CN108017479A - 芳香族化合物的制造方法 - Google Patents
芳香族化合物的制造方法 Download PDFInfo
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- CN108017479A CN108017479A CN201711054403.4A CN201711054403A CN108017479A CN 108017479 A CN108017479 A CN 108017479A CN 201711054403 A CN201711054403 A CN 201711054403A CN 108017479 A CN108017479 A CN 108017479A
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- 238000000034 method Methods 0.000 title claims abstract description 26
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- -1 aromatic nitro compound Chemical class 0.000 claims abstract description 50
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000003863 metallic catalyst Substances 0.000 claims abstract description 13
- 150000001642 boronic acid derivatives Chemical class 0.000 claims abstract description 9
- 238000006880 cross-coupling reaction Methods 0.000 claims abstract description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 18
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims 2
- 150000003624 transition metals Chemical group 0.000 claims 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 150000002816 nickel compounds Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- 239000006227 byproduct Substances 0.000 abstract description 6
- 229910052736 halogen Inorganic materials 0.000 abstract description 6
- 125000005843 halogen group Chemical group 0.000 abstract description 6
- 150000002367 halogens Chemical class 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 6
- 230000004044 response Effects 0.000 abstract description 5
- 238000005859 coupling reaction Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
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- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical class 0.000 abstract 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 75
- 238000005160 1H NMR spectroscopy Methods 0.000 description 73
- 125000001424 substituent group Chemical group 0.000 description 50
- 239000002585 base Substances 0.000 description 33
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- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical class COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 21
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- 229910052799 carbon Inorganic materials 0.000 description 19
- 239000007787 solid Substances 0.000 description 19
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 18
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
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- 239000002904 solvent Substances 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
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- 238000004587 chromatography analysis Methods 0.000 description 9
- 230000006835 compression Effects 0.000 description 9
- 238000007906 compression Methods 0.000 description 9
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical group C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 9
- 125000001072 heteroaryl group Chemical group 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 9
- 238000004293 19F NMR spectroscopy Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- VOAAEKKFGLPLLU-UHFFFAOYSA-N (4-methoxyphenyl)boronic acid Chemical class COC1=CC=C(B(O)O)C=C1 VOAAEKKFGLPLLU-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000003513 alkali Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 150000004677 hydrates Chemical class 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 7
- 235000019798 tripotassium phosphate Nutrition 0.000 description 7
- CFBYEGUGFPZCNF-UHFFFAOYSA-N 2-nitroanisole Chemical class COC1=CC=CC=C1[N+]([O-])=O CFBYEGUGFPZCNF-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- VMXRUUFRMHNVDM-UHFFFAOYSA-N 1-phenyldibenzothiophene Chemical group C1=CC=CC=C1C1=CC=CC2=C1C1=CC=CC=C1S2 VMXRUUFRMHNVDM-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- YHGPYBQVSJBGHH-UHFFFAOYSA-H iron(3+);trisulfate;pentahydrate Chemical compound O.O.O.O.O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YHGPYBQVSJBGHH-UHFFFAOYSA-H 0.000 description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 5
