec-hexyl bromide, phenyl-tert-hexyl bromide, phenyl neohexyl bromide, 5-phenyl-2-methylpentyl bromide, 5-phenyl-3-methylpentyl bromide, 4-phenyl-1, 2-dimethylbutyl bromide, 4-phenyl-2,2-dimethylbutyl bromide, 4-phenyl-1-ethylbutyl bromide, 4-phenyl-2-ethylbutyl bromide, phenylcyclopropyl bromide, phenylcyclobutyl bromide, phenylcyclopentyl Bromide, phenylcyclohexyl bromide, etc., such as methyl bromide, ethyl bromide, n-propyl bromide, isopropyl bromide, phenyl methyl bromide, phenyl ethyl bromide, phenyl-n-propyl bromide, phenyl iso B pills bromide and the like are preferable, phenyl bromide, phenylethyl bromide, phenyl -n- propyl bromide, phenyl isopropyl bromide are preferred.
炭素数6〜14のアリール基を置換基として有する又は無置換の炭素数1〜20のアルキルヨードとしては、炭素数6〜14のアリール基を置換基として有する又は無置換の炭素数1〜10のアルキルヨードが好ましく、炭素数6〜14のアリール基を置換基として有する又は無置換の炭素数1〜6のアルキルヨードがより好ましい。上記置換基としてのアリール基としては、例えばフェニル基、ナフチル基、アントラセニル基等が挙げられ、フェニル基が好ましい。 As a C1-C14 aryl group which has a C6-C14 aryl group as a substituent, or an unsubstituted C1-C20 alkyl iodo, it has a C6-C14 aryl group as a substituent, or is unsubstituted C1-C10 And an alkyliodine having 1 to 6 carbon atoms as a substituent or an unsubstituted alkyliodine having 1 to 6 carbon atoms is more preferable. Examples of the aryl group as the substituent include a phenyl group, a naphthyl group, and an anthracenyl group, and a phenyl group is preferable.
炭素数6〜14のアリール基を置換基として有する又は無置換の炭素数1〜20のアルキルヨードの好ましい具体例としては、例えばメチルヨード、エチルヨード、n-プロピルヨード、イソプロピルヨード、n-ブチルヨード、イソブチルヨード、sec-ブチルヨード、tert-ブチルヨード、n-ペンチルヨード、イソペンチルヨード、sec-ペンチルヨード、tert-ペンチルヨード、ネオペンチルヨード、2-メチルブチルヨード、1-エチルプロピルヨード、n-ヘキシルヨード、イソヘキシルヨード、sec-ヘキシルヨード、tert-ヘキシルヨード、ネオヘキシルヨード、2-メチルペンチルヨード、3-メチルペンチルヨード、1,2-ジメチルブチルヨード、2,2-ジメチルブチルヨード、1-エチルブチルヨード、2-エチルブチルヨード、シクロプロピルヨード、シクロブチルヨード、シクロペンチルヨード、シクロヘキシルヨード、フェニルメチルヨード、フェニルエチルヨード、フェニル-n-プロピルヨード、フェニルイソプロピルヨード、フェニル-n-ブチルヨード、フェニルイソブチルヨード、フェニル-sec-ブチルヨード、フェニル-tert-ブチルヨード、フェニル-n-ペンチルヨード、フェニルイソペンチルヨード、フェニル-sec-ペンチルヨード、フェニル-tert-ペンチルヨード、フェニルネオペンチルヨード、4-フェニル-2-メチルブチルヨード、3-フェニル-1-エチルプロピルヨード、フェニル-n-ヘキシルヨード、フェニルイソヘキシルヨード、フェニル-sec-ヘキシルヨード、フェニル-tert-ヘキシルヨード、フェニルネオヘキシルヨード、5-フェニル-2-メチルペンチルヨード、5-フェニル-3-メチルペンチルヨード、4-フェニル-1,2-ジメチルブチルヨード、4-フェニル-2,2-ジメチルブチルヨード、4-フェニル-1-エチルブチルヨード、4-フェニル-2-エチルブチルヨード、フェニルシクロプロピルヨード、フェニルシクロブチルヨード、フェニルシクロペンチルヨード、フェニルシクロヘキシルヨード等が挙げられる。 Preferable specific examples of the alkyliodine having a C6-C14 aryl group as a substituent or unsubstituted C1-C20 include, for example, methyliodine, ethyliodide, n-propyliodine, isopropyliodide, n-butyliodine, isobutyl Iodo, sec-butyliodide, tert-butyliodine, n-pentyliodide, isopentyliodine, sec-pentyliodide, tert-pentyliodine, neopentyliodine, 2-methylbutyliodine, 1-ethylpropyliodine, n-hexyliodine, Isohexyl iodide, sec-hexyl iodide, tert-hexyl iodide, neohexyl iodide, 2-methylpentyl iodide, 3-methylpentyl iodide, 1,2-dimethylbutyl iodide, 2,2-dimethylbutyl iodide, 1-ethylbutyl Iodo, 2-ethylbutyliodide, cyclopropyliodine, cyclobutyliodine , Cyclopentyliodine, cyclohexyliodine, phenylmethyliodine, phenylethyliodine, phenyl-n-propyliodine, phenylisopropyliodine, phenyl-n-butyliodine, phenylisobutyliodine, phenyl-sec-butyliodine, phenyl-tert-butyliodine, phenyl- n-pentyliodine, phenylisopentyliodine, phenyl-sec-pentyliodine, phenyl-tert-pentyliodine, phenylneopentyliodine, 4-phenyl-2-methylbutyliodine, 3-phenyl-1-ethylpropyliodine, phenyl -n-hexyliodine, phenylisohexyliodine, phenyl-sec-hexyliodine, phenyl-tert-hexyliodine, phenylneohexyliodide, 5-phenyl-2-methylpentyliodide, 5-phenyl-3-methylpentyliodide, 4-phenyl-1,2-di Butylbutyl iodide, 4-phenyl-2,2-dimethylbutyliodide, 4-phenyl-1-ethylbutyliodide, 4-phenyl-2-ethylbutyliodine, phenylcyclopropyliodine, phenylcyclobutyliodine, phenylcyclopentyliodide, Phenyl cyclohexyl iodo etc. are mentioned.
炭素数2〜20のアルケニルブロマイドとしては、炭素数2〜10のアルケニルブロマイドが好ましく、炭素数2〜6のアルケニルブロマイドがより好ましい。好ましい具体例としては、例えばビニルブロマイド、アリルブロマイド、1-プロペニルブロマイド、イソプロペニルブロマイド、1-ブテニルブロマイド、2-ブテニルブロマイド、3-ブテニルブロマイド、2-メチルアリルブロマイド、1-ペンテニルブロマイド、2-ペンテニルブロマイド、3-ペンテニルブロマイド、4-ペンテニルブロマイド、2-ブロモ-3-メチルブテン、1-ヘキセニルブロマイド、2-ヘキセニルブロマイド、3-ヘキセニルブロマイド、5-ヘキセニルブロマイド、2-メチル-2-ペンテニルブロマイド、1-シクロブテニルブロマイド、1-シクロペンテニルブロマイド、1-シクロヘキセニルブロマイド等が挙げられ、2-ブロモ-3-メチルブテンが好ましい。 As a C2-C20 alkenyl bromide, a C2-C10 alkenyl bromide is preferable and a C2-C6 alkenyl bromide is more preferable. Preferred examples include vinyl bromide, allyl bromide, 1-propenyl bromide, isopropenyl bromide, 1-butenyl bromide, 2-butenyl bromide, 3-butenyl bromide, 2-methylallyl bromide, 1-pentenyl bromide. 2-pentenyl bromide, 3-pentenyl bromide, 4-pentenyl bromide, 2-bromo-3-methylbutene, 1-hexenyl bromide, 2-hexenyl bromide, 3-hexenyl bromide, 5-hexenyl bromide, 2-methyl-2- Examples include pentenyl bromide, 1-cyclobutenyl bromide, 1-cyclopentenyl bromide, 1-cyclohexenyl bromide, and 2-bromo-3-methylbutene is preferred.
炭素数2〜20のアルケニルヨードとしては、炭素数2〜10のアルケニルヨードが好ましく、炭素数2〜6のアルケニルヨードがより好ましい。好ましい具体例としては、例えばビニルヨード、アリルヨード、1-プロペニルヨード、イソプロペニルヨード、1-ブテニルヨード、2-ブテニルヨード、3-ブテニルヨード、2-メチルアリルヨード、1-ペンテニルヨード、2-ペンテニルヨード、3-ペンテニルヨード、4-ペンテニルヨード、2-メチル-2-ブテニルヨード、1-ヘキセニルヨード、2-ヘキセニルヨード、3-ヘキセニルヨード、5-ヘキセニルヨード、2-メチル-2-ペンテニルヨード、1-シクロブテニルヨード、1-シクロペンテニルヨード、1-シクロヘキセニルヨード等が挙げられる。 As a C2-C20 alkenyl iodide, a C2-C10 alkenyl iodide is preferable and a C2-C6 alkenyl iodine is more preferable. Preferable specific examples include, for example, vinyl iodide, allyl iodide, 1-propenyl iodide, isopropenyl iodide, 1-butenyl iodide, 2-butenyl iodide, 3-butenyl iodide, 2-methylallyl iodide, 1-pentenyl iodide, 2-pentenyl iodide, 3-pentenyl iodide, Pentenyliodine, 4-pentenyliodine, 2-methyl-2-butenyliodine, 1-hexenyliodine, 2-hexenyliodine, 3-hexenyliodine, 5-hexenyliodine, 2-methyl-2-pentenyliodine, 1-cyclobutenyl Examples include iodo, 1-cyclopentenyl iodo, 1-cyclohexenyl iodo and the like.
炭素数2〜20のアルキニルブロマイドとしては、炭素数2〜10のアルキニルブロマイドが好ましく、炭素数2〜6のアルキニルブロマイドがより好ましい。好ましい具体例としては、例えばエチニルブロマイド、1-プロピニルブロマイド、2-プロピニルブロマイド、1-ブチニルブロマイド、2-ブチニルブロマイド、3-ブチニルブロマイド、1-メチル-2-プロピニルブロマイド、1-ペンチニルブロマイド、2-ペンチニルブロマイド、3-ペンチニルブロマイド、4-ペンチニルブロマイド、1-メチル-3-ブチニルブロマイド、1-ヘキシニルブロマイド、2-ヘキシニルブロマイド、3-ヘキシニルブロマイド、4-ヘキシニルブロマイド、5-ヘキシニルブロマイド、2-メチル-4-へプチニルブロマイド等が挙げられる。 As a C2-C20 alkynyl bromide, a C2-C10 alkynyl bromide is preferable and a C2-C6 alkynyl bromide is more preferable. Preferable specific examples include, for example, ethynyl bromide, 1-propynyl bromide, 2-propynyl bromide, 1-butynyl bromide, 2-butynyl bromide, 3-butynyl bromide, 1-methyl-2-propynyl bromide, 1-pentyl Nyl bromide, 2-pentynyl bromide, 3-pentynyl bromide, 4-pentynyl bromide, 1-methyl-3-butynyl bromide, 1-hexynyl bromide, 2-hexynyl bromide, 3-hexynyl bromide, 4 -Hexynyl bromide, 5-hexynyl bromide, 2-methyl-4-heptynyl bromide and the like.
炭素数2〜20のアルキニルヨードとしては、炭素数2〜10のアルキニルヨードが好ましく、炭素数2〜6のアルキニルヨードがより好ましい。好ましい具体例としては、例えばエチニルヨード、1-プロピニルヨード、2-プロピニルヨード、1-ブチニルヨード、2-ブチニルヨード、3-ブチニルヨード、1-メチル-2-プロピニルヨード、1-ペンチニルヨード、2-ペンチニルヨード、3-ペンチニルヨード、4-ペンチニルヨード、1-メチル-3-ブチニルヨード、1-ヘキシニルヨード、2-ヘキシニルヨード、3-ヘキシニルヨード、4-ヘキシニルヨード、5-ヘキシニルヨード、2-メチル-4-へプチニルヨード等が挙げられる。 As a C2-C20 alkynyl iodide, a C2-C10 alkynyl iodine is preferable and a C2-C6 alkynyl iodine is more preferable. Preferable specific examples include, for example, ethynyl iodide, 1-propynyl iodide, 2-propynyl iodide, 1-butynyl iodide, 2-butynyl iodide, 3-butynyl iodide, 1-methyl-2-propynyl iodide, 1-pentynyl iodide, 2-pentyl iodide Nyliodo, 3-pentynyliodine, 4-pentynyliodine, 1-methyl-3-butynyliodine, 1-hexynyliodine, 2-hexynyliodine, 3-hexynyliodine, 4-hexynyliodine, 5-hexynyliodide, 2-methyl-4-to Putinyl iodine and the like can be mentioned.
上記一般式(V)で示される有機ハロゲン化合物は、市販のものであっても、自体公知の方法により製造したものであっても何れでもよい。 The organic halogen compound represented by the general formula (V) may be either a commercially available product or a product produced by a method known per se.
[一般式(VI)で示される化合物]
一般式(VI)で示される化合物におけるR3の炭素数1〜6のアルキル基としては、直鎖状、分枝状或いは環状でもよく、好ましくは炭素数1〜3、より好ましくは炭素数1のものが挙げられる。具体的には、例えばメチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、イソペンチル基、sec-ペンチル基、tert-ペンチル基、ネオペンチル基、2-メチルブチル基、1-エチルプロピル基、n-ヘキシル基、イソヘキシル基、sec-ヘキシル基、tert-ヘキシル基、ネオヘキシル基、2-メチルペンチル基、3-メチルペンチル基、1,2-ジメチルブチル基、2,2-ジメチルブチル基、1-エチルブチル基、2-エチルブチル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等が挙げられる。中でも、メチル基、エチル基、n-プロピル基、イソプロピル基が好ましく、メチル基がより好ましい。
[Compound represented by formula (VI)]
The alkyl group having 1 to 6 carbon atoms of R 3 in the compound represented by the general formula (VI) may be linear, branched or cyclic, preferably 1 to 3 carbon atoms, more preferably 1 carbon atom. Can be mentioned. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group Tert-pentyl group, neopentyl group, 2-methylbutyl group, 1-ethylpropyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2-methylpentyl group, 3-methyl Examples include pentyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like. Of these, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are preferable, and a methyl group is more preferable.
一般式(VI)で示される化合物におけるR3の炭素数6〜10のアリール基としては、例えばフェニル基、ナフチル基等が挙げられる。 Examples of the aryl group having 6 to 10 carbon atoms of R 3 in the compound represented by the general formula (VI) include a phenyl group and a naphthyl group.
3個のR3は、それぞれ同じであっても異なっていてもよいが、異なる2種類の基で構成されるのが好ましく、例えば1個がアリール基で残りの2個がアルキル基から選ばれる同じ基、或いは1個がアルキル基で残りの2個がアリール基から選ばれる同じ基等が好ましい。より具体的には例えば1個がフェニル基で残りの2個がメチル基、1個がメチル基で残り2個がフェニル基等の組合せが好ましい。 The three R 3 groups may be the same or different, but are preferably composed of two different groups, for example, one is an aryl group and the remaining two are selected from an alkyl group. The same group or the same group in which one is an alkyl group and the remaining two are selected from an aryl group is preferable. More specifically, for example, a combination of one phenyl group and the remaining two methyl groups, one methyl group and the remaining two phenyl groups is preferable.
一般式(VI)で示される化合物におけるR4の炭素数1〜3のアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基が挙げられ、メチル基が好ましい。4個のR4は、それぞれ同じであっても異なっていてもよいが、全てが同じであるのが好ましい。 Examples of the alkyl group having 1 to 3 carbon atoms of R 4 in the compound represented by the general formula (VI) include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and a methyl group is preferable. The four R 4 s may be the same or different from each other, but all are preferably the same.
一般式(VI)で示される化合物の好ましいものとしては、例えば以下のものが挙げられる。
Preferred examples of the compound represented by the general formula (VI) include the following.
上記一般式(VI)で示される化合物は、市販のものであっても、自体公知の方法により製造したものであっても何れでもよい。 The compound represented by the general formula (VI) may be either a commercially available product or a compound produced by a method known per se.
[本発明に係る一般式(VII)で示される化合物]
(式中、R及びR4は、上記と同じ。)
一般式(VII)におけるRの具体例及び好ましい具体例は、一般式(V)のRと同じものが挙げられる。
[Compound represented by formula (VII) according to the present invention]
(In the formula, R and R 4 are the same as above.)
Specific examples and preferred specific examples of R in the general formula (VII) include the same as R in the general formula (V).
一般式(VII)におけるR4の具体例及び好ましい具体例は、一般式(VI)のR4と同じものが挙げられる。 Specific examples and preferred specific examples of R 4 in the general formula (VII) include the same as R 4 in the general formula (VI).
一般式(VII)で示される化合物の具体例としては、下記一般式[VI−1]〜[VI−6]が挙げられ、[VI−1]が特に好ましい。
(式中、Rは上記と同じ。)
Specific examples of the compound represented by the general formula (VII) include the following general formulas [VI-1] to [VI-6], and [VI-1] is particularly preferable.
(In the formula, R is the same as above.)
[本発明に係るナトリウムアルコキシド又はカリウムアルコキシド]
本発明に係るナトリウムアルコキシドとしては、通常炭素数1〜6、好ましくは炭素数1〜4のものが挙げられ、具体的には、ナトリウムメトキシド、ナトリウムエトキシド、ナトリウムn-プロポキシド、ナトリウムイソプロポキシド、ナトリウムn-ブトキシド、ナトリウムイソブトキシド、ナトリウムsec-ブトキシド、ナトリウムtert-ブトキシド、ナトリウムn-ペンチルオキシド、ナトリウムイソペンチルオキシド、ナトリウムsec-ペンチルオキシド、ナトリウムtert-ペンチルオキシド、ナトリウムネオペンチルオキシド、ナトリウムn-ヘキシルオキシド、ナトリウムイソヘキシルオキシド、ナトリウムsec-ヘキシルオキシド、ナトリウムtert-ヘキシルオキシド、ナトリウムネオヘキシルオキシド等が挙げられ、ナトリウムメトキシド、ナトリウムエトキシド、ナトリウムn-プロポキシド、ナトリウムイソプロポキシド、ナトリウムn-ブトキシド、ナトリウムtert-ブトキシド等が好ましく、ナトリウムメトキシドがより好ましい。
[Sodium alkoxide or potassium alkoxide according to the present invention]
Examples of the sodium alkoxide according to the present invention include those having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Specifically, sodium methoxide, sodium ethoxide, sodium n-propoxide, sodium Propoxide, sodium n-butoxide, sodium isobutoxide, sodium sec-butoxide, sodium tert-butoxide, sodium n-pentyl oxide, sodium isopentyl oxide, sodium sec-pentyl oxide, sodium tert-pentyl oxide, sodium neopentyl oxide, Examples include sodium n-hexyl oxide, sodium isohexyl oxide, sodium sec-hexyl oxide, sodium tert-hexyl oxide, sodium neohexyl oxide, sodium methoxide, sodium Tokishido, sodium n- propoxide, sodium isopropoxide, sodium n- butoxide, sodium tert- butoxide, and more preferably sodium methoxide.
本発明に係るカリウムアルコキシドとしては、通常炭素数1〜6、好ましくは炭素数1〜4のものが挙げられ、具体的には、カリウムメトキシド、カリウムエトキシド、カリウムn-プロポキシド、カリウムイソプロポキシド、カリウムn-ブトキシド、カリウムイソブトキシド、カリウムsec-ブトキシド、カリウムtert-ブトキシド、カリウムn-ペンチルオキシド、カリウムイソペンチルオキシド、カリウムsec-ペンチルオキシド、カリウムtert-ペンチルオキシド、カリウムネオペンチルオキシド、カリウムn-ヘキシルオキシド、カリウムイソヘキシルオキシド、カリウムsec-ヘキシルオキシド、カリウムtert-ヘキシルオキシド、カリウムネオヘキシルオキシド等が挙げられ、カリウムメトキシド、カリウムエトキシド、カリウムn-プロポキシド、カリウムイソプロポキシド、カリウムn-ブトキシド、カリウムtert-ブトキシド等が好ましい。 Examples of the potassium alkoxide according to the present invention include those having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and specifically include potassium methoxide, potassium ethoxide, potassium n-propoxide, potassium isopropanol. Propoxide, potassium n-butoxide, potassium isobutoxide, potassium sec-butoxide, potassium tert-butoxide, potassium n-pentyl oxide, potassium isopentyl oxide, potassium sec-pentyl oxide, potassium tert-pentyl oxide, potassium neopentyl oxide, Examples include potassium n-hexyl oxide, potassium isohexyl oxide, potassium sec-hexyl oxide, potassium tert-hexyl oxide, potassium neohexyl oxide, potassium methoxide, potassium ethoxide, potassium n-propoxide, potassium Isopropoxide, potassium n-butoxide, potassium tert-butoxide and the like are preferable.
[本発明の一般式(VII)で示される化合物の製造方法(本発明の製造方法)]
本発明の製造方法は、上記一般式(V)で示される有機ハロゲン化合物と上記一般式(VI)で示される化合物とを、ナトリウムアルコキシド又はカリウムアルコキシドの存在下で反応させることによりなされる。この反応の結果、一般式(V)で示される化合物中の臭素原子又はヨウ素原子は、一般式(VI)で示される化合物中のジオールホウ素基で置換され、一般式(VII)で示される化合物が製造される。
[Production method of the compound represented by the general formula (VII) of the present invention (production method of the present invention)]
The production method of the present invention is performed by reacting the organic halogen compound represented by the general formula (V) with the compound represented by the general formula (VI) in the presence of sodium alkoxide or potassium alkoxide. As a result of this reaction, the bromine atom or iodine atom in the compound represented by the general formula (V) is substituted with the diol boron group in the compound represented by the general formula (VI), and the compound represented by the general formula (VII) Is manufactured.
本発明の一般式(VII)で示される化合物の製造方法における一般式(VI)で示される化合物の使用量は、一般式(V)で示される化合物に対して、通常1〜5当量、好ましくは1〜2当量、より好ましくは1〜1.5当量、更に好ましくは1.2〜1.5当量である。 The amount of the compound represented by the general formula (VI) in the process for producing the compound represented by the general formula (VII) of the present invention is usually 1 to 5 equivalents, preferably with respect to the compound represented by the general formula (V). Is 1 to 2 equivalents, more preferably 1 to 1.5 equivalents, still more preferably 1.2 to 1.5 equivalents.
本発明の一般式(VII)で示される化合物の製造方法におけるナトリウムメトキシド又はカリウムメトキシドの使用量は、一般式(V)で示される化合物に対して、通常1〜5当量、好ましくは1〜2当量、より好ましくは1〜1.5当量、更に好ましくは1〜1.2当量である。 The amount of sodium methoxide or potassium methoxide used in the process for producing the compound represented by the general formula (VII) of the present invention is usually 1 to 5 equivalents, preferably 1 with respect to the compound represented by the general formula (V). ˜2 equivalents, more preferably 1 to 1.5 equivalents, still more preferably 1 to 1.2 equivalents.