- 125000001624 naphthyl group Chemical group 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 125000005493 quinolyl group Chemical group 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- RJKGJBPXVHTNJL-UHFFFAOYSA-N 1-nitronaphthalene Chemical class C1=CC=C2C([N+](=O)[O-])=CC=CC2=C1 RJKGJBPXVHTNJL-UHFFFAOYSA-N 0.000 description 4
- PABWCQBWXPHCBX-UHFFFAOYSA-N 1-phenyldibenzofuran Chemical group C1=CC=CC=C1C1=CC=CC2=C1C1=CC=CC=C1O2 PABWCQBWXPHCBX-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 150000002815 nickel Chemical class 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000012230 colorless oil Substances 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
- 150000007529 inorganic bases Chemical class 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000005956 isoquinolyl group Chemical group 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000002941 palladium compounds Chemical class 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- ZYMCBJWUWHHVRX-UHFFFAOYSA-N (4-nitrophenyl)-phenylmethanone Chemical class C1=CC([N+](=O)[O-])=CC=C1C(=O)C1=CC=CC=C1 ZYMCBJWUWHHVRX-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical class CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- TURIHPLQSRVWHU-UHFFFAOYSA-N 2-phenylnaphthalene Chemical compound C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=C1 TURIHPLQSRVWHU-UHFFFAOYSA-N 0.000 description 2
- VIJYEGDOKCKUOL-UHFFFAOYSA-N 9-phenylcarbazole Chemical class C1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 VIJYEGDOKCKUOL-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- HCIMXTXCDVBLOA-UHFFFAOYSA-N [4-(trifluoromethyl)phenoxy]boronic acid Chemical class OB(O)OC1=CC=C(C(F)(F)F)C=C1 HCIMXTXCDVBLOA-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 125000003678 cyclohexadienyl group Chemical group C1(=CC=CCC1)* 0.000 description 2
- 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 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 125000003373 pyrazinyl group Chemical group 0.000 description 2
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 2
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- ZXDTWWZIHJEZOG-UHFFFAOYSA-N (2,6-dimethylphenyl)boronic acid Chemical class CC1=CC=CC(C)=C1B(O)O ZXDTWWZIHJEZOG-UHFFFAOYSA-N 0.000 description 1
- HTGQCLJTWPSFNL-UHFFFAOYSA-N (2-methylphenoxy)boronic acid Chemical compound CC1=CC=CC=C1OB(O)O HTGQCLJTWPSFNL-UHFFFAOYSA-N 0.000 description 1
- KYLUAQBYONVMCP-UHFFFAOYSA-N (2-methylphenyl)phosphane Chemical class CC1=CC=CC=C1P KYLUAQBYONVMCP-UHFFFAOYSA-N 0.000 description 1
- NLLGFYPSWCMUIV-UHFFFAOYSA-N (3-methoxyphenyl)boronic acid Chemical class COC1=CC=CC(B(O)O)=C1 NLLGFYPSWCMUIV-UHFFFAOYSA-N 0.000 description 1
- OBQRODBYVNIZJU-UHFFFAOYSA-N (4-acetylphenyl)boronic acid Chemical class CC(=O)C1=CC=C(B(O)O)C=C1 OBQRODBYVNIZJU-UHFFFAOYSA-N 0.000 description 1
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- BIWQNIMLAISTBV-UHFFFAOYSA-N (4-methylphenyl)boronic acid Chemical class CC1=CC=C(B(O)O)C=C1 BIWQNIMLAISTBV-UHFFFAOYSA-N 0.000 description 1
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- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- QNMBSXGYAQZCTN-UHFFFAOYSA-N thiophen-3-ylboronic acid Chemical compound OB(O)C=1C=CSC=1 QNMBSXGYAQZCTN-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Abstract
本发明提供一种芳香族化合物的制造方法,其是为了解决下述技术问题而完成的:在选择卤原子作为偶联反应原料化合物的离去基团的情况下,由于在反应后会副产有害的卤素废弃物,因此存在的废液的处理、工艺繁琐、环境负担高问题;在不需要以卤原子为离去基团的碳‑氢活化交叉偶联反应中,虽不会副产卤素废弃物,但对反应基质具有诸多限制,仍然存在局限于有限的分子构筑法的问题。本发明的芳香族化合物的制造方法的特征在于,在金属催化剂存在下使芳香族硝基化合物和硼酸化合物进行交叉偶联反应。
Description
技术领域
本发明涉及芳香族化合物的制造方法,更具体而言,涉及以芳香族硝基化合物和硼酸化合物为原料进行交叉偶联反应而制造芳香族化合物的方法。
背景技术