本発明の一般式(VII)で示される化合物の製造方法は、有機溶媒中でなされるのが好ましい。該有機溶媒としては、エーテル系溶媒が好ましく、具体的には、例えばジエチルエーテル、エチレングリコールジエチルエーテル、ジブチルエーテル、tert-ブチルメチルエーテル、ジオキサン、ジオキソラン、ジメトキシエタン、ジエトキシエタン、テトラヒドロフラン等が挙げられる。中でもジメトキシエタン、テトラヒドロフラン、ジオキサンが好ましい。該有機溶媒の使用量は、一般式(V)で示される化合物1mmolに対して、通常1〜50mL、好ましくは1〜10mL、より好ましくは5〜10mLである。 The method for producing the compound represented by the general formula (VII) of the present invention is preferably carried out in an organic solvent. The organic solvent is preferably an ether solvent, and specific examples include diethyl ether, ethylene glycol diethyl ether, dibutyl ether, tert-butyl methyl ether, dioxane, dioxolane, dimethoxyethane, diethoxyethane, tetrahydrofuran and the like. It is done. Of these, dimethoxyethane, tetrahydrofuran and dioxane are preferred. The amount of the organic solvent to be used is generally 1 to 50 mL, preferably 1 to 10 mL, more preferably 5 to 10 mL with respect to 1 mmol of the compound represented by the general formula (V).
本発明の一般式(VII)で示される化合物の製造方法における反応温度は、通常0〜100℃、好ましくは20〜60℃、より好ましくは20〜40℃である。反応時間は、一般式(V)で示される化合物が全て反応する時間であればよく、通常0.5〜5時間、好ましくは0.5〜3時間、より好ましくは1〜2時間である。 The reaction temperature in the production method of the compound represented by the general formula (VII) of the present invention is usually 0 to 100 ° C, preferably 20 to 60 ° C, more preferably 20 to 40 ° C. Reaction time should just be time for which all the compounds shown by general formula (V) react, and are 0.5 to 5 hours normally, Preferably it is 0.5 to 3 hours, More preferably, it is 1-2 hours.
本発明の一般式(VII)で示される化合物の製造方法としては、具体的には例えば、上記一般式(V)で示される化合物と、一般式(V)で示される化合物に対して1〜2当量の一般式(VI)で示される化合物とを、一般式(V)で示される化合物に対して1〜1.5当量のナトリウムメトキシド又はカリウムメトキシドの存在下、上記有機溶媒1〜100mL中0〜90℃で0.5〜3時間反応させればよい。より具体的には例えば、ブロモベンゼン1mmolと(ジメチルフェニルシリル)ボロン酸ピナコールエステル1〜2mmolとを、ナトリウムメトキシド又はカリウムメトキシド1〜1.5mmolの存在下、エーテル系有機溶媒10〜20mL中20〜40℃で、1〜2時間反応させることにより、フェニルボロン酸ピナコールエステル又はその誘導体を得ることができる。 Specific examples of the method for producing the compound represented by the general formula (VII) of the present invention include 1 to the compound represented by the general formula (V) and the compound represented by the general formula (V). 2 equivalents of the compound represented by the general formula (VI) in the presence of 1 to 1.5 equivalents of sodium methoxide or potassium methoxide with respect to the compound represented by the general formula (V) What is necessary is just to make it react for 0.5 to 3 hours at 0-90 degreeC in 100 mL. More specifically, for example, 1 mmol of bromobenzene and 1-2 mmol of (dimethylphenylsilyl) boronic acid pinacol ester in the presence of sodium methoxide or 1-1.5 mmol of potassium methoxide in 10-20 mL of an ether organic solvent. By reacting at 20 to 40 ° C. for 1 to 2 hours, phenylboronic acid pinacol ester or a derivative thereof can be obtained.
実施例1 4−メトキシフェニルボロン酸ピナコールエステルの製造方法
アルゴン雰囲気下でカリウムメトキシド(KOMe)(ALDRICH社製)42.1 mg(0.6 mmol)、1,2−ジメトキシエタン(DME)5 ml、及び(ジメチルフェニルシリル)ボロン酸ピナコールエステル(ALDRICH社製)196.7mg(0.75 mmol)を加え、30℃で10分間撹拌した。その後、4−ブロモアニソール(和光純薬工業(株)製)93.5 mg(0.50 mmol)を滴下し、1時間反応させた後に、反応混合物をガスクロマトグラフィー(GC)を用いて分析し、反応が完了しているかを確認した。
Example 1 Method for producing 4-methoxyphenylboronic acid pinacol ester 42.1 mg (0.6 mmol) of potassium methoxide (KOMe) (manufactured by ALDRICH), 5 ml of 1,2-dimethoxyethane (DME), and (under argon atmosphere) 196.7 mg (0.75 mmol) of dimethylphenylsilyl) boronic acid pinacol ester (manufactured by ALDRICH) was added, and the mixture was stirred at 30 ° C. for 10 minutes. Thereafter, 93.5 mg (0.50 mmol) of 4-bromoanisole (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise and reacted for 1 hour, and then the reaction mixture was analyzed using gas chromatography (GC). Confirmed completion.
反応後に0℃に冷却し、フッ化テトラブチルアンモニウム(TBAF)(1.0 M,800 μl)を加え、3時間撹拌した。その後、混合溶液に水100 mlを加え、次いでジエチルエーテル50 mlで目的物を抽出した。有機層を水50 mlで2回洗浄した後、硫酸マグネシウムを加えて乾燥した。硫酸マグネシウムをろ過後、ろ液のジエチルエーテルを留去した。得られた粗生成物を、ホウ素含浸シリカゲルカラムクロマトグラフィを用いて0−5% ヘキサン/ジエチルエーテル溶離液で精製し、無色オイル状の4−メトキシフェニルボロン酸ピナコールエステルを得た。GCから算出した収率は92%、単離時の収率は77%であった。 After the reaction, the reaction mixture was cooled to 0 ° C., tetrabutylammonium fluoride (TBAF) (1.0 M, 800 μl) was added, and the mixture was stirred for 3 hours. Thereafter, 100 ml of water was added to the mixed solution, and then the target product was extracted with 50 ml of diethyl ether. The organic layer was washed twice with 50 ml of water and then dried by adding magnesium sulfate. After filtering the magnesium sulfate, the diethyl ether in the filtrate was distilled off. The obtained crude product was purified with a boron-impregnated silica gel column chromatography with an eluent of 0-5% hexane / diethyl ether to obtain 4-methoxyphenylboronic acid pinacol ester as colorless oil. The yield calculated from GC was 92%, and the yield at the time of isolation was 77%.
該反応の反応スキームを以下に示す。尚、カッコ内のシリル化生成物は目的物以外の副産物を表す。
上記反応の条件[ハロゲン化アリールのハロゲンの種類(X)、使用溶媒、使用塩基、及び反応温度]、GCから算出した収率、及びホウ素化生成物対シリル化生成物の比(B/Si)について表1に示す。
The reaction scheme of this reaction is shown below. The silylated product in parentheses represents a by-product other than the target product.
Conditions for the above reaction [halogen type of aryl halide (X), solvent used, base used, and reaction temperature], yield calculated from GC, and ratio of boronated product to silylated product (B / Si ) Is shown in Table 1.
尚、得られた4−メトキシフェニルボロン酸ピナコールエステルの物性データを以下に示す。
〔物性データ〕
1H NMR(400 MHz,CDCl3):δ=1.33(s,12H),3.83(s,3H),6.90(dt,J=2.3,8.7 Hz,2H),7.75(dt,J=2.1,8.7 Hz,2H);13C NMR(100 MHz,CDCl3):δ=24.9(CH3),55.2(CH3),83.6(C),113.4(CH),136.6(CH),162.2(C);HRMS-APCI m/z [M+H]+ calcd C13H20O3 10B,234.15363;found,234.15370.
The physical property data of the obtained 4-methoxyphenylboronic acid pinacol ester is shown below.
[Physical property data]
1 H NMR (400 MHz, CDCl 3 ): δ = 1.33 (s, 12H), 3.83 (s, 3H), 6.90 (dt, J = 2.3, 8.7 Hz, 2H), 7.75 (dt, J = 2.1, 8.7 13 C NMR (100 MHz, CDCl 3 ): δ = 24.9 (CH 3 ), 55.2 (CH 3 ), 83.6 (C), 113.4 (CH), 136.6 (CH), 162.2 (C); HRMS-APCI m / z [M + H] + calcd C 13 H 20 O 3 10 B, 234.15363; found, 234.15370.
実施例2 テトラヒドロフランを溶媒として用いた4−メトキシフェニルボロン酸ピナコールエステルの製造方法
実施例1の使用溶媒DMEの代わりにテトラヒドロフラン(THF)(和光純薬工業(株)製)を用いた以外は実施例1と同様の方法により行い、4−メトキシフェニルボロン酸ピナコールエステルを得た。
該反応の条件[ハロゲン化アリールのハロゲンの種類(X)、使用溶媒、使用塩基、及び反応温度]、GCから算出した収率、及びB/Siについて、実施例1のそれらと併せて表1に示す。尚、得られた生成物の物性データは実施例1と同じであった。
Example 2 Production method of 4-methoxyphenylboronic acid pinacol ester using tetrahydrofuran as a solvent Implementation was performed except that tetrahydrofuran (THF) (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of the solvent DME used in Example 1. In the same manner as in Example 1, 4-methoxyphenylboronic acid pinacol ester was obtained.
The reaction conditions [halogen type of aryl halide (X), solvent used, base used, and reaction temperature], yield calculated from GC, and B / Si are shown in Table 1 together with those of Example 1. Shown in The physical property data of the obtained product was the same as in Example 1.
比較例1−4 各種有機溶媒を用いた4−メトキシフェニルボロン酸ピナコールエステルの製造方法
実施例1の使用溶媒DMEの代わりに、それぞれトルエン、ジクロロメタン(CH2Cl2)、N,N-ジメチルホルムアミド(DMF)、又はメタノール(MeOH)を用いた以外は実施例1と同様の方法により行った。
Comparative Example 1-4 Method for producing 4-methoxyphenylboronic acid pinacol ester using various organic solvents Toluene, dichloromethane (CH 2 Cl 2 ) and N, N-dimethylformamide were used in place of the solvent DME used in Example 1. (DMF) or methanol (MeOH) was used, and the same method as in Example 1 was used.
該反応の条件[ハロゲン化アリールのハロゲンの種類(X)、使用溶媒、使用塩基、及び反応温度]、GCから算出した収率、及びB/Siについて実施例1及び2のそれらと併せて表1に示す。尚、得られた生成物の物性データは実施例1と同じであった。 Conditions of the reaction [type of halogen of aryl halide (X), solvent used, base used, reaction temperature], yield calculated from GC, and B / Si are shown together with those of Examples 1 and 2. Shown in 1. The physical property data of the obtained product was the same as in Example 1.
表1の結果より、1,2−ジメトキシエタン(DME)やテトラヒドロフラン(THF)等のエーテル系溶媒を用いると効率よく反応が進み、85%以上の高い収率で目的物が得られること分かった。一方、トルエン、ジクロロメタン(CH2Cl2)、N,N-ジメチルホルムアミド(DMF)、メタノールを用いた場合、収率が非常に低かった。特に、DMF及びメタノールでは、反応が進まないことが分かった。 From the results in Table 1, it was found that when an ether solvent such as 1,2-dimethoxyethane (DME) or tetrahydrofuran (THF) was used, the reaction proceeded efficiently and the target product was obtained with a high yield of 85% or more. . On the other hand, when toluene, dichloromethane (CH 2 Cl 2 ), N, N-dimethylformamide (DMF), and methanol were used, the yield was very low. In particular, it was found that the reaction did not proceed with DMF and methanol.
実施例3−4 反応温度の違いによる反応への影響
実施例1の反応温度を50℃及び0℃に変えた以外は実施例1と同様の方法により行い、4−メトキシフェニルボロン酸ピナコールエステルを得た。
Example 3-4 Effect on reaction due to difference in reaction temperature Except that the reaction temperature of Example 1 was changed to 50 ° C. and 0 ° C., it was carried out in the same manner as in Example 1, and 4-methoxyphenylboronic acid pinacol ester was obtained. Obtained.
該反応の条件[ハロゲン化アリールのハロゲンの種類(X)、使用溶媒、使用塩基、及び反応温度]、GCから算出した収率、及びB/Siについて、実施例1のそれらと併せて表2に示す。尚、得られた生成物の物性データは実施例1と同じであった。 The reaction conditions [halogen type (X) of aryl halide, solvent used, base used, reaction temperature], yield calculated from GC, and B / Si are shown in Table 2 together with those of Example 1. Shown in The physical property data of the obtained product was the same as in Example 1.
表2の結果より、30℃での反応が最も効率よいが、50℃や0℃でも80%以上の高い収率で目的物が得られることが分かった。尚、0℃の場合、ホウ素化生成物に対するシリル化生成物の比率が、30℃及び50℃と比較して若干上がることが分かった。 From the results in Table 2, it was found that the reaction at 30 ° C. was most efficient, but the target product was obtained at a high yield of 80% or higher even at 50 ° C. or 0 ° C. In addition, in the case of 0 degreeC, it turned out that the ratio of the silylated product with respect to a boronation product raises a little compared with 30 degreeC and 50 degreeC.
実施例5−6 各種塩基を用いた4−メトキシフェニルボロン酸ピナコールエステルの製造方法
実施例1の使用塩基KOMeの代わりにナトリウムメトキシド(NaOMe)又はカリウムtert-ブトキシド(KOtBu)を用いた以外は実施例1と同様の方法により行い、4−メトキシフェニルボロン酸ピナコールエステルを得た。
該反応の条件[ハロゲン化アリールのハロゲンの種類(X)、使用溶媒、使用塩基、及び反応温度]、GCから算出した収率、及びB/Siについて表3に示す。尚、得られた生成物の物性データは実施例1と同じであった。
Example 5-6 Method for Producing 4-Methoxyphenylboronic Acid Pinacol Ester Using Various Bases Use of Example 1 Sodium methoxide (NaOMe) or potassium tert-butoxide (KO t Bu) was used in place of KOMe. Except that, 4-methoxyphenylboronic acid pinacol ester was obtained in the same manner as in Example 1.
Table 3 shows the reaction conditions [halogen type (X) of aryl halide, solvent used, base used, reaction temperature], yield calculated from GC, and B / Si. The physical property data of the obtained product was the same as in Example 1.
比較例5−10 各種塩基を用いた4−メトキシフェニルボロン酸ピナコールエステルの製造方法
実施例1の使用塩基KOMeの代わりにそれぞれリチウムメトキシド(LiOMe)、酢酸カリウム(KOAc)、炭酸カリウム(K2CO3)、フッ化カリウム(KF)、又はジアザビシクロウンデセン(DBU)(和光純薬工業(株)製)を用いた以外は実施例1と同様の方法により行った。また、比較例10では、塩基を使用しなかった以外は実施例1と同様の方法により行った。
該反応の条件[ハロゲン化アリールのハロゲンの種類(X)、使用溶媒、使用塩基、及び反応温度]、GCから算出した収率、及びB/Siについて、実施例5及び6のそれらと併せて表3に示す。
Comparative Example 5-10 Method for Producing 4-Methoxyphenylboronic Acid Pinacol Ester Using Various Bases Used in Example 1 Lithium methoxide (LiOMe), potassium acetate (KOAc), potassium carbonate (K 2 ) instead of KOMe This was carried out in the same manner as in Example 1 except that CO 3 ), potassium fluoride (KF), or diazabicycloundecene (DBU) (manufactured by Wako Pure Chemical Industries, Ltd.) was used. Moreover, in the comparative example 10, it carried out by the method similar to Example 1 except not using a base.
The reaction conditions [halogen type (X) of aryl halide, solvent used, base used, and reaction temperature], yield calculated from GC, and B / Si were combined with those of Examples 5 and 6. Table 3 shows.
表3の結果より、ナトリウムメトキシド及びカリウムtert-ブトキシドを塩基として用いるとホウ素置換反応が進むことが分かった。一方、リチウムメトキシド(LiOMe)、酢酸カリウム(KOAc)、炭酸カリウム(K2CO3)、フッ化カリウム(KF)、又はジアザビシクロウンデセン(DBU)を塩基として用いた場合には反応が進まないことが分かった。
実施例1、2、5及び6の結果より、ナトリウムアルコキシドやカリウムアルコキシドを用いるとホウ素置換反応が効率よく進むことが分かった。
From the results in Table 3, it was found that boron substitution reaction proceeds when sodium methoxide and potassium tert-butoxide are used as bases. On the other hand, when lithium methoxide (LiOMe), potassium acetate (KOAc), potassium carbonate (K 2 CO 3 ), potassium fluoride (KF), or diazabicycloundecene (DBU) is used as the base, the reaction I found out that it was not going.
From the results of Examples 1, 2, 5 and 6, it was found that boron substitution reaction proceeds efficiently when sodium alkoxide or potassium alkoxide is used.
実施例7 ヨウ化物を出発物質としたジオールホウ素化合物の製造方法
実施例1の4−ブロモアニソールの代わりに4−ヨードアニソールを用いた以外は実施例1と同様の方法により行い、4−メトキシフェニルボロン酸ピナコールエステルを得た。
該反応の条件[ハロゲン化アリールのハロゲンの種類(X)、使用溶媒、使用塩基、及び反応温度]、GCから算出した収率、及びB/Siについて、実施例1のそれらと併せて表4に示す。尚、得られた生成物の物性データは実施例1と同じであった。
Example 7 Production Method of Diol Boron Compound Using Iodide as Starting Material 4- methoxyphenyl was prepared in the same manner as in Example 1 except that 4-iodoanisole was used instead of 4- bromoanisole in Example 1. Boronic acid pinacol ester was obtained.
Table 4 shows the reaction conditions [halogen type of aryl halide (X), solvent used, base used, reaction temperature], yield calculated from GC, and B / Si together with those of Example 1. Shown in The physical property data of the obtained product was the same as in Example 1.
比較例11 塩化物を出発物質としたジオールホウ素化合物の製造方法
実施例7の4−ヨードアニソールの代わりに4−クロロアニソールを用いた以外は実施例7と同様の方法により行い、4−メトキシフェニルボロン酸ピナコールエステルを得た。
該反応の条件[ハロゲン化アリールのハロゲンの種類(X)、使用溶媒、使用塩基、及び反応温度]、GCから算出した収率、及びB/Siについて、実施例1及び7のそれらと併せて表4に示す。尚、得られた生成物の物性データは実施例1と同じであった。
Comparative Example 11 Production Method of Diol Boron Compound Using Chloride as Starting Material 4-methoxyphenyl was prepared in the same manner as in Example 7 except that 4-chloroanisole was used instead of 4- iodoanisole in Example 7. Boronic acid pinacol ester was obtained.
The reaction conditions [halogen type (X) of aryl halide, solvent used, base used, and reaction temperature], yield calculated from GC, and B / Si were combined with those of Examples 1 and 7. Table 4 shows. The physical property data of the obtained product was the same as in Example 1.
表4の結果より、臭素及びヨウ素が置換基の場合は、ホウ素置換反応が効率よく進むことが分かった。一方、ハロゲン原子であっても置換基が塩素の場合は、ホウ素置換反応があまり進まないことが分かった。 From the results in Table 4, it was found that when bromine and iodine are substituents, the boron substitution reaction proceeds efficiently. On the other hand, it was found that even if it is a halogen atom, when the substituent is chlorine, the boron substitution reaction does not proceed so much.
実施例8 溶媒量の違いによるジオールホウ素化合物の製造方法
実施例1の溶媒DMEの使用量5 mlを0.5 mlに変えた以外は実施例1と同様の方法により行い、4−メトキシフェニルボロン酸ピナコールエステルを得た。
Example 8 Production Method of Diol Boron Compound by Difference in Solvent Amount According to the same method as in Example 1 except that 5 ml of solvent DME used in Example 1 was changed to 0.5 ml, 4-methoxyphenylboronic acid pinacol An ester was obtained.
該反応の条件[ハロゲン化アリールのハロゲンの種類(X)、使用溶媒、使用塩基、及び反応温度]、GCから算出した収率、及びB/Siについて、実施例1のそれらと併せて表5に示す。尚、得られた生成物の物性データは実施例1と同じであった。 Table 5 shows the reaction conditions [type of halogen of aryl halide (X), solvent used, base used, reaction temperature], yield calculated from GC, and B / Si together with those of Example 1. Shown in The physical property data of the obtained product was the same as in Example 1.
実施例9−23 各種出発物質を用いたジオールホウ素化合物の製造方法
実施例1の出発物質4−ブロモアニソールの代わりに表6に示す各種臭化アリールを用いた以外は実施例1と同様の方法により行い、ボロン酸ピナコールエステルを得た。
該反応の単離時の収率及びGC又はNMRから算出した収率についてそれぞれ表6に示す。
Examples 9-23 Production method of diol boron compound using various starting materials The same method as in Example 1 except that various aryl bromides shown in Table 6 were used instead of the starting material 4- bromoanisole of Example 1. The boronic acid pinacol ester was obtained.
The yield at the time of isolation of the reaction and the yield calculated from GC or NMR are shown in Table 6, respectively.
表6の結果より、種々の出発物質(基質)を用いた場合であっても、ホウ素置換反応が効率よく進むことが分かった。 From the results in Table 6, it was found that the boron substitution reaction proceeded efficiently even when various starting materials (substrates) were used.
尚、実施例9−23により得られたボロン酸ピナコールエステルの物性データは以下の通りである。
〔物性データ〕
実施例9で得られたp−トリルボロン酸ピナコールエステル:1H NMR(400 MHz,CDCl3):δ=1.33(s,12H),2.36(s,3H),7.18(d,J=7.3 Hz,2H),7.70(d,J=8.2 Hz,2H);13C NMR(100 MHz,CDCl3):δ=21.7(CH3),24.8(CH3),83.6(C),128.5(CH),134.8(CH),141.4(C);HRMS-EI m/z [M-Me]+ calcd C12H16O2 10B,202.12797;found,202.12779;anal. calcd for C13H19BO2:C,71.59,H,8.78;found,C,71.61,H,8.92.
The physical property data of the boronic acid pinacol ester obtained in Examples 9-23 are as follows.
[Physical property data]
P-Tolylboronic acid pinacol ester obtained in Example 9: 1 H NMR (400 MHz, CDCl 3 ): δ = 1.33 (s, 12H), 2.36 (s, 3H), 7.18 (d, J = 7.3 Hz, 2H), 7.70 (d, J = 8.2 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ): δ = 21.7 (CH 3 ), 24.8 (CH 3 ), 83.6 (C), 128.5 (CH), 134.8 (CH), 141.4 (C); HRMS-EI m / z [M-Me] + calcd C 12 H 16 O 2 10 B, 202.12797; found, 202.12779; anal. Calcd for C13H19BO2: C, 71.59, H, 8.78; found, C, 71.61, H, 8.92.