多取代的芳香族化合物已被广泛用于医药农药、天然物合成、液晶及有机电致发光元件等领域,作为其分子骨架构筑法,已开发出了多种方法。其中,使用芳香族硼酸衍生物的偶联芳香族化合物的合成反应(铃木交叉偶联反应)是特别有用的方法之一,已被实施了广泛的改良(非专利文献1)。
作为铃木交叉偶联反应的原料,通常被使用的是具有离去基团的芳香族化合物。作为离去基团,最常用的是氯原子、溴原子及碘原子等卤原子。另外,最近还报道了由不具有卤原子等离去基团的芳香族化合物直接实施交叉偶联反应(碳-氢活化)的方法(非专利文献2)。
现有技术文献
非专利文献
非专利文献1:铃木章,有机合成化学協会誌(有机合成化学协会杂志),2005,63,312
非专利文献2:Journal of Organic Chemistry,78(6),2639-2648;2013
发明内容
发明要解决的问题
在选择卤原子作为上述离去基团的情况下,反应后会副产有害的卤素废弃物,因此存在废液的处理、工艺繁琐、环境负担高的问题。在不需要以卤原子为离去基团的碳-氢活化交叉偶联反应中,虽不会副产卤素废弃物,但对反应基质具有诸多限制,存在仍然局限于有限的分子构筑法的问题。
解决问题的方法
作为在不副产卤素废弃物的情况下制造期望的芳香族化合物的方法,申请人等发现了下述方法:在金属催化剂存在下使芳香族硝基化合物和硼酸化合物进行交叉偶联反应。
发明的效果
根据本发明,由于不会副产有害的卤素废弃物,因此能够降低环境负担,能够提供工业上优异的制造工艺。另外,与现有技术相比,反应基质的自由度/选择度宽,能够在工业上高效地制造目标的芳香族化合物。需要说明的是,对于所得芳香族化合物,通过柱色谱法、蒸馏及重结晶等简易的纯化操作,可以获得高纯度的芳香族化合物。或者,可以根据需要进一步经过数个阶段的工序而转换为其它化合物。需要说明的是,由于此前并没有以硝基为离去基团的交叉偶联反应,因此,通过使用本发明的方法,能够提出以往不存在的分子骨架构筑工艺。
具体实施方式
以下,针对本发明进行具体说明。
本发明是以在金属催化剂存在下使芳香族硝基化合物和硼酸化合物进行交叉偶联反应为特征的芳香族化合物的制造方法。
作为芳香族硝基化合物,并无特殊限定,可示例出例如:硝基化芳香族烃化合物、硝基化杂芳族化合物。作为该芳香族硝基化合物,并无特殊限定,但也可以以下述通式(1)表示。
[化学式1]
(式中,Ar1表示任选具有取代基的芳香族烃基或任选具有取代基的杂芳族基团,n表示1~5的整数。)
作为上述任选具有取代基的芳香族烃基,并无特殊限定,可示例出例如:任选具有取代基的苯基、任选具有取代基的联苯基、任选具有取代基的萘基、任选具有取代基的蒽基、任选具有取代基的芘基、任选具有取代基的三联苯基、任选具有取代基的菲基、任选具有取代基的苝基、任选具有取代基的苯并菲基等。
作为上述任选具有取代基的杂芳族基团,并无特殊限定,可列举例如:任选具有取代基的呋喃基、任选具有取代基的苯并呋喃基、任选具有取代基的二苯并呋喃基、任选具有取代基的苯基二苯并呋喃基、任选具有取代基的二苯并呋喃基苯基、任选具有取代基的噻吩基、任选具有取代基的苯并噻吩基、任选具有取代基的二苯并噻吩基、任选具有取代基的苯基二苯并噻吩基、任选具有取代基的二苯并噻吩基苯基、任选具有取代基的吡啶基、任选具有取代基的嘧啶基、任选具有取代基的吡嗪基、任选具有取代基的喹啉基、任选具有取代基的异喹啉基、任选具有取代基的咔唑基、任选具有取代基的9-苯基咔唑基、任选具有取代基的吖啶基、任选具有取代基的苯并噻唑基、任选具有取代基的喹唑啉基、任选具有取代基的喹喔啉基、任选具有取代基的1,6-萘啶基、或任选具有取代基的1,8-萘啶基等。
另外,作为上述任选具有取代基的芳香族烃基上及任选具有取代基的杂芳族基团上的取代基,并无特殊限定,可列举例如:甲基、乙基、碳原子数3~18的烷基(例如,正丙基、异丙基、正丁基、仲丁基、叔丁基、正己基、环己基、环己二烯基、辛基、苄基、或苯乙基等)、碳原子数1-18的卤代烷基(例如,三氟甲基等)、甲氧基、乙氧基、碳原子数3-18的烷氧基(例如,正丙氧基、异丙氧基、正丁氧基、仲丁氧基、叔丁氧基、正己氧基、环己氧基、环己二烯氧基、辛氧基、苄氧基、苯乙氧基等)、碳原子数1-18的卤代烷氧基(例如,三氟甲氧基等)、苯基、甲苯基、吡啶基、嘧啶基、咔唑基、二苯并噻吩基、或二苯并呋喃基等。
关于Ar1,从芳香族化合物的制造效率优异的方面出发,优选为任选具有取代基的碳原子数6~30的芳香族烃基、或任选具有取代基的碳原子数3~30的杂芳族基团,更优选为任选具有取代基的碳原子数6~20的芳香族烃基、或任选具有取代基的碳原子数3~20的杂芳族基团,更具体而言,进一步优选为苯基、联苯基、萘基、三联苯基、二苯并呋喃基、苯基二苯并呋喃基、二苯并呋喃基苯基、二苯并噻吩基、苯基二苯并噻吩基、二苯并噻吩基苯基、吡啶基、苯基吡啶基、吡啶基苯基、嘧啶基、吡嗪基、喹啉基、异喹啉基、咔唑基、或9-苯基咔唑基(这些取代基也可以被甲基、丁基、己基、辛基、甲氧基、苯基、甲苯基、吡啶基、嘧啶基、咔唑基、二苯并噻吩基、二苯并呋喃基取代),更优选为苯基、联苯基、萘基、二苯并呋喃基、苯基二苯并呋喃基、二苯并呋喃基苯基、二苯并噻吩基、苯基二苯并噻吩基、二苯并噻吩基苯基、吡啶基、喹啉基、或咔唑基(这些取代基也可以被甲基、丁基、己基、辛基、或甲氧基取代)。
作为上述硼酸化合物,并无特殊限定,可示例出例如:脂肪族硼酸化合物、芳香族硼化合物、或杂芳族硼酸化合物等。作为该硼酸化合物,并无特殊限定,例如可以以下述通式(2)表示。
[化学式2]
Ar2-B(OR1)2 (2)
(式中,Ar2表示碳原子数1~18的烷基、任选具有取代基的芳香族烃基、或任选具有取代基的杂芳族基团。R1各自独立地表示氢原子、碳原子数1~4的烷基或苯基,2个R1也可以连结而形成包含氧原子及硼原子的环。)
作为上述碳原子数1~18的烷基,并无特殊限定,可示例出例如:甲基、乙基、正丙基、异丙基、正丁基、仲丁基、叔丁基、正己基、环己基、环己二烯基、辛基、苄基、或苯乙基等。
关于上述任选具有取代基的芳香族烃基及任选具有取代基的杂芳族基团,分别与上述Ar1中的任选具有取代基的芳香族烃基及任选具有取代基的杂芳族基团相同。
关于Ar2,从芳香族化合物的制造效率优异的方面出发,优选为碳原子数1~18的烷基、任选具有取代基的碳原子数6~30的芳香族烃基、或任选具有取代基的碳原子数3~30的杂芳族基团,更优选为碳原子数1~18的烷基、任选具有取代基的碳原子数6~20的芳香族烃基、或任选具有取代基的碳原子数3~20的杂芳族基团,更具体而言,优选为:苯基、联苯基、萘基、三联苯基、二苯并呋喃基、苯基二苯并呋喃基、二苯并呋喃基苯基、二苯并噻吩基、苯基二苯并噻吩基、二苯并噻吩基苯基、吡啶基、苯基吡啶基、吡啶基苯基、嘧啶基、吡嗪基、喹啉基、异喹啉基、咔唑基、或9-苯基咔唑基(这些取代基也可以被甲基、丁基、己基、辛基、甲氧基、苯基、甲苯基、吡啶基、嘧啶基、咔唑基、二苯并噻吩基、二苯并呋喃基取代),更优选为苯基、联苯基、萘基、二苯并呋喃基、苯基二苯并呋喃基、二苯并呋喃基苯基、二苯并噻吩基、苯基二苯并噻吩基、二苯并噻吩基苯基、吡啶基、喹啉基、或咔唑基(这些取代基也可以被甲基、丁基、己基、辛基、或甲氧基取代)。
需要说明的是,在本发明中,在使用了上述通式(1)所示的化合物和上述通式(2)所示的化合物的情况下,可得到下述通式(3)所示的芳香族化合物。
[化学式3]
(式中,Ar1、Ar2及n表示与通式(1)及(2)中相同的含义。)
本发明中,由于硝基会离去,因此在键合了硝基的碳上会形成新的键。
在本发明的制造方法中,以上述芳香族硝基化合物(摩尔)÷上述硼酸化合物(摩尔)表示的摩尔比并无特殊限定,但优选在0.1~10.0的范围。从经济性的观点出发,关于该摩尔比,更优选为0.2~5.0、更优选为0.33~3.0、进一步优选为0.5~2.0的范围。
n表示1~5的整数。从高选择性地合成目标的芳香族化合物的观点出发,优选为1~3的整数,进一步优选为1~2的整数。
作为上述金属催化剂,并无特殊限定,可列举钯催化剂或镍催化剂。作为钯催化剂,并无特殊限定,可列举例如:氯化钯(II)、溴化钯(II)、乙酸钯(II)、乙酰丙酮钯(II)、双(苄腈)二氯化钯(II)、双(乙腈)二氯化钯(II)、双(三苯基膦)二氯化钯(II)、二氯四氨合钯(II)、(环辛-1,5-二烯)二氯化钯(II)、三氟乙酸钯(II)等2价钯化合物、三(二亚苄基丙酮)二钯(0)、三(二亚苄基丙酮)二钯氯仿络合物(0)、四(三苯基膦)钯(0)等0价钯化合物。另外,还可以示例出聚合物固定型钯催化剂、钯碳等固定化钯催化剂。需要说明的是,关于这些钯催化剂,也可以使其中共存膦化合物等配位性化合物。作为该配位性化合物,并无特殊限定,可列举例如:三苯基膦、三(邻甲苯基)膦、三(均三甲苯基)膦等单啮芳基膦、三(环己基)膦、三(异丙基)膦、三(叔丁基)膦等单啮烷基膦、2-二环己基膦基-2’,6’-二甲氧基联苯、2-二环己基膦基-2’,6’-二异丙氧基联苯、2-二环己基膦基-2’-甲基联苯、2-二环己基膦基-2’,4’,6’-三异丙基联苯、2-(二叔丁基膦基)-2’,4’,6’-三异丙基联苯、2-二环己基膦基-3,6-二甲氧基-2’,4’,6’-三异丙基联苯、2-(二环己基膦基)联苯、2-(二叔丁基膦基)-2’-(N,N-二甲基氨基)联苯、2-二环己基膦基-2’-(N,N-二甲基氨基)联苯等Buchwald膦配体、1,2-双(二苯基膦基)乙烷、1,2-双(二苯基膦基)丙烷、1,2-双(二环己基膦基)乙烷、1,2-双(二苯基膦基)丁烷、1,2-双(二苯基膦基)二茂铁等二啮膦、1,3-双(2,6-二异丙基苯基)-4,5-二氢-1H-咪唑鎓氯盐、1,3-双(2,6-二异丙基苯基)咪唑鎓氯盐、1,3-双(2,4,6-三甲基苯基)-4,5-二氢-1H-咪唑鎓氯盐等N-杂碳烯配体等。另外,在使钯催化剂中共存膦化合物等配位性化合物的情况下,也可以使用预先将上述钯化合物、膦化合物或N-杂碳烯化合物混合而制备的物质并使其反应。
作为镍催化剂,可列举例如由镍盐和上述膦形成的化合物。所述镍盐表示以镍元素为有效成分的化合物,例如,表示0价~2价的镍盐。具体可列举:氟化镍(II)、氯化镍(II)、溴化镍(II)、碘化镍(II)等卤化镍、镍(0)粉末、硫酸镍(II)、硝酸镍(II)、高氯酸镍(II)等无机盐、甲酸镍(II)、草酸镍(II)、乙酸镍(II)、苯甲酸镍(II)、乙酰丙酮镍(II)等有机酸镍盐。
这些金属催化剂中,从使目标反应进行的观点出发,优选使用钯催化剂。
另外,从使目标反应高选择性地进行的观点出发,优选使金属催化剂中共存Buchwald膦配体,其中尤其优选2-二环己基膦基-3,6-二甲氧基-2’,4’,6’-三异丙基联苯。
需要说明的是,作为Buchwald膦配体,并无特殊限定,可列举例如下述通式(4)所示的膦化合物。
[化学式4]
(式中,R1各自独立地表示环己基或叔丁基。R2各自独立地表示氢原子、甲基、甲氧基、异丙基、异丙氧基、二甲基氨基、或磺酸基。)
金属催化剂的使用量并无特殊限定,但相对于芳香族硝基化合物1摩尔通常为0.01~20摩尔%的范围。如果金属催化剂在上述范围内,则能够以高选择率合成芳香族偶联反应物,但从减少昂贵的金属催化剂的使用量的方面考虑,更优选的金属催化剂使用量为:相对于芳香族硝基化合物1摩尔,以金属换算在0.01~10摩尔%的范围。
本发明中,优选使用碱。作为可使用的碱,从无机碱和/或有机碱中选择即可,并无特殊限定,但优选为氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、碳酸铷、碳酸铯、磷酸钾、磷酸钠、氟化钾、氟化铯等无机碱、甲醇钠、乙醇钠、甲醇钾、乙醇钾、叔丁醇锂、叔丁醇钠、叔丁醇钾等碱金属醇盐、三乙胺、三丁胺、吡啶、二氮杂双环十一碳烯、二氮杂双环壬烯等有机碱,从使目标的芳香族化合物的选择率提高的观点出发,进一步优选为碳酸铷、碳酸铯、磷酸钾、磷酸钠、氟化铯等无机碱。
就可使用的碱的量而言,相对于所使用的芳香族硝基化合物,优选使用1.0倍摩尔以上。碱的量低于1.0倍摩尔时,可能导致目标的芳香族偶联反应物的收率降低。即使明显过量地加入碱也不会使目标的芳香族偶联反应物的收率发生变化,但由于会导致反应结束后的后处理操作变得繁琐,因此更优选的碱的量为1.0~5.0倍摩尔的范围。
本反应通常在惰性溶剂存在下进行。作为可使用的溶剂,只要是不会显著阻碍本反应的溶剂则没有特殊限定,可列举:苯、甲苯、二甲苯等芳香族类有机溶剂、***、二异丙基醚、二丁基醚、四氢呋喃、二甲氧基乙烷、1,4-二烷、环戊基甲基醚、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇二丁基醚、三乙二醇二甲基醚等醚类有机溶剂、乙腈、二甲基甲酰胺、二甲亚砜、六甲基磷酰三胺等。这些溶剂中,更优选:***、二甲氧基乙烷、二异丙基醚、二丁基醚、四氢呋喃、1,4-二烷、环戊基甲基醚、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇二丁基醚、三乙二醇二甲基醚等醚类有机溶剂。
本反应可以在常压下,氮气、氩气等不活泼气体氛围中进行,另外,也可以在加压下进行。反应可在20~250℃的范围内进行,但为了提高目标的芳香族化合物的收率,优选在50~200℃的范围内进行,更优选在100~160℃的范围内进行,进一步优选在120℃~150度的范围内进行。
本反应中,作为添加剂,也可以使用相转移催化剂。作为相转移催化剂,并没有特殊限定,具体可列举:24-冠-8、18-冠-6、15-冠-5、12-冠-4等冠醚类、四(正丁基)氯化铵、四(正丁基)溴化铵、苄基三乙基氯化铵、三乙基正十二烷基氯化铵、三乙基正十二烷基溴化铵、三甲基正十六烷基氯化铵、三甲基正十六烷基溴化铵等季铵盐。
本反应需要的反应时间根据芳香族硝基化合物、硼酸化合物、金属催化剂、碱的量、种类及反应温度等不同而并不是一定的,但优选从数分钟~72小时的范围内选择。
实施例
以下,结合实施例对本发明进行具体说明。但本发明的解释完全不受限于这些实施例。
测定设备:岛津制作所公司制气相色谱GC2014(分析条件使用色谱柱:SGE公司制BP-1、检测器:FID@290℃)、NMR日本电子株式会社制ECS-400(1H NMR、400MHz;13C NMR、101MHz)、中压柱色谱Shoko Scientific公司制Purif-espoir2。
实施例1
在氮气下向15mL螺口瓶管中加入搅拌子、4-硝基苯甲醚92mg(0.60mmol)、苯基硼酸110mg(0.90mmol)、乙酰丙酮钯(II)9.1mg(0.030mmol)、2-二环己基膦基-3,6-二甲氧基-2’,4’,6’-三异丙基联苯64mg(0.12mmol)、磷酸三钾n水合物480mg(1.8mmol)、18-冠-616mg(0.060mmol)、及1,4-二烷3mL。将瓶管盖严之后,于130℃加热搅拌24小时。接着,将反应液冷却至室温。向该反应液中添加二氯甲烷,使其通过硅藻土而进行了过滤。将浓缩滤液得到的残渣溶解于***(20mL),加入了30%过氧化氢水溶液(5mL)。室温下搅拌1小时之后,利用蒸馏水(10mL)和饱和硫酸铁(II)水溶液(10mL)进行了洗涤。利用***(20mL×3)进行萃取之后,利用饱和食盐水(10mL)对收集的有机层进行洗涤。利用无水硫酸镁进行干燥之后,将浓缩得到的残渣利用中压柱色谱(使用Biotage SNAP Ultra柱(粒径25μm)、展开溶剂=己烷/乙酸乙酯)进行纯化,得到了白色粉末形式的目标的4-甲氧基联苯84mg(收率76%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ7.59-7.51(m、4H)、7.42(t、J=7.4Hz、2H)、7.31(t、J=7.4Hz、1H)、6.99(d、J=8.1Hz、2H)、3.86(s、3H)
13C-NMR(CDCL3)=δ159.1、140.8、133.7、128.7、128.1、126.7、126.6、114.2、55.3。
实施例2
在氮气下向15mL螺口瓶管中加入搅拌子、4-硝基联苯119mg(0.60mmol)、苯基硼酸110mg(0.90mmol)、乙酰丙酮钯(II)9.1mg(0.030mmol)、2-二环己基膦基-3,6-二甲氧基-2’,4’,6’-三异丙基联苯64mg(0.12mmol)、氟化铯270mg(1.8mmol)、及1,4-二烷3mL。将瓶管盖严之后,于150℃加热搅拌24小时。接着,将反应液冷却至室温。向该反应液中添加二氯甲烷,使其通过硅藻土而进行了过滤。将浓缩滤液得到的残渣溶解于***(20mL),加入了30%过氧化氢水溶液(5mL)。室温下搅拌1小时之后,利用蒸馏水(10mL)和饱和硫酸铁(II)水溶液(10mL)进行了洗涤。利用***(20mL×3)进行萃取之后,利用饱和食盐水(10mL)对收集的有机层进行洗涤。利用无水硫酸镁进行干燥之后,将浓缩得到的残渣利用中压柱色谱(使用Biotage SNAP Ultra柱(粒径25μm)、展开溶剂=己烷/乙酸乙酯)进行纯化,得到了白色粉末形式的目标的对三联苯90mg(收率65%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ7.72-7.64(m、8H)、7.48(t、J=7.5Hz、4H)、7.38(t、J=7.3Hz、2H)
13C-NMR(CDCL3)=δ140.7、140.1、128.8、127.5、127.3、127.0。
实施例3
在氮气下向15mL螺口瓶管中加入搅拌子、4-(三氟甲基)硝基苯115mg(0.60mmol)、苯基硼酸110mg(0.90mmol)、乙酰丙酮钯(II)9.1mg(0.030mmol)、2-二环己基膦基-3,6-二甲氧基-2’,4’,6’-三异丙基联苯64mg(0.12mmol)、氟化铯270mg(1.8mmol)、及1,4-二烷3mL。将瓶管盖严之后,于130℃加热搅拌24小时。接着,将反应液冷却至室温。向该反应液中添加二氯甲烷,使其通过硅藻土而进行了过滤。将浓缩滤液得到的残渣利用中压柱色谱(使用Biotage SNAP Ultra柱(粒径25μm)、展开溶剂=己烷/乙酸乙酯)进行纯化,得到了白色粉末形式的目标的4-(三氟甲基)联苯74mg(收率55%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ7.70(s、4H)、7.61(d、J=6.9Hz、2H)、7.48(t、J=7.3Hz、2H)、7.42(d、J=7.3Hz、1H)