実施例10で得られたm−トリルボロン酸ピナコールエステル:1H NMR(400 MHz,CDCl3):δ=1.34(s,12H),2.35(s,3H),7.24-7.30(m,2H),7.58-7.65(m,2H);13C NMR(100 MHz,CDCl3):δ=21.3(CH3),24.8(CH3),83.7(C),127.7(CH),131.8(CH),132.0(CH),135.3(CH),137.1(C);HRMS-APCI m/z [M+H]+ calcd C13H20O2 10B,218.15872;found,218.15869;anal. calcd for C13H19BO2:C,71.59,H,8.78;found,C,71.61,H,8.97.
実施例11で得られたo−トリルボロン酸ピナコールエステル:1H NMR(400 MHz,CDCl3):δ=1.34(s,12H),2.54(s,3H),7.14-7.18(m,2H),7.31(dt,J=1.6,7.6 Hz,1H),7.76(dd,J=1.5,7.7 Hz,1H);13C NMR(100 MHz,CDCl3):δ=22.2(CH3),24.8(CH3),83.3(C),124.7(CH),129.7(CH),130.8(CH),135.8(CH),144.8(C);HRMS-ESI m/z [M+H]+ calcd for C13H20 10BO2,218.15872;found,218.15859;anal. calcd for C13H19BO2:C,71.59,H,8.78;found,C,71.77,H,8.95.
M-Tolylboronic acid pinacol ester obtained in Example 10: 1 H NMR (400 MHz, CDCl 3 ): δ = 1.34 (s, 12H), 2.35 (s, 3H), 7.24-7.30 (m, 2H), 7.58-7.65 (m, 2H); 13 C NMR (100 MHz, CDCl 3 ): δ = 21.3 (CH 3 ), 24.8 (CH 3 ), 83.7 (C), 127.7 (CH), 131.8 (CH), 132.0 (CH), 135.3 (CH), 137.1 (C); HRMS-APCI m / z [M + H] + calcd C 13 H 20 O 2 10 B, 218.15872; found, 218.15869; anal. Calcd for C 13 H 19 BO 2 : C, 71.59, H, 8.78; found, C, 71.61, H, 8.97.
O-Tolylboronic acid pinacol ester obtained in Example 11: 1 H NMR (400 MHz, CDCl 3 ): δ = 1.34 (s, 12H), 2.54 (s, 3H), 7.14-7.18 (m, 2H), 7.31 (dt, J = 1.6, 7.6 Hz, 1H), 7.76 (dd, J = 1.5, 7.7 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ = 22.2 (CH 3 ), 24.8 (CH 3 ), 83.3 (C), 124.7 (CH), 129.7 (CH), 130.8 (CH), 135.8 (CH), 144.8 (C); HRMS-ESI m / z [M + H] + calcd for C 13 H 20 10 BO 2 , 218.15872; found, 218.15859; anal. Calcd for C 13 H 19 BO 2 : C, 71.59, H, 8.78; found, C, 71.77, H, 8.95.
実施例12で得られたフェニルボロン酸ピナコールエステル:1H NMR(400 MHz,CDCl3):δ=1.35(s,12H),7.33−7.41(m,2H),7.46(tt,J=2.0,7.5 Hz,1H),7.76−7.84(m,2H);13C NMR(100 MHz,CDCl3):δ=24.9(CH3),83.7(C),127.7(CH),131.2(CH),134.7(CH);HRMS-ESI m/z [M+H]+ calcd for C12H18O2 10B,204.14307;found,204.14297;anal. calcd for C12H17BO2:C,70.63,H,8.40;found,C,70.52,H,8.63. Phenylboronic acid pinacol ester obtained in Example 12: 1 H NMR (400 MHz, CDCl 3 ): δ = 1.35 (s, 12H), 7.33-7.41 (m, 2H), 7.46 (tt, J = 2.0, 7.5 Hz, 1H), 7.76-7.84 (m, 2H); 13 C NMR (100 MHz, CDCl 3 ): δ = 24.9 (CH 3 ), 83.7 (C), 127.7 (CH), 131.2 (CH), 134.7 (CH); HRMS-ESI m / z [M + H] + calcd for C 12 H 18 O 2 10 B, 204.14307; found, 204.14297; anal. Calcd for C 12 H 17 BO 2 : C, 70.63, H, 8.40; found, C, 70.52, H, 8.63.
実施例13で得られた4−フルオロフェニルボロン酸ピナコールエステル:1H NMR(400 MHz,CDCl3):δ=1.34(s,12H),7.05(tt,J=2.3,9.2 Hz,2H),7.76−7.83(m,2H);13C NMR(100 MHz,CDCl3):δ=24.8(CH3),83.9(C),114.8(d,J=20.1 Hz,CH),136.9(d,J=8.6 Hz,CH),165.1(d,J=252.0 Hz,C);HRMS-ESI m/z [M+H]+ calcd for C12H17 10B FO2,222.13365;found,222.13355. 4-fluorophenylboronic acid pinacol ester obtained in Example 13: 1 H NMR (400 MHz, CDCl 3 ): δ = 1.34 (s, 12H), 7.05 (tt, J = 2.3, 9.2 Hz, 2H), 7.76-7.83 (m, 2H); 13 C NMR (100 MHz, CDCl 3 ): δ = 24.8 (CH 3 ), 83.9 (C), 114.8 (d, J = 20.1 Hz, CH), 136.9 (d, J = 8.6 Hz, CH), 165.1 (d, J = 252.0 Hz, C); HRMS-ESI m / z [M + H] + calcd for C 12 H 17 10 B FO 2 , 222.13365; found, 222.13355.
実施例14で得られた4−クロロフェニルボロン酸ピナコールエステル:1H NMR(400 MHz,CDCl3):δ=1.34(s,12H),7.34(dt,J=1.8,8.7 Hz,2H),7.70−7.75(m,2H);13C NMR(100 MHz,CDCl3):δ=24.8(CH3),84.0(C),128.0(CH),136.1(CH),137.5(C);HRMS-ESI m/z [M+H]+ calcd for C12H17 10BClO2,238.10410;found,238.10370;anal. calcd for C12H16BClO2:C,60.43,H,6.76;Found,C,60.25,H,6.81. 4-chlorophenylboronic acid pinacol ester obtained in Example 14: 1 H NMR (400 MHz, CDCl 3 ): δ = 1.34 (s, 12H), 7.34 (dt, J = 1.8, 8.7 Hz, 2H), 7.70 −7.75 (m, 2H); 13 C NMR (100 MHz, CDCl 3 ): δ = 24.8 (CH 3 ), 84.0 (C), 128.0 (CH), 136.1 (CH), 137.5 (C); HRMS-ESI m / z [M + H] + calcd for C 12 H 17 10 BClO 2 , 238.10410; found, 238.10370; anal. calcd for C 12 H 16 BClO 2 : C, 60.43, H, 6.76; Found, C, 60.25, H, 6.81.
実施例15で得られた(4−ボロン酸ピナコールエステル)安息香酸tert−ブチル:1H NMR(400 MHz,CDCl3):δ=1.36(s,12H),1.60(s,9H),7.81−7.87(m,2H),7.93−7.98(m,2H);13C NMR(100 MHz,CDCl3):δ=24.9(CH3),28.2(CH3),81.1(C),84.1(C),128.4(CH),134.2(C),134.5(CH),165.8(C);HRMS-ESI m/z [M+Na]+ calcd for C17H25O410BNa,326.17744;found,326.17768;anal. calcd for C17H25BO4:C,67.12,H,8.28;found,C,67.09,H,8.37. Tert-Butyl (4-boronic acid pinacol ester) benzoate obtained in Example 15: 1 H NMR (400 MHz, CDCl 3 ): δ = 1.36 (s, 12H), 1.60 (s, 9H), 7.81- 7.87 (m, 2H), 7.93-7.98 (m, 2H); 13 C NMR (100 MHz, CDCl 3 ): δ = 24.9 (CH 3 ), 28.2 (CH 3 ), 81.1 (C), 84.1 (C) , 128.4 (CH), 134.2 (C), 134.5 (CH), 165.8 (C); HRMS-ESI m / z [M + Na] + calcd for C 17 H 25 O4 10 BNa, 326.17744; found, 326.17768; calcd for C 17 H 25 BO 4 : C, 67.12, H, 8.28; found, C, 67.09, H, 8.37.
実施例16で得られた(4−ボロン酸ピナコールエステル)安息香酸エチル:1H NMR(400 MHz,CDCl3):δ=1.36(s,12H),1.40(t,J=7.3 Hz,3H),4.38(q,J=7.3 Hz,2H),7.84−7.89(m, 2H),8.00−8.05(m,2H);13C NMR(100 MHz,CDCl3):δ=14.3(CH3),24.9(CH3),61.0(CH2),84.1(C),128.5(CH),132.6(C),134.6(CH),166.6(C);HRMS-ESI m/z [M+H]+ calcd for C15H22O4 10B,276.16420;found,276.16446;anal. calcd for C15H21BO4:C,65.24,H,7.67;found,C,65.32,H,7.81. Ethyl (4-boronic acid pinacol ester) benzoate obtained in Example 16: 1 H NMR (400 MHz, CDCl 3 ): δ = 1.36 (s, 12H), 1.40 (t, J = 7.3 Hz, 3H) , 4.38 (q, J = 7.3 Hz, 2H), 7.84-7.89 (m, 2H), 8.00-8.05 (m, 2H); 13 C NMR (100 MHz, CDCl 3 ): δ = 14.3 (CH 3 ), 24.9 (CH 3 ), 61.0 (CH 2 ), 84.1 (C), 128.5 (CH), 132.6 (C), 134.6 (CH), 166.6 (C); HRMS-ESI m / z [M + H] + calcd for C 15 H 22 O 4 10 B, 276.16420; found, 276.16446; anal. calcd for C 15 H 21 BO 4 : C, 65.24, H, 7.67; found, C, 65.32, H, 7.81.
実施例17で得られた(4−ボロン酸ピナコールエステル)N,N−ジエチル安息香酸:1H NMR(400 MHz,CDCl3):δ=1.30−1.15 (m, 3H), 1.15−1.10 (m, 3H), 1.35 (s, 12H), 3.30−3.10 (m, 2H), 3.64−3.40 (m, 2H), 7.36 (d, J = 8.2 Hz, 2H), 7.83 (d, J = 8.2 Hz, 2H);13C NMR(100 MHz,CDCl3):δ=12.9 (CH3), 14.2 (CH3), 24.8 (CH3), 39.2 (CH2) 43.2 (CH2), 84.0 (C), 125.4 (CH), 134.7 (CH), 139.8 (C), 171.1 (C);HRMS-ESI m/z [M+H]+ calcd for C17H27O3N10B,303.21148;found,303.21192. (4-boronic acid pinacol ester) N, N-diethylbenzoic acid obtained in Example 17: 1 H NMR (400 MHz, CDCl 3 ): δ = 1.30-1.15 (m, 3H), 1.15-1.10 (m , 3H), 1.35 (s, 12H), 3.30−3.10 (m, 2H), 3.64−3.40 (m, 2H), 7.36 (d, J = 8.2 Hz, 2H), 7.83 (d, J = 8.2 Hz, 13 C NMR (100 MHz, CDCl 3 ): δ = 12.9 (CH 3 ), 14.2 (CH 3 ), 24.8 (CH 3 ), 39.2 (CH 2 ) 43.2 (CH 2 ), 84.0 (C), 125.4 (CH), 134.7 (CH), 139.8 (C), 171.1 (C); HRMS-ESI m / z [M + H] + calcd for C 17 H 27 O 3 N 10 B, 303.21148; found, 303.21192.