13C-NMR(CDCL3)=144.7、139.8、129.3(q、J=32.6Hz)、129.0、128.2、127.4、127.3、125.7(q、J=3.8Hz)、124.2(q、J=271.2Hz)。
实施例4
代替在实施例2中使用的4-硝基联苯119mg(0.60mmol)而使用了3-硝基苯甲酸甲酯109mg(0.60mmol),除此以外,实施同样的实验操作,得到了无色油状物形式的3-苯基苯甲酸甲酯86mg(收率68%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ8.29(s、1H)、8.03(d、J=7.7Hz、1H)、7.79(d、J=7.7Hz、1H)、7.63(d、J=8.1Hz、2H)、7.52(t、J=7.7Hz、1H)、7.47(t、J=7.7Hz、2H)、7.39(t、J=7.0Hz、1H)、3.95(s、3H)
13C-NMR(CDCL3)=δ167.0、141.4、140.1、131.5、130.6、128.9、128.8、128.3、128.2、127.7、127.1、52.2。
实施例5
在氮气下向15mL螺口瓶管中加入搅拌子、3,5-二氟硝基苯95mg(0.60mmol)、苯基硼酸110mg(0.90mmol)、乙酰丙酮钯(II)9.1mg(0.030mmol)、2-二环己基膦基-3,6-二甲氧基-2’,4’,6’-三异丙基联苯64mg(0.12mmol)、氟化铯270mg(1.8mmol)、及1,4-二烷3mL。将瓶管盖严之后,于130℃加热搅拌24小时。接着,将反应液冷却至室温。向该反应液中添加二氯甲烷,使其通过硅藻土而进行了过滤。将浓缩滤液得到的残渣利用中压柱色谱(使用Biotage SNAP Ultra柱(粒径25μm)、展开溶剂=己烷/乙酸乙酯)进行纯化,得到了无色油状物形式的3,5-二氟联苯86mg(收率68%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ7.55(d、J=7.8Hz、2H)、7.46(t、J=7.3Hz、2H)、7.40(tt、J=6.9、1.4Hz、1H)、7.11(dd、J=8.7、2.3Hz、2H)、6.79(tt、J=8.7、2.3Hz,1H)
13C-NMR(CDCL3)=δ163.3(dd、J=247.8、12.9Hz)、144.5(t、J=9.1Hz)、138.9、129.0、128.4、127.0、109.9(dd、J=19.2、6.7Hz)、102.5(t、J=25.9Hz)。
实施例6
在氮气下向15mL螺口瓶管中加入搅拌子、1-硝基萘104mg(0.60mmol)、苯基硼酸110mg(0.90mmol)、乙酰丙酮钯(II)9.1mg(0.030mmol)、2-二环己基膦基-3,6-二甲氧基-2’,4’,6’-三异丙基联苯64mg(0.12mmol)、磷酸三钾n水合物480mg(1.8mmol)、及1,4-二烷3mL。将瓶管盖严之后,于130℃加热搅拌12小时。接着,将反应液冷却至室温。向该反应液中添加二氯甲烷,使其通过硅藻土而进行了过滤后,将浓缩得到的残渣利用中压柱色谱(使用Biotage SNAP Ultra柱(粒径25μm)、展开溶剂=己烷/乙酸乙酯)进行纯化,得到了无色油状物形式的目标的1-苯基萘101mg(收率82%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ7.97-7.87(m、3H)、7.59-7.42(m、9H)
13C-NMR(CDCL3)=δ140.7、140.2、133.7、131.6、130.0、128.2、127.6、127.2、126.9、126.0、125.7、125.3。
实施例7
代替在实施例6中使用的1-硝基萘104mg(0.60mmol)而使用了2-硝基萘104mg(0.60mmol),除此以外,实施同样的实验操作,得到了白色粉末形式的2-苯基萘100mg(收率81%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ8.06(s、1H)、7.92(t、J=8.7Hz、2H)、7.88(d、J=7.4Hz、1H)、7.79-7.71(m、3H)、7.55-7.46(m、4H)、7.40(t、J=7.0Hz、1H)
13C-NMR(CDCL3)=δ141.1、138.5、133.6、132.6、128.8、128.4、128.2、127.6、127.4、127.3、126.3、125.9、125.8、125.6。
实施例8
代替在实施例6中使用的1-硝基萘104mg(0.60mmol)而使用了3-硝基吡啶74mg(0.60mmol),除此以外,实施同样的实验操作,得到了无色油状物形式的3-苯基吡啶73mg(收率79%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ8.86(bs、1H)、8.59(d、J=4.7Hz、1H)、7.87(bd、J=8.1、Hz、1H)、7.59(d、J=8.1Hz、2H)、7.48(t、J=7.4Hz、2H)、7.45-7.33(m、2H)
13C-NMR(CDCL3)=δ148.5、148.3、137.8、136.6、134.3、129.0、128.1、127.1、123.5。
实施例9
在实施例1中代替苯基硼酸110mg(0.90mmol)而使用了4-甲基苯基硼酸122mg(0.90mmol),且未添加16mg(0.060mmol)的18-冠-6,除此以外,实施同样的实验操作,得到了白色固体形式的4-甲基-4’-甲氧基联苯95mg(收率79%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ7.52(d、J=8.7Hz、2H)、7.45(d、J=7.4Hz、2H)、7.23(d、J=8.1Hz、2H)、6.97(d、J=8.1Hz、2H)、3.85(s、3H)、2.39(s、3H)
13C-NMR(CDCL3)=δ158.9、137.9、136.3、133.7、129.4、127.9、126.6、114.1、55.3、21.0。
实施例10
代替实施例1中的苯基硼酸110mg(0.90mmol)而使用了4-氟苯基硼酸126mg(0.90mmol)、且未添加16mg(0.060mmol)的18-冠-6,除此以外,实施同样的实验操作,得到了白色固体形式的4-氟-4’-甲氧基联苯88mg(收率73%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ7.54-7.45(m、4H)、7.16-7.07(m、2H)、6.99(d、J=8.7Hz、2H)、3.86(s、3H)
13C-NMR(CDCL3)=δ162.0(d、J=245.4Hz)、159.1、136.9(d、J=2.9Hz)、132.8、128.2(d、J=8.6Hz)、128.0、115.5(d、J=21.1Hz)、114.2、55.3。
实施例11
代替在实施例1中使用的4-硝基苯甲醚92mg(0.60mmol)而使用了4-(4-硝基苯基)吗啉125mg(0.60mmol),除此以外,实施同样的实验操作,得到了白色固体形式的4-(1,1’-联苯基-4-基)吗啉90mg(收率63%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ7.63-7.54(m、4H)、7.45(t、J=7.4Hz、2H)、7.33(t、J=7.4Hz、1H)、7.01(d、J=8.7Hz、2H)、3.91(t、J=7.4Hz、4H)、3.23(t、J=4.4Hz、4H)
13C-NMR(CDCL3)=δ150.5、140.7、132.6、128.6、127.7、126.6、115.7、66.8、49.1。
实施例12
代替实施例1中的4-硝基苯甲醚92mg(0.60mmol)而使用了4-硝基甲苯82mg(0.60mmol)、且代替苯基硼酸110mg(0.90mmol)而使用了4-甲氧基苯基硼酸137mg(0.90mmol),除此以外,实施同样的实验操作,得到了白色固体形式的4-甲氧基-4’-甲基-1,1’-联苯93mg(收率78%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ7.52(d、J=8.7Hz、2H)、7.46(d、J=7.4Hz、2H)、7.23(d、J=8.1Hz、2H)、6.97(d、J=8.1Hz、2H)、3.85(s、3H)、2.39(s、3H)
13C-NMR(CDCL3)=δ158.9、137.9、136.3、133.7、129.4、127.9、126.5、114.1、55.2、21.0。