実施例18で得られた(4−ボロン酸ピナコールエステル)N,N−ジエチルアニリン:1H NMR(400 MHz,CDCl3):δ=1.32 (s, 12H), 2.98 (s, 6H), 6.69 (dt, J = 2.3, 9.2 Hz, 2H), 7.69 (dt, J = 2.3, 9.2 Hz, 2H);13C NMR(100 MHz,CDCl3):δ=24.9 (CH3), 40.2 (CH3), 83.3 (C), 111.3 (CH), 136.2 (CH), 152.6 (C);HRMS-EI m/z [M-Me]+ calcd for C13H19 10BNO2, 231.15452;found,231.15344;anal. calcd for C14H22BNO2:C,68.04,H,8.97,N,5.67,found,C,68.04,H,9.00,N,5.46. (4-boronic acid pinacol ester) N, N-diethylaniline obtained in Example 18: 1 H NMR (400 MHz, CDCl 3 ): δ = 1.32 (s, 12H), 2.98 (s, 6H), 6.69 (dt, J = 2.3, 9.2 Hz, 2H), 7.69 (dt, J = 2.3, 9.2 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ): δ = 24.9 (CH 3 ), 40.2 (CH 3 ), 83.3 (C), 111.3 (CH), 136.2 (CH), 152.6 (C); HRMS-EI m / z [M-Me] + calcd for C 13 H 19 10 BNO 2 , 231.15452; found, 231.15344; anal. calcd for C 14 H 22 BNO 2 : C, 68.04, H, 8.97, N, 5.67, found, C, 68.04, H, 9.00, N, 5.46.
実施例19で得られた1−メチル(5−ボロン酸ピナコールエステル)インドール:1H NMR(400 MHz,CDCl3):δ=1.37 (s, 12H), 3.79 (s, 3H), 6.50 (dd, J = 0.9, 3.2 Hz, 1H), 7.04 (d, J = 3.2 Hz, 1H), 7.32 (d, J = 8.7 Hz, 1H), 7.66 (dd, J = 0.9, 8.2 Hz, 1H), 8.16 (s, 1H);13C NMR(100 MHz,CDCl3):δ=24.9 (CH3), 32.8 (CH3), 83.4 (C) 101.6 (CH), 108.6 (CH), 127.6 (CH), 128.2 (C), 128.8 (CH), 128.9 (CH), 138.6 (C);HRMS-EI m/z [M-Me]+ calcd for C15H20 10BNO2,256.16234;found,256.16149. 1-methyl (5-boronic acid pinacol ester) indole obtained in Example 19: 1 H NMR (400 MHz, CDCl 3 ): δ = 1.37 (s, 12H), 3.79 (s, 3H), 6.50 (dd , J = 0.9, 3.2 Hz, 1H), 7.04 (d, J = 3.2 Hz, 1H), 7.32 (d, J = 8.7 Hz, 1H), 7.66 (dd, J = 0.9, 8.2 Hz, 1H), 8.16 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ = 24.9 (CH 3 ), 32.8 (CH 3 ), 83.4 (C) 101.6 (CH), 108.6 (CH), 127.6 (CH), 128.2 (C), 128.8 (CH), 128.9 (CH), 138.6 (C); HRMS-EI m / z [M-Me] + calcd for C 15 H 20 10 BNO 2 , 256.16234; found, 256.16149.
実施例20で得られた2−(3−メチル−2−ブテニル)ボロン酸ピナコールエステル:1H NMR(400 MHz,CDCl3):δ=1.27 (s, 12H), 1.67 (s, 3H), 1.72 (s, 3H), 1.98 (d, J = 1.8 Hz, 3H);13C NMR(100 MHz,CDCl3):δ=16.5 (CH3), 21.2 (CH3), 24.4 (CH3), 24.8 (CH3), 82.7 (C), 148.2 (C);HRMS-EI m/z [M-Me]+ calcd for C11H21 10BO2,195.16709;found,195.16723. 2- (3-Methyl-2-butenyl) boronic acid pinacol ester obtained in Example 20: 1 H NMR (400 MHz, CDCl 3 ): δ = 1.27 (s, 12H), 1.67 (s, 3H), 1.72 (s, 3H), 1.98 (d, J = 1.8 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = 16.5 (CH 3 ), 21.2 (CH 3 ), 24.4 (CH 3 ), 24.8 (CH 3 ), 82.7 (C), 148.2 (C); HRMS-EI m / z [M-Me] + calcd for C 11 H 21 10 BO 2 , 195.16709; found, 195.16723.
実施例21で得られた(2,6−ジメチルフェニル)ボロン酸ピナコールエステル:1H NMR(400 MHz,CDCl3):δ=1.39 (s, 12H), 2.39 (s, 6H), 6.94 (d, J = 7.8 Hz, 2H), 7.12 (t, J = 7.8 Hz, 1H);13C NMR(100 MHz,CDCl3):δ=22.2 (CH3), 24.9 (CH3), 83.6 (C),126.4 (CH), 129.1 (CH), 141.7 (C);HRMS-EI m/z [M-Me]+ calcd for C14H21 10BO2,231.16709;found,231.16664;anal. calcd for C14H21BO2:C,72.44,H,9.12:found,C,72.25,H,9.13. (2,6-Dimethylphenyl) boronic acid pinacol ester obtained in Example 21: 1 H NMR (400 MHz, CDCl 3 ): δ = 1.39 (s, 12H), 2.39 (s, 6H), 6.94 (d , J = 7.8 Hz, 2H), 7.12 (t, J = 7.8 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ = 22.2 (CH 3 ), 24.9 (CH 3 ), 83.6 (C) , 126.4 (CH), 129.1 (CH), 141.7 (C); HRMS-EI m / z [M-Me] + calcd for C 14 H 21 10 BO 2 , 231.16709; found, 231.16664; anal. Calcd for C14H21BO2: C, 72.44, H, 9.12: found, C, 72.25, H, 9.13.
実施例22で得られた9−アントラセンボロン酸ピナコールエステル:1H NMR(400 MHz,CDCl3):δ=1.57 (s, 12H), 7.40−7.52 (m, 4H), 7.95−8.20 (m, 2H), 8.38−8.52 (m, 3H);13C NMR(100 MHz,CDCl3):δ=25.2 (CH3), 84.4 (C) 124.9 (CH), 125.8 (CH), 128.3 (CH), 128.8 (CH), 129.5 (CH), 131.1 (C), 135.9 (C);HRMS-EI m/z [M-Me]+ calcd for C20H21 10BO2,303.16709;found,303.16766. 9-anthraceneboronic acid pinacol ester obtained in Example 22: 1 H NMR (400 MHz, CDCl 3 ): δ = 1.57 (s, 12H), 7.40-7.52 (m, 4H), 7.95-8.20 (m, 2H), 8.38−8.52 (m, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = 25.2 (CH 3 ), 84.4 (C) 124.9 (CH), 125.8 (CH), 128.3 (CH), 128.8 (CH), 129.5 (CH), 131.1 (C), 135.9 (C); HRMS-EI m / z [M-Me] + calcd for C 20 H 21 10 BO 2 , 303.16709; found, 303.16766.
実施例23で得られた(2,4,6−トリイソプロピルフェニル)ボロン酸ピナコールエステル:1H NMR(400 MHz,CDCl3):δ=1.21 (d, J = 7.0 Hz, 6H), 1.25 (d, J = 7.0 Hz, 12 H), 1.37 (s, 12H), 2.84 (sep, J = 7.1 Hz, 1H), 2.96 (sep, J = 7.0, 2H), 6.93 (s, 2H);13C NMR(100 MHz,CDCl3):δ=24.0 (CH3), 24.4 (CH3), 24.9 (CH3), 34.0 (CH), 34.5 (CH), 83.6 (C), 119.6 (CH), 149.7 (C), 151.8 (C);HRMS-ESI m/z [M+H]+ calcd for C21H36 10BO2,330.28392;found,330.28359. (2,4,6-Triisopropylphenyl) boronic acid pinacol ester obtained in Example 23: 1 H NMR (400 MHz, CDCl 3 ): δ = 1.21 (d, J = 7.0 Hz, 6H), 1.25 ( d, J = 7.0 Hz, 12 H), 1.37 (s, 12H), 2.84 (sep, J = 7.1 Hz, 1H), 2.96 (sep, J = 7.0, 2H), 6.93 (s, 2H); 13 C NMR (100 MHz, CDCl 3 ): δ = 24.0 (CH 3 ), 24.4 (CH 3 ), 24.9 (CH 3 ), 34.0 (CH), 34.5 (CH), 83.6 (C), 119.6 (CH), 149.7 (C), 151.8 (C); HRMS-ESI m / z [M + H] + calcd for C 21 H 36 10 BO 2 , 330.28392; found, 330.28359.
実施例24 フェネチルボロン酸ピナコールエステルの製造方法
実施例1の出発物質4−ブロモアニソールを(2−ブロモエチル)ベンゼンに、溶媒DMEをジオキサンに、反応温度30℃を100℃に変えた以外は実施例1と同様の方法により行い、フェネチルボロン酸ピナコールエステルを得た。
該反応の条件[出発物質、使用溶媒、使用塩基、及び反応温度]、NMRから算出した収率、及びB/Siについて表7に示す。
尚、得られたフェネチルボロン酸ピナコールエステルの物性データを以下に示す。
〔物性データ〕
1H NMR(400 MHz,CDCl3):δ=1.14(t,J=8.4 Hz,2H),1.22(s,12H),2.75(t,J=8.4 Hz,2H),7.10-7.29(m,5H);13C NMR(100 MHz,CDCl3):δ=12.5(br,BCH2),24.9(CH3),30.1(CH2),83.2(C),125.6(CH),128.1(CH2),128.3(CH),144.5(C);HRMS-EI m/z [M]+ calcd C14H21 10BO2,231.16709;found,231.16694.
Example 24 Production Method of Phenethylboronic Acid Pinacol Ester Example 1 except that starting material 4-bromoanisole of Example 1 was changed to (2-bromoethyl) benzene, solvent DME to dioxane, and reaction temperature 30 ° C. to 100 ° C. 1 to obtain phenethylboronic acid pinacol ester.
Table 7 shows the reaction conditions [starting material, solvent used, base used, and reaction temperature], yield calculated from NMR, and B / Si.
In addition, the physical property data of the obtained phenethyl boronic acid pinacol ester are shown below.
[Physical property data]
1 H NMR (400 MHz, CDCl 3 ): δ = 1.14 (t, J = 8.4 Hz, 2H), 1.22 (s, 12H), 2.75 (t, J = 8.4 Hz, 2H), 7.10-7.29 (m, 13 C NMR (100 MHz, CDCl 3 ): δ = 12.5 (br, BCH 2 ), 24.9 (CH 3 ), 30.1 (CH 2 ), 83.2 (C), 125.6 (CH), 128.1 (CH 2 ), 128.3 (CH), 144.5 (C); HRMS-EI m / z [M] + calcd C 14 H 21 10 BO 2 , 231.16709; found, 231.16694.
実施例25 (4−アリルオキシフェニル)ボロン酸ピナコールエステルの製造方法
実施例1の出発物質4−ブロモアニソールの代わりに4−アリルオキシフェニルブロマイドを用いた以外は実施例1と同様の方法により行い、(4−アリルオキシフェニル)ボロン酸ピナコールエステルを得た。
該反応の出発物質及びNMRから算出した収率について表8に示す。
尚、得られた(4−アリルオキシフェニル)ボロン酸ピナコールエステルの物性データを以下に示す。
Example 25 (4-Allyloxyphenyl) boronic acid pinacol ester production method The same procedure as in Example 1 except that 4-allyloxyphenyl bromide was used instead of the starting material 4-bromoanisole of Example 1. , (4-allyloxyphenyl) boronic acid pinacol ester was obtained.
The starting materials for the reaction and the yields calculated from NMR are shown in Table 8.
The physical property data of the obtained (4-allyloxyphenyl) boronic acid pinacol ester is shown below.
〔物性データ〕
1H NMR(400 MHz,CDCl3):δ=1.33(s,12H),4.47-4.63(m,2H),5.29(dd,J=1.5,11.0 Hz,1H),5.41(dd,J=1.5,17.6 Hz,1H),6.05(ddt,J=5.6,10.6,17.0 Hz,1H),6.83-6.95(m,2H),7.67-7.80(m,2H);13C NMR(100 MHz,CDCl3):δ=24.8(CH3),68.4(CH2),83.5(C),114.0(CH),117.6(CH2),133.0(CH),136.4(CH),161.1(C);HRMS-EI m/z [M]+ calcd C15H21 10BO3,259.16201;found,259.16174;anal. calcd for C15H21BO3:C,69.26,H,8.14;found,C,69.24,H,8.32.
[Physical property data]
1 H NMR (400 MHz, CDCl 3 ): δ = 1.33 (s, 12H), 4.47-4.63 (m, 2H), 5.29 (dd, J = 1.5, 11.0 Hz, 1H), 5.41 (dd, J = 1.5 , 17.6 Hz, 1H), 6.05 (ddt, J = 5.6, 10.6, 17.0 Hz, 1H), 6.83-6.95 (m, 2H), 7.67-7.80 (m, 2H); 13 C NMR (100 MHz, CDCl 3 ): Δ = 24.8 (CH 3 ), 68.4 (CH 2 ), 83.5 (C), 114.0 (CH), 117.6 (CH 2 ), 133.0 (CH), 136.4 (CH), 161.1 (C); HRMS-EI m / z [M] + calcd C 15 H 21 10
実施例26 2−(3−ブテニル)フェニルボロン酸ピナコールエステルの製造方法
実施例1の出発物質4−ブロモアニソールの代わりにo−(3−ブテニル)ブロモベンゼンを用いた以外は実施例1と同様の方法により行い、2−(3−ブテニル)フェニルボロン酸ピナコールエステルを得た。
該反応の出発物質及びNMRから算出した収率について、実施例25のそれらと併せて表8に示す。
尚、得られた2−(3−ブテニル)フェニルボロン酸ピナコールエステルの物性データを以下に示す。
Example 26 Method for producing 2- (3-butenyl) phenylboronic acid pinacol ester Same as Example 1 except that o- (3-butenyl) bromobenzene was used instead of the starting material 4-bromoanisole of Example 1. To give 2- (3-butenyl) phenylboronic acid pinacol ester.
The starting material of the reaction and the yield calculated from NMR are shown in Table 8 together with those of Example 25.
The physical property data of the obtained 2- (3-butenyl) phenylboronic acid pinacol ester is shown below.
〔物性データ〕
1H NMR(400 MHz,CDCl3):δ=1.34(s,12H),2.25-2.35(m,2H),2.96(t,J=8.1 Hz,2H),4.91-4.98(m,1H),5.03(dq,J=1.8,17.5 Hz,1H),5.89(ddt,J=6.9,10.4,17.4 Hz,1H),7.14-7.21(m,2H),7.34(dt,J=1.5,7.7 Hz,1H),7.74-7.80(m,1H);13C NMR(100 MHz,CDCl3):δ=24.8(CH3),35.4(CH2),37.5(CH2),83.3(C),114.3(CH2),125.1(CH),129.2(CH),130.8(CH),136.1(CH),138.7(CH),149.0(C);HRMS-ESI m/z [M+H]+ calcd for C16H24 10BO2,258.19002;found,258.18970;anal. calcd for C16H23BO2:C,74.47,H,8.98;found,C,74.47,H,9.24.
[Physical property data]
1 H NMR (400 MHz, CDCl 3 ): δ = 1.34 (s, 12H), 2.25-2.35 (m, 2H), 2.96 (t, J = 8.1 Hz, 2H), 4.91-4.98 (m, 1H), 5.03 (dq, J = 1.8, 17.5 Hz, 1H), 5.89 (ddt, J = 6.9, 10.4, 17.4 Hz, 1H), 7.14-7.21 (m, 2H), 7.34 (dt, J = 1.5, 7.7 Hz, 1H), 7.74-7.80 (m, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ = 24.8 (CH 3 ), 35.4 (CH 2 ), 37.5 (CH 2 ), 83.3 (C), 114.3 ( CH 2 ), 125.1 (CH), 129.2 (CH), 130.8 (CH), 136.1 (CH), 138.7 (CH), 149.0 (C); HRMS-ESI m / z [M + H] + calcd for C 16 H 24 10 BO 2 , 258.19002; found, 258.18970; anal. Calcd for C 16 H 23 BO 2 : C, 74.47, H, 8.98; found, C, 74.47, H, 9.24.
実施例27 ホウ素置換反応及び鈴木−宮浦カップリングの連続反応
アルゴン雰囲気下でKOMe 42.1 mg(0.6 mmol)、DME 5 ml、及び(ジメチルフェニルシリル)ボロン酸ピナコールエステル196.7 mg(0.75 mmol)を、30℃で10分間撹拌した。その後、4−ブロモアニソール93.5 mg(0.50 mmol)を滴下し、1時間反応させた後に、反応混合物をガスクロマトグラフィー(GC)で分析し、反応が完了しているかを確認した。
Example 27 Continuous reaction of boron substitution reaction and Suzuki-Miyaura coupling Under argon atmosphere, KOMe 42.1 mg (0.6 mmol),
反応後に0℃に冷却し、TBAF(1.0 M,800 μl)を加え、3時間撹拌した。その後、混合溶液に水100 mlを加え、次いでジエチルエーテル50 mlで3回抽出を行った。有機層に硫酸マグネシウムを加えて乾燥し、ろ過後、ろ液のジエチルエーテルを留去した。
窒素雰囲気下で反応物に、DMF 2 ml、K2CO3 276 mg(1.0 mmol)、1−ヨード−4−ニトロベンゼン249 mg(1.0 mmol)、及びテトラキス(トリフェニルホスフィン)パラジウム(Pd(PPh3)4)29 mg(0.025 mmol,5 mol%)を加え、90℃で24時間撹拌反応させた。
反応後に室温に冷却し、反応液に水100 mlを加え、次いでジエチルエーテル50 mlで3回抽出を行った。有機層に硫酸マグネシウムを加えて乾燥し、ろ過後、ろ液のジエチルエーテルを留去した。得られた粗生成物を、シリカゲルカラムクロマトグラフィを用い、ヘキサンを溶離液として精製し、4−メトキシ−4’−ニトロビフェニルを得た。
該反応の反応スキームを以下に示す。
上記反応の出発物質及び単離時の収率について表9に示す。
After the reaction, the mixture was cooled to 0 ° C., TBAF (1.0 M, 800 μl) was added, and the mixture was stirred for 3 hours. Thereafter, 100 ml of water was added to the mixed solution, followed by extraction three times with 50 ml of diethyl ether. Magnesium sulfate was added to the organic layer for drying, and after filtration, the diethyl ether in the filtrate was distilled off.
Under nitrogen atmosphere, the reaction was mixed with 2 ml of DMF, 276 mg (1.0 mmol) of K 2 CO 3 , 249 mg (1.0 mmol) of 1-iodo-4-nitrobenzene, and tetrakis (triphenylphosphine) palladium (Pd (PPh 3 4 ) 29 mg (0.025 mmol, 5 mol%) was added, and the reaction was stirred at 90 ° C. for 24 hours.
After the reaction, the reaction solution was cooled to room temperature, 100 ml of water was added to the reaction solution, and then extracted three times with 50 ml of diethyl ether. Magnesium sulfate was added to the organic layer for drying, and after filtration, the diethyl ether in the filtrate was distilled off. The resulting crude product was purified using silica gel column chromatography with hexane as an eluent to give 4-methoxy-4′-nitrobiphenyl.
The reaction scheme of this reaction is shown below.
Table 9 shows the starting materials for the above reaction and the yield at the time of isolation.
尚、得られた4−メトキシ−4’−ニトロビフェニルの物性データを以下に示す。
〔物性データ〕
1H NMR(400 MHz,CDCl3):δ=3.86(s,3H),7.01(dt,J=2.6,9.2 Hz,2H),7.56 (dt,J=2.7,9.2 Hz,2H),7.66(dt,J=2.3,9.2 Hz,2H),8.24(dt,J=2.3,9.2 Hz,2H);13C NMR(100 MHz,CDCl3):δ=55.3(CH3),114.5(CH),124.0(CH),126.9(CH),128.5(CH),130.9(C),146.4(C),147.1(C),160.4(C).
The physical property data of the obtained 4-methoxy-4′-nitrobiphenyl is shown below.
[Physical property data]
1 H NMR (400 MHz, CDCl 3 ): δ = 3.86 (s, 3H), 7.01 (dt, J = 2.6, 9.2 Hz, 2H), 7.56 (dt, J = 2.7, 9.2 Hz, 2H), 7.66 ( dt, J = 2.3, 9.2 Hz, 2H), 8.24 (dt, J = 2.3, 9.2 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ): δ = 55.3 (CH 3 ), 114.5 (CH), 124.0 (CH), 126.9 (CH), 128.5 (CH), 130.9 (C), 146.4 (C), 147.1 (C), 160.4 (C).
実施例28−29 各種出発物質を用いたホウ素置換反応及び鈴木−宮浦カップリングの連続反応
実施例27の出発物質4−ブロモアニソールの代わりに表9の実施例28又は29に記載の臭化アリールを用いた以外は実施例27と同様の方法により行い、カップリング生成物を得た。
該反応の出発物質及び単離時の収率について、実施例28のそれらと併せて表9に示す。
Examples 28-29 Boron Substitution Reaction Using Various Starting Materials and Suzuki-Miyaura Coupling Reactions Example 27 Starting Material 4-Bromoanisole Instead of the aryl bromide described in Example 28 or 29 of Table 9 A coupling product was obtained in the same manner as in Example 27 except that was used.
The starting materials for the reaction and the yield at the time of isolation are shown in Table 9 together with those of Example 28.
尚、実施例28又は29により得られたカップリング生成物の物性データは以下の通りである。
〔物性データ〕
3−メチル−4’−ニトロビフェニル:1H NMR(400 MHz,CDCl3):δ=2.43(s,3H),7.25(d,J=7.3 Hz,1H),7.33−7.44(m,2H),7.70(dt,J=2.3,9.2 Hz,2H),8.25(dt,J=2.3,9.2 Hz,2H);13C NMR(100 MHz,CDCl3):δ=21.4(CH3),123.9(CH),124.4(CH),127.7(CH),128.0(CH),129.0(CH),129.6(CH),138.6(C),138.8(C),146.9(C),147.7(C).
4−フルオロ−4’−ニトロビフェニル:1H NMR(400 MHz,CDCl3):δ=7.15−7.22(m,2H),7.55−7.63(m,2H),7.69(dt,J=2.3,9.2 Hz,2H),8.28(dt,J=2.3,8.7 Hz,2H);13C NMR(100 MHz,CDCl3):δ=116.1(d,J=22.0 Hz,CH),124.1(CH), 127.6(CH),129.8(d,J=8.6 Hz,CH),134.8 (d,J=2.9 Hz,CH),146.5(C),147.0(C),163.3(d,J=251 Hz,C).
The physical property data of the coupling product obtained in Example 28 or 29 are as follows.
[Physical property data]
3-methyl-4′-nitrobiphenyl: 1 H NMR (400 MHz, CDCl 3 ): δ = 2.43 (s, 3H), 7.25 (d, J = 7.3 Hz, 1H), 7.33-7.44 (m, 2H) , 7.70 (dt, J = 2.3, 9.2 Hz, 2H), 8.25 (dt, J = 2.3, 9.2 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ): δ = 21.4 (CH 3 ), 123.9 ( CH), 124.4 (CH), 127.7 (CH), 128.0 (CH), 129.0 (CH), 129.6 (CH), 138.6 (C), 138.8 (C), 146.9 (C), 147.7 (C).