实施例13
代替实施例1中的4-硝基苯甲醚92mg(0.60mmol)而使用了硝基苯62μL(0.60mmol)、代替苯基硼酸110mg(0.90mmol)而使用了4-甲氧基苯基硼酸137mg(0.90mmol),除此以外,实施同样的实验操作,得到了白色固体形式的4-甲氧基-1,1’-联苯93mg(收率78%)。通过1H及13C-NMR实施目标物的鉴定,得到了与实施例1中得到的化合物相同的图谱数据。
实施例14
代替实施例1中的4-硝基苯甲醚92mg(0.60mmol)而使用了2-(4-硝基苯基)-1,3-二氧戊环117mg(0.60mmol)、代替苯基硼酸110mg(0.90mmol)而使用了4-甲氧基苯基硼酸137mg(0.90mmol),除此以外,实施了同样的反应操作。接着,将反应液冷却至室温。向该反应液中添加3N盐酸水溶液3.0mL及异丙醇10mL,于80℃加热搅拌3小时。其后,将反应液冷却至室温,中和反应液之后,添加二氯甲烷,使其通过硅藻土而进行了过滤。将浓缩滤液得到的残渣溶解于***(20mL),加入了30%过氧化氢水溶液(5mL)。室温下搅拌1小时之后,利用蒸馏水(10mL)和饱和硫酸铁(II)水溶液(10mL)进行了洗涤。利用***(20mL×3)进行萃取之后,利用饱和食盐水(10mL)对收集的有机层进行洗涤。利用无水硫酸镁进行干燥之后,将浓缩得到的残渣利用中压柱色谱(使用Biotage SNAP Ultra柱(粒径25μm)、展开溶剂=己烷/乙酸乙酯)进行纯化,得到了白色固体形式的目标的4’-甲氧基-[1,1’-联苯基]-4-甲醛77mg(收率61%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ10.03(s、1H)、7.93(d、J=8.4Hz、2H)、7.72(d、J=8.1Hz、2H)、7.60(d、J=8.1Hz、2H)、7.01(d、J=8.7Hz、2H)、3.87(s、3H)
13C-NMR(CDCL3)=δ191.9、160.1、146.7、134.6、132.0、130.3、128.5、127.0、114.4、55.3。
实施例15
代替在实施例1中使用的4-硝基苯甲醚92mg(0.60mmol)而使用了2-甲基-2-(4-硝基苯基)-1,3-二氧戊环125mg(0.60mmol),除此以外,实施了同样的反应操作。接着,将反应液冷却至室温。向该反应液中添加3N盐酸水溶液3.0mL及异丙醇10mL,于80℃加热搅拌3小时。其后,将反应液冷却至室温,中和反应液之后,添加二氯甲烷,使其通过硅藻土而进行了过滤。将浓缩滤液得到的残渣溶解于***(20mL),加入了30%过氧化氢水溶液(5mL)。室温下搅拌1小时之后,利用蒸馏水(10mL)和饱和硫酸铁(II)水溶液(10mL)进行了洗涤。利用***(20mL×3)进行萃取之后,利用饱和食盐水(10mL)对收集的有机层进行洗涤。利用无水硫酸镁进行干燥之后,将浓缩得到的残渣利用中压柱色谱(使用Biotage SNAP Ultra柱(粒径25μm)、展开溶剂=己烷/乙酸乙酯)进行纯化,得到了白色固体形式的目标的1-([1,1’-联苯基]-4-基)乙烷-1-酮85mg(收率72%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ8.04(d、J=8.1Hz、2H)、7.69(d、J=8.1Hz、2H)、7.63(d、J=8.1Hz、2H)、7.48(t、J=7.4Hz、2H)、7.41(t、J=7.4Hz、1H)、2.64(s、3H)
13C-NMR(CDCL3)=δ197.7、145.7、139.8、135.7、128.9、128.8、128.2、127.2、127.1、26.6。
实施例16
代替实施例1中的4-硝基苯甲醚92mg(0.60mmol)而使用了1-硝基-4-(三氟甲基)苯115mg(0.60mmol)、代替苯基硼酸110mg(0.90mmol)而使用了4-甲氧基苯基硼酸182mg(1.20mmol)、代替磷酸三钾n水合物480mg(1.8mmol)而使用了氟化铯0.27g(1.8mmol)、未添加16mg(0.060mmol)的18-冠-6、且代替1,4-二烷3mL而使用了甲苯3mL,除此以外,实施同样的实验操作,得到了白色固体形式的4-甲氧基-4’-(三氟甲基)-1,1’-联苯82mg(收率54%)。通过1H、13C及19F-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ7.71-7.62(m、4H)、7.56(d、J=8.7Hz、2H)、7.02(d、J=8.7Hz、2H)、3.87(s、3H)
13C-NMR(CDCL3)=δ159.8、144.2、132.1、128.6(q、J=32.6Hz)、128.3、126.8、125.6(q、J=3.8Hz)、124.4(q、J=272Hz)、114.4、55.3
19F-NMR(CDCL3)=δ62.16。
实施例17
代替实施例1中的4-硝基苯甲醚92mg(0.60mmol)而使用了1-氟-4-硝基苯85mg(0.60mmol)、代替苯基硼酸110mg(0.90mmol)而使用了4-甲氧基苯基硼酸137mg(0.90mmol)、代替磷酸三钾n水合物480mg(1.8mmol)而使用了氟化铯0.46g(3.0mmol)、未添加16mg(0.060mmol)的18-冠-6、且代替1,4-二烷3mL而使用了甲苯3mL,除此以外,实施同样的实验操作,得到了白色固体形式的4-氟-4’-甲氧基-1,1’-联苯56mg(收率46%)。通过1H、13C及19F-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ7.54-7.45(m、4H)、7.16-7.07(m、2H)、6.99(d、J=8.7Hz、2H)、3.86(s、3H)
13C-NMR(CDCL3)=δ162.0(d、J=245.4Hz)、159.1、136.9(d、J=2.9Hz)、132.8、128.2(d、J=8.6Hz)、128.0、115.5(d、J=21.1Hz)、114.2、55.3
19F-NMR(CDCL3)=δ116.59。
实施例18
代替在实施例1中使用的4-硝基苯甲醚92mg(0.60mmol)而使用了3-硝基苯甲醚92mg(0.60mmol),除此以外,实施同样的实验操作,得到了无色透明油形式的3-甲氧基-1,1’-联苯82mg(收率74%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ7.61(d、J=8.1Hz、2H)、7.45(t、J=7.4Hz、2H)、7.42-7.33(m、2H)、7.20(d、J=7.4Hz、1H)、7.15(s、1H)、6.92(d、J=7.4Hz、1H)、3.88(s、3H)
13C-NMR(CDCL3)=δ159.9、142.7、141.1、129.7、128.7、127.4、127.2、119.7、112.9、112.6、55.3。
实施例19
代替实施例1中的4-硝基苯甲醚92mg(0.60mmol)而使用了1,3-二甲基-5-硝基苯91mg(0.60mmol)、代替苯基硼酸110mg(0.90mmol)而使用了4-甲氧基苯基硼酸182mg(1.20mmol),除此以外,实施同样的实验操作,得到了白色固体形式的4’-甲氧基-3,5-二甲基-1,1’-联苯90mg(收率71%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ7.52(d、J=8.7Hz、2H)、7.18(s、2H)、7.00-6.94(m、3H)、3.86(s、3H)、2.38(s、6H)
13C-NMR(CDCL3)=δ159.0、140.8、138.2、134.0、128.3、128.1、124.7、114.0、55.3、21.4。
实施例20
代替在实施例1中使用的4-硝基苯甲醚92mg(0.60mmol)而使用了1-(甲磺酰基)-3-硝基苯121mg(0.60mmol),除此以外,实施同样的实验操作,得到了白色固体形式的3-(甲磺酰基)-1,1’-联苯91mg(收率65%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ8.16(s、1H)、7.89(dd、J=19.5、8.1Hz、2H)、7.68-7.58(m、3H)、7.48(t、J=7.4Hz、2H)、7.42(t、J=7.4Hz、1H)、3.10(s、3H)
13C-NMR(CDCL3)=δ142.6、141.0、138.9、132.2、129.8、129.0、128.3、127.1、125.8、125.7、44.4。
实施例21