4-fluoro-4′-nitrobiphenyl: 1 H NMR (400 MHz, CDCl 3 ): δ = 7.15−7.22 (m, 2H), 7.55−7.63 (m, 2H), 7.69 (dt, J = 2.3, 9.2) Hz, 2H), 8.28 (dt , J = 2.3,8.7 Hz, 2H); 13 C NMR (100 MHz, CDCl 3): δ = 116.1 (d, J = 22.0 Hz, CH), 124.1 (CH), 127.6 (CH), 129.8 (d, J = 8.6 Hz, CH), 134.8 (d, J = 2.9 Hz, CH), 146.5 (C), 147.0 (C), 163.3 (d, J = 251 Hz, C).
実施例30 フェニルボロン酸ピナコールエステルの反応時間による収率の変化
アルゴン雰囲気下でKOMe 84.2mg(0.12 mmol)、DME 5 ml、及び(ジメチルフェニルシリル)ボロン酸ピナコールエステル 39.34mg(0.15 mmol)を加え、30℃で10分間撹拌した。その後、ブロモベンゼン15.7mg(0.10 mmol)を滴下し、混合物の反応速度をガスクロマトグラフィー(GC)を用いて分析した。この反応によりフェニルボロン酸ピナコールエステルを得た。
得られた結果(metal free)を図1に示す。
Example 30 Change in yield of phenylboronic acid pinacol ester depending on the reaction time Under argon atmosphere, KOMe 84.2 mg (0.12 mmol),
The obtained result (metal free) is shown in FIG.
比較例12−22 遷移金属を用いたフェニルボロン酸ピナコールエステルの反応時間による収率の変化
実施例10の出発物質KOMeと共に表10に記載した各種遷移金属を表10に記載の量を加えた以外は実施例10と同様の方法により行い、フェニルボロン酸ピナコールエステルを得た。
尚、該反応の添加した遷移金属の種類及び添加量について表10に示す。
得られた結果を実施例30の結果と合わせて図1に示す。
Comparative Example 12-22 Change in Yield with Reaction Time of Phenylboronic Acid Pinacol Ester Using Transition Metal Various transition metals described in Table 10 together with the starting material KOMe of Example 10 except that the amounts described in Table 10 were added Was carried out in the same manner as in Example 10 to obtain phenylboronic acid pinacol ester.
In addition, it shows in Table 10 about the kind and addition amount of the transition metal which this reaction added.
The obtained results are shown in FIG. 1 together with the results of Example 30.
図1の結果から、種々の遷移金属を添加した場合と比較して、金属を添加しない本発明の方法では、高い収率でフェニルボロン酸ピナコールエステルが得られることが分かった。 From the results of FIG. 1, it was found that phenylboronic acid pinacol ester was obtained in a high yield by the method of the present invention in which no metal was added as compared with the case where various transition metals were added.
本発明の製造方法によれば、グリニヤール試薬やリチウム反応剤を用いる従来法のような0℃より低い温度で反応させる必要がなく、簡便に目的のジオールホウ素化合物を得ることができる。また、本発明の製造方法は、パラジウム等の重金属を用いる必要がないため、医薬品の製造にも適している。 According to the production method of the present invention, it is not necessary to carry out the reaction at a temperature lower than 0 ° C. as in the conventional method using a Grignard reagent or a lithium reagent, and the desired diol boron compound can be easily obtained. In addition, the production method of the present invention does not require the use of heavy metals such as palladium, and is therefore suitable for the production of pharmaceuticals.
更に、本発明の反応は臭素原子またはヨウ素原子以外の置換基との反応性が低いため、本発明の方法により、各種置換基を有する化合物を基質として、該化合物由来のジオールホウ素化合物を得ることができる。 Furthermore, since the reaction of the present invention has low reactivity with substituents other than bromine atoms or iodine atoms, a diol boron compound derived from the compound is obtained by using the compound having various substituents as a substrate by the method of the present invention. Can do.
図1中の−●−は実施例30の結果(metal free)を、−▲−は比較例20の結果([Ir(OMe)(cod)]2)を、−■−は比較例12の結果(Cu(OAc)2)を、−◆−は比較例14の結果(NiCl2)を、−○−は比較例22の結果([RuCl2(p-cymene)]2)を、−△−は比較例13の結果(CuCl)を、−□−は比較例18の結果(AgOAc)を、−◇−は比較例21の結果([RhCl(cod)]2)を、・・・●・・・は比較例16の結果酢酸パラジウム(Pd(OAc)2)を、・・・▲・・・は比較例17の結果(CoCl2)を、・・・■・・・は比較例19の結果(PtCl2(cod))を、・・・◆・・・は比較例15の結果(FeCl3)をそれぞれ表す。 In FIG. 1, − ● − indicates the result (metal free) of Example 30, − ▲ − indicates the result of Comparative Example 20 ([Ir (OMe) (cod)] 2 ), − ■ − indicates that of Comparative Example 12. The result (Cu (OAc) 2 ), − ♦ − indicates the result of Comparative Example 14 (NiCl 2 ), − ◯ − indicates the result of Comparative Example 22 ([RuCl 2 (p-cymene)] 2 ), −Δ − Indicates the result of Comparative Example 13 (CuCl), − □ − indicates the result of Comparative Example 18 (AgOAc), − ◇ − indicates the result of Comparative Example 21 ([RhCl (cod)] 2 ),. ... are the results of palladium acetate of Comparative example 16 (Pd (OAc) 2) , ··· ▲ ··· are of Comparative example 17 results (CoCl 2), ··· ■ ··· Comparative example 19 The results (PtCl 2 (cod)),...,... Represent the results of Comparative Example 15 (FeCl 3 ), respectively.
Claims (5)
(式中、Xは臭素原子又はヨウ素原子を表し、Rは、炭素数1〜20のアルキル基、炭素数2〜20のアルケニル基、炭素数6〜14のアリール基、窒素原子、酸素原子及び硫黄原子から選ばれる異性原子を1〜3個含む単環式複素環と芳香族環1個が縮合して成る二環系複素環基、或いは、窒素原子、酸素原子及び硫黄原子から選ばれる異性原子を1〜3個含む単環式複素環と芳香族環2個が縮合して成る三環系複素環基を表し、これらの基は、炭素数1〜6のアルキル基、炭素数2〜6のアルケニル基、炭素数1〜6のアルコキシ基、炭素数2〜7のアルコキシカルボニル基、炭素数2〜6のアルケニルオキシ基、炭素数2〜12のアルキルカルバモイル基、炭素数6〜14のアリール基、フルオロ基、クロロ基、又は炭素数2〜12のアルキルアミノ基を置換基として有していてもよい。但し、Rが二環系複素環基又は三環系複素環基である場合、Xは当該二環系複素環基又は三環系複素環基を構成する芳香族環上の炭素原子に結合している。)と、下記一般式(VI)で示される化合物
(式中、3個のR3はそれぞれ独立して、炭素数1〜6のアルキル基又は炭素数6〜10のアリール基を表し、4個のR4はそれぞれ独立して、炭素数1〜3のアルキル基を表す。)とを、ナトリウムアルコキシド又はカリウムアルコキシドの存在下で反応させることを特徴とする、下記一般式(VII)で示される化合物
(式中、R及びR4は、上記と同じ。)の製造方法。 Organohalogen compounds represented by the following general formula (V)
(In the formula, X represents a bromine atom or an iodine atom, and R represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitrogen atom, an oxygen atom, and A bicyclic heterocyclic group formed by condensation of a monocyclic heterocyclic ring containing 1 to 3 isomeric atoms selected from sulfur atoms and one aromatic ring, or an isomer selected from nitrogen, oxygen and sulfur atoms A tricyclic heterocyclic group formed by condensation of a monocyclic heterocyclic ring containing 1 to 3 atoms and two aromatic rings is represented by an alkyl group having 1 to 6 carbon atoms, 2 to 2 carbon atoms. 6 alkenyl groups, alkoxy groups having 1 to 6 carbon atoms, alkoxycarbonyl groups having 2 to 7 carbon atoms, alkenyloxy groups having 2 to 6 carbon atoms, alkylcarbamoyl groups having 2 to 12 carbon atoms, and 6 to 14 carbon atoms An aryl group, a fluoro group, a chloro group, or an aryl group having 2 to 12 carbon atoms The Kiruamino group which may have a substituent. However, when R is bicyclic heterocyclic group or tricyclic heterocyclic group, X is the bicyclic heterocyclic group or tricyclic heterocyclic group And a compound represented by the following general formula (VI):
(In the formula, three R 3 s each independently represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and four R 4 s each independently represent one to 1 carbon atoms. And a compound represented by the following general formula (VII), wherein the compound is reacted in the presence of sodium alkoxide or potassium alkoxide:
(Wherein R and R 4 are the same as above).
(式中、Xは臭素原子又はヨウ素原子を表し、p1は0〜5の整数を表し、p1個のR1は、それぞれ独立して炭素数1〜6のアルキル基、炭素数2〜6のアルケニル基、炭素数1〜6のアルコキシ基、炭素数2〜7のアルコキシカルボニル基、炭素数2〜6のアルケニルオキシ基、炭素数2〜12のアルキルカルバモイル基、炭素数6〜14のアリール基、フルオロ基、クロロ基、又は炭素数2〜12のアルキルアミノ基を表す。)、下記一般式(II)で示される化合物
(式中、X及びR1は上記と同じ。p2は0〜7の整数を表す。)、下記一般式(III)で示される化合物
(式中、X及びR1は上記と同じ。p3は0〜9の整数を表す。)、下記一般式(IV)で示される化合物
(式中、Xは上記と同じ。R2は炭素数1〜6のアルキル基を表す。)、炭素数6〜14のアリール基を置換基として有する又は無置換の炭素数1〜20のアルキルブロマイド、炭素数6〜14のアリール基を置換基として有する又は無置換の炭素数1〜20のアルキルヨード、炭素数2〜20のアルケニルブロマイド、或いは、炭素数2〜20のアルケニルヨードである、請求項1記載の製造方法。 The organic halogen compound represented by the general formula (V) is a compound represented by the following general formula (I)
(In the formula, X represents a bromine atom or an iodine atom, p 1 represents an integer of 0 to 5, and p 1 R 1 s are each independently an alkyl group having 1 to 6 carbon atoms or 2 to 2 carbon atoms. 6 alkenyl groups, alkoxy groups having 1 to 6 carbon atoms, alkoxycarbonyl groups having 2 to 7 carbon atoms, alkenyloxy groups having 2 to 6 carbon atoms, alkylcarbamoyl groups having 2 to 12 carbon atoms, and 6 to 14 carbon atoms An aryl group, a fluoro group, a chloro group, or an alkylamino group having 2 to 12 carbon atoms), a compound represented by the following general formula (II)
(Wherein X and R 1 are the same as described above; p 2 represents an integer of 0 to 7), a compound represented by the following general formula (III)
(Wherein X and R 1 are the same as described above; p 3 represents an integer of 0 to 9), a compound represented by the following general formula (IV)
(In the formula, X is the same as above. R 2 represents an alkyl group having 1 to 6 carbon atoms.), An aryl group having 6 to 14 carbon atoms as a substituent or an unsubstituted alkyl group having 1 to 20 carbon atoms. A bromide, an aryliodine having 6 to 14 carbon atoms as an substituent or an unsubstituted alkyliodine having 1 to 20 carbons, an alkenyl bromide having 2 to 20 carbons, or an alkenyl iodo having 2 to 20 carbons; The manufacturing method according to claim 1.
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