代替实施例1中的4-硝基苯甲醚92mg(0.60mmol)而使用了2-硝基甲苯82mg(0.60mmol)、代替苯基硼酸110mg(0.90mmol)而使用了4-甲氧基苯基硼酸137mg(0.90mmol),除此以外,实施同样的实验操作,得到了无色透明油形式的4-甲氧基-2’-甲基-1,1’-联苯81mg(收率68%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ7.29-7.20(m、6H)、6.95(d、J=8.7Hz、2H)、3.85(s、3H)、2.28(s、3H)
13C-NMR(CDCL3)=δ158.5、141.5、135.5、134.3、130.3、130.2、129.9、126.9、125.7、113.4、55.3、20.5。
实施例22
代替在实施例1中使用的4-硝基苯甲醚92mg(0.60mmol)而使用了2-硝基苯甲醚92mg(0.60mmol),除此以外,实施同样的实验操作,得到了无色透明油形式的2-甲氧基-1,1’-联苯93mg(收率84%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ7.58-7.52(m、2H)、7.42(t、J=7.4Hz、2H)、7.38-7.30(m、3H)、7.04(t、J=7.4Hz、1H)、7.00(d、J=8.7Hz、1H)、3.82(s、3H)。
13C-NMR(CDCL3)=δ156.4、138.5、130.9、130.7、129.5、128.6、127.9、126.9、120.8、112.2、55.5。
实施例23
代替实施例1中的4-硝基苯甲醚92mg(0.60mmol)而使用了9-硝基蒽134mg(0.60mmol)、代替磷酸三钾n水合物480mg(1.8mmol)而使用了氟化铯0.46g(3.0mmol)、未添加16mg(0.060mmol)的18-冠-6、代替1,4-二烷3mL而使用了甲苯3mL,除此以外,实施同样的实验操作,得到了白色固体形式的9-苯基蒽67mg(收率44%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ8.53(s、1H)、8.08(d、J=8.1Hz、2H)、7.72(d、J=9.4Hz、2H)、7.66-7.55(m、3H)、7.53-7.45(m、4H)、7.42-7.35(m、2H)
13C-NMR(CDCL3)=δ138.7、137.0、131.3、131.2、130.2、128.32、128.30、127.4、126.8、126.5、125.3、125.1。
实施例24
代替在实施例1中使用的4-硝基苯甲醚92mg(0.60mmol)而使用了2-甲氧基-3-硝基吡啶92mg(0.60mmol),除此以外,实施同样的实验操作,得到了无色透明油形式的2-甲氧基-3-苯基吡啶89mg(收率80%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ8.18(dd、J=4.7、1.3Hz、1H)、7.62(dd、J=7.4、1.3Hz、1H)、7.57(d、J=8.1Hz、2H)、7.44(t、J=7.7Hz、2H)、7.36(t、J=7.0Hz、1H)、6.98(dd、J=6.7、4.7Hz、1H)、3.98(s、3H)
13C-NMR(CDCL3)=δ160.8、145.7、138.6、136.7、129.1、128.2、127.5、124.6、117.1、53.5。
实施例25
代替实施例1中的4-硝基苯甲醚92mg(0.60mmol)而使用了5-硝基喹啉104mg(0.60mmol)、且未添加16mg(0.060mmol)的18-冠-6,除此以外,实施同样的实验操作,得到了淡黄色固体形式的5-苯基喹啉87mg(收率71%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ8.95-8.90(m、1H)、8.24(d、J=8.7、1H)、8.14(d、J=8.7Hz、1H)、7.76(t、J=8.1、Hz、1H)、7.55-7.41(m、6H)、7.34(dd、J=8.7、4.4Hz、1H)
13C-NMR(CDCL3)=δ150.2、148.5、140.4、139.3、134.3、130.0、128.92、128.86、128.4、127.6、127.2、126.6、121.0。
实施例26
代替在实施例1中使用的4-硝基苯甲醚92mg(0.60mmol)而使用了5-硝基异喹啉104mg(0.60mmol),除此以外,实施同样的实验操作,得到了黄色油形式的5-苯基异喹啉86mg(收率70%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ9.31(s、1H)、8.47(d、J=5.4、1H)、7.97(t、J=4.4Hz、1H)、7.72(d、J=6.0、Hz、1H)、7.64(d、J=4.0Hz、2H)、7.54-7.41(m、5H)
13C-NMR(CDCL3)=δ152.6、143.1、139.1、138.8、134.0、130.9、129.7、128.8、128.4、127.7、127.1、126.8、118.5。
实施例27
代替实施例1中的苯基硼酸110mg(0.90mmol)而使用了4-叔丁基苯基硼酸160mg(0.90mmol),除此以外,实施同样的实验操作,得到了白色固体形式的4-(叔丁基)-4’-甲氧基-1,1’-联苯116mg(收率80%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ7.60-7.52(m、4H)、7.51-7.46(m、2H)、7.01(d、J=8.1、2H)、3.88(s、3H)、1.41(s、9H)
13C-NMR(CDCL3)=δ158.9、149.6、137.9、133.6、128.0、126.3、125.6、114.1、55.3、34.4、31.4。
实施例28
代替实施例1中的4-硝基苯甲醚92mg(0.60mmol)而使用了硝基苯62μL(0.60mmol)、代替苯基硼酸110mg(0.90mmol)而使用了[1,1’-联苯基]-4-基-硼酸178mg(0.90mmol),除此以外,实施同样的实验操作,得到了白色粉末形式的对三联苯91mg(收率66%)。通过1H及13C-NMR实施目标物的鉴定,得到了与实施例2中得到的化合物相同的图谱数据。
实施例29
代替实施例1中的4-硝基苯甲醚92mg(0.60mmol)而使用了2-硝基苯甲醚92mg(0.60mmol)、代替苯基硼酸110mg(0.90mmol)而使用了4-乙酰基苯基硼酸197mg(1.20mmol),除此以外,实施同样的实验操作,得到了白色固体形式的1-(2’-甲氧基-[1,1’-联苯基]-4-基)乙烷-1-酮91mg(收率66%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ8.01(bd、J=7.4Hz、2H)、7.65(bd、J=8.1Hz、2H)、7.42-7.32(m、2H)、7.06(t、J=7.4Hz、1H)、7.01(d、J=8.1Hz、1H)、3.83(s、3H)、2.64(s、3H)
13C-NMR(CDCL3)=δ197.8、156.4、143.5、135.4、130.6、129.6、129.4、129.3、128.0、120.9、111.2、55.5、26.6。
实施例30
代替实施例1中的4-硝基苯甲醚92mg(0.60mmol)而使用了2-硝基苯甲醚92mg(0.60mmol)、代替苯基硼酸110mg(0.90mmol)而使用了4-(甲氧基羰基)苯基硼酸162mg(0.90mmol),除此以外,实施同样的实验操作,得到了白色固体形式的2’-甲氧基-[1,1’-联苯基]-4-羧酸甲酯95mg(收率66%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ8.09(d、J=8.7Hz、2H)、7.62(d、J=8.1Hz、2H)、7.41-7.32(m、2H)、7.06(t、J=7.7Hz、1H)、7.01(d、J=8.1Hz、1H)、3.94(s、3H)、3.82(s、3H)
13C-NMR(CDCL3)=δ167.1、156.4、143.3、130.7、129.5、129.3、129.2、128.4、120.9、111.3、55.5、52.0。
实施例31
代替实施例1中的4-硝基苯甲醚92mg(0.60mmol)而使用了2-硝基苯甲醚92mg(0.60mmol)、代替苯基硼酸110mg(0.90mmol)而使用了4-(三氟甲基)苯基硼酸171mg(0.90mmol),除此以外,实施同样的实验操作,得到了无色透明油形式的2-甲氧基-4’-(三氟甲基)-1,1’-联苯98mg(收率65%)。通过1H、13C及19F-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ7.74-7.66(m、4H)、7.42(t、J=7.7Hz、1H)、7.36(d、J=7.4Hz、1H)、7.12(t、J=7.4Hz、1H)、7.05(d、J=8.1Hz、1H)、3.86(s、3H)
13C-NMR(CDCL3)=δ156.4、142.2、130.7、129.8、129.5、129.1、128.9(q、J=32.6Hz)、124.8(q、J=3.8Hz)、124.4(q、J=272.2Hz)、120.9、111.3、55.5
19F-NMR(CDCL3)=δ62.8。
实施例32
代替实施例1中的4-硝基苯甲醚92mg(0.60mmol)而使用了3-硝基苯甲酸甲酯109mg(0.60mmol)、代替苯基硼酸110mg(0.90mmol)而使用了4-(三氟甲基)苯基硼酸171mg(0.90mmol)、代替磷酸三钾n水合物480mg(1.8mmol)而使用了氟化铯0.46g(3.0mmol)、且未添加16mg(0.060mmol)的18-冠-6,除此以外,实施同样的实验操作,得到了无色透明油形式的4’-(三氟甲基)-1,1’-联苯基-3-羧酸甲酯106mg(收率63%)。通过1H、13C及19F-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ8.29(bs、1H)、8.08(d、J=8.1Hz、1H)、7.79(d、J=7.4Hz、1H)、7.76-7.70(m、4H)、7.55(t、J=8.1Hz、1H)、3.96(s、3H)
13C-NMR(CDCL3)=δ166.8、143.6、140.0、131.6、130.9、129.8(q、J=32.6Hz)、129.2、129.1、128.4、127.5、125.8(q、J=3.8Hz)、124.2(q、J=272.2Hz)、52.3
19F-NMR(CDCL3)=δ62.4。
实施例33
代替实施例1中的4-硝基苯甲醚92mg(0.60mmol)而使用了硝基苯74mg(0.60mmol)、代替苯基硼酸110mg(0.90mmol)而使用了3-甲氧基苯基硼酸137mg(0.90mmol),除此以外,实施同样的实验操作,得到了无色透明油形式的3-甲氧基-1,1’-联苯79mg(收率72%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ7.60(d、J=8.1Hz、2H)、7.45(t、J=7.4Hz、2H)、7.42-7.32(m、2H)、7.20(d、J=8.1Hz、1H)、7.14(s、1H)、6.92(d、J=8.1Hz、1H)、3.89(s、3H)
13C-NMR(CDCL3)=δ159.9、142.7、141.1、129.7、128.7、127.4、127.2、119.7、112.9、112.6、55.3。
实施例34
代替实施例1中的4-硝基苯甲醚92mg(0.60mmol)而使用了2-硝基苯甲醚92mg(0.60mmol)、代替苯基硼酸110mg(0.90mmol)而使用了邻甲苯基硼酸122mg(0.90mmol),除此以外,实施同样的实验操作,得到了无色透明油形式的2-甲氧基-2’-甲基-1,1’-联苯79mg(收率67%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ7.34(t、J=8.1Hz、1H)、7.28-7.12(m、5H)、7.01(t、J=7.4Hz、1H)、6.96(d、J=8.1Hz、1H)、3.76(s、3H))、2.14(s、3H)
13C-NMR(CDCL3)=δ156.6、138.6、136.8、131.0、130.8、130.0、129.6、128.5、127.3、125.4、120.4、110.6、55.4、19.9。
实施例35
代替实施例1中的4-硝基苯甲醚92mg(0.60mmol)而使用了1-硝基萘104mg(0.60mmol)、代替苯基硼酸110mg(0.90mmol)而使用了2,6-二甲基苯基硼酸135mg(0.90mmol),除此以外,实施同样的实验操作,得到了白色固体形式的1-(2,6-二甲基苯基)萘50mg(收率36%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ7.91(d、J=7.8Hz、1H)、7.86(d、J=8.2Hz、1H)、7.55(t、J=7.8Hz、1H)、7.47(t、J=6.9Hz、1H)、7.38-7.32(m、2H)、7.30-7.22(m、2H)、7.20-7.16(m、2H)、1.91(s、6H)
13C-NMR(CDCL3)=δ139.6、138.7、137.0、133.7、131.7、128.3、127.3、127.24、127.17、126.4、126.0、125.75、125.68、125.3、20.4。
实施例36
代替实施例1中的4-硝基苯甲醚92mg(0.60mmol)而使用了2-硝基苯甲醚92mg(0.60mmol)、代替苯基硼酸110mg(0.90mmol)而使用了2-萘硼酸155mg(0.90mmol),除此以外,实施同样的实验操作,得到了白色固体形式的2-(2-甲氧基苯基)萘113mg(收率81%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ8.04(s、1H)、7.96-7.90(m、3H)、7.77(d、J=8.1Hz、1H)、7.58-7.48(m、3H)、7.42(t、J=7.7Hz、1H)、7.14(t、J=7.4Hz、1H)、7.08(d、J=8.1Hz、1H)、3.88(s、3H)
13C-NMR(CDCL3)=δ156.6、136.2、133.4、132.4、131.1、130.6、128.7、128.1(2C)、127.5、127.1、125.8、125.7、120.9、111.2、55.5。
实施例37
代替实施例1中的4-硝基苯甲醚92mg(0.60mmol)而使用了2-甲氧基-3-硝基吡啶92mg(0.60mmol)、代替苯基硼酸110mg(0.90mmol)而使用了3-噻吩硼酸115mg(0.90mmol),除此以外,实施同样的实验操作,得到了白色固体形式的2-甲氧基-3-(噻吩-3-基)吡啶54mg(收率47%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ8.12(bd、J=4.7Hz、1H)、7.78(bd、J=7.4Hz、1H)、7.75-7.71(m、1H)、7.47(bd、J=4.7Hz、1H)、7.37(dd、J=4.7、3.4Hz、1H)、6.95(dd、J=7.4、4.7Hz、1H)、4.04(s、3H)
13C-NMR(CDCL3)=δ160.5、145.1、137.0、136.4、127.7、125.0、123.8、119.2、117.0、53.5。
实施例38
在设置有温度计及冷凝管的50mL四颈烧瓶中加入搅拌子、4-硝基苯甲醚92mg(0.60mmol)、苯基硼酸110mg(0.90mmol)、乙酰丙酮钯(II)9.1mg(0.030mmol)、2-二环己基膦基-3,6-二甲氧基-2’,4’,6’-三异丙基联苯64mg(0.12mmol)、磷酸三钾n水合物480mg(1.8mmol)、18-冠-616mg(0.060mmol)、及二乙二醇二甲基醚3mL。将四颈***空气层部利用氮气置换之后,在常压下、于130℃加热搅拌24小时。接着,将反应液冷却至室温。向该反应液中添加二氯甲烷,使其通过硅藻土而进行了过滤。将浓缩滤液得到的残渣溶解于***(20mL),加入了30%过氧化氢水溶液(5mL)。室温下搅拌1小时之后,利用蒸馏水(10mL)和饱和硫酸铁(II)水溶液(10mL)进行了洗涤。利用***(20mL×3)进行萃取之后,利用饱和食盐水(10mL)对收集的有机层进行洗涤。利用无水硫酸镁进行干燥之后,将浓缩得到的残渣利用中压柱色谱(使用Biotage SNAP Ultra柱(粒径25μm)、展开溶剂=己烷/乙酸乙酯)进行纯化,得到了白色粉末形式的目标的4-甲氧基联苯53mg(收率48%)。通过1H及13C-NMR实施了目标物的鉴定。
1H-NMR(CDCL3)=δ7.59-7.51(m、4H)、7.42(t、J=7.4Hz、2H)、7.31(t、J=7.4Hz、1H)、6.99(d、J=8.1Hz、2H)、3.86(s、3H)。
13C-NMR(CDCL3)=δ159.1、140.8、133.7、128.7、128.1、126.7、126.6、114.2、55.3。
实施例的总结示于下述表1~3。
[表1]
[表2]
[表3]
Claims (5)
1.芳香族化合物的制造方法,其包括:在金属催化剂存在下使芳香族硝基化合物和硼酸化合物进行交叉偶联反应。
2.根据权利要求1所述的制造方法,其中,硼酸化合物为芳香族硼酸化合物,反应产物为偶联芳香族化合物。
3.根据权利要求1所述的制造方法,其中,金属催化剂为过渡金属催化剂。
4.根据权利要求3所述的制造方法,其中,过渡金属催化剂为钯或镍化合物。
5.根据权利要求1所述的制造方法,其中,使膦化合物共存。
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