CN103739417B - A kind of method synthesizing aromatic primary amine in recirculated water phase system - Google Patents
A kind of method synthesizing aromatic primary amine in recirculated water phase system Download PDFInfo
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- CN103739417B CN103739417B CN201310751904.3A CN201310751904A CN103739417B CN 103739417 B CN103739417 B CN 103739417B CN 201310751904 A CN201310751904 A CN 201310751904A CN 103739417 B CN103739417 B CN 103739417B
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- primary amine
- aromatic primary
- copper
- phase system
- ammonia
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 50
- -1 aromatic primary amine Chemical class 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 38
- 239000010949 copper Substances 0.000 claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 150000001502 aryl halides Chemical class 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 7
- 229920000768 polyamine Polymers 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 3
- 239000010452 phosphate Substances 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 48
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 5
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 5
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 3
- RUSUZAGBORAKPY-UHFFFAOYSA-N acetic acid;n'-[2-(2-aminoethylamino)ethyl]ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCNCCN RUSUZAGBORAKPY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid Substances OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 150000001503 aryl iodides Chemical class 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 239000000575 pesticide Substances 0.000 abstract description 3
- 239000003444 phase transfer catalyst Substances 0.000 abstract description 3
- 229930014626 natural product Natural products 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 66
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 63
- 238000003786 synthesis reaction Methods 0.000 description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 21
- 238000004440 column chromatography Methods 0.000 description 21
- 230000006837 decompression Effects 0.000 description 21
- 239000000706 filtrate Substances 0.000 description 21
- 238000000926 separation method Methods 0.000 description 21
- 229910002027 silica gel Inorganic materials 0.000 description 21
- 239000000741 silica gel Substances 0.000 description 21
- 229960001866 silicon dioxide Drugs 0.000 description 21
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 19
- 238000005160 1H NMR spectroscopy Methods 0.000 description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 15
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 14
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 12
- CUYKNJBYIJFRCU-UHFFFAOYSA-N 3-aminopyridine Chemical compound NC1=CC=CN=C1 CUYKNJBYIJFRCU-UHFFFAOYSA-N 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 3
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 2
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 description 2
- XEFRNCLPPFDWAC-UHFFFAOYSA-N 3,4,5-trimethoxyaniline Chemical compound COC1=CC(N)=CC(OC)=C1OC XEFRNCLPPFDWAC-UHFFFAOYSA-N 0.000 description 2
- MKARNSWMMBGSHX-UHFFFAOYSA-N 3,5-dimethylaniline Chemical compound CC1=CC(C)=CC(N)=C1 MKARNSWMMBGSHX-UHFFFAOYSA-N 0.000 description 2
- PNPCRKVUWYDDST-UHFFFAOYSA-N 3-chloroaniline Chemical compound NC1=CC=CC(Cl)=C1 PNPCRKVUWYDDST-UHFFFAOYSA-N 0.000 description 2
- QIKYZXDTTPVVAC-UHFFFAOYSA-N 4-Aminobenzamide Chemical compound NC(=O)C1=CC=C(N)C=C1 QIKYZXDTTPVVAC-UHFFFAOYSA-N 0.000 description 2
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 2
- KRZCOLNOCZKSDF-UHFFFAOYSA-N 4-fluoroaniline Chemical compound NC1=CC=C(F)C=C1 KRZCOLNOCZKSDF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 125000001475 halogen functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NCBZRJODKRCREW-UHFFFAOYSA-N m-anisidine Chemical compound COC1=CC=CC(N)=C1 NCBZRJODKRCREW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- HTDQSWDEWGSAMN-UHFFFAOYSA-N 1-bromo-2-methoxybenzene Chemical compound COC1=CC=CC=C1Br HTDQSWDEWGSAMN-UHFFFAOYSA-N 0.000 description 1
- PLDWAJLZAAHOGG-UHFFFAOYSA-N 1-bromo-3-methoxybenzene Chemical compound COC1=CC=CC(Br)=C1 PLDWAJLZAAHOGG-UHFFFAOYSA-N 0.000 description 1
- NHDODQWIKUYWMW-UHFFFAOYSA-N 1-bromo-4-chlorobenzene Chemical compound ClC1=CC=C(Br)C=C1 NHDODQWIKUYWMW-UHFFFAOYSA-N 0.000 description 1
- AITNMTXHTIIIBB-UHFFFAOYSA-N 1-bromo-4-fluorobenzene Chemical compound FC1=CC=C(Br)C=C1 AITNMTXHTIIIBB-UHFFFAOYSA-N 0.000 description 1
- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 description 1
- JXMZUNPWVXQADG-UHFFFAOYSA-N 1-iodo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1I JXMZUNPWVXQADG-UHFFFAOYSA-N 0.000 description 1
- ZLMKEENUYIUKKC-UHFFFAOYSA-N 1-iodo-3,5-dimethylbenzene Chemical compound CC1=CC(C)=CC(I)=C1 ZLMKEENUYIUKKC-UHFFFAOYSA-N 0.000 description 1
- UDHAWRUAECEBHC-UHFFFAOYSA-N 1-iodo-4-methylbenzene Chemical compound CC1=CC=C(I)C=C1 UDHAWRUAECEBHC-UHFFFAOYSA-N 0.000 description 1
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 description 1
- NYPYPOZNGOXYSU-UHFFFAOYSA-N 3-bromopyridine Chemical compound BrC1=CC=CN=C1 NYPYPOZNGOXYSU-UHFFFAOYSA-N 0.000 description 1
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 1
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 1
- ZRWNRAJCPNLYAK-UHFFFAOYSA-N 4-bromobenzamide Chemical compound NC(=O)C1=CC=C(Br)C=C1 ZRWNRAJCPNLYAK-UHFFFAOYSA-N 0.000 description 1
- TUXYZHVUPGXXQG-UHFFFAOYSA-N 4-bromobenzoic acid Chemical compound OC(=O)C1=CC=C(Br)C=C1 TUXYZHVUPGXXQG-UHFFFAOYSA-N 0.000 description 1
- XAOOZMATJDXDQJ-UHFFFAOYSA-N 5-bromo-1,2,3-trimethoxybenzene Chemical class COC1=CC(Br)=CC(OC)=C1OC XAOOZMATJDXDQJ-UHFFFAOYSA-N 0.000 description 1
- FBOYMIDCHINJKC-UHFFFAOYSA-N 5-bromo-1,3-benzodioxole Chemical compound BrC1=CC=C2OCOC2=C1 FBOYMIDCHINJKC-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- QLBHNVFOQLIYTH-UHFFFAOYSA-L dipotassium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [K+].[K+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O QLBHNVFOQLIYTH-UHFFFAOYSA-L 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010797 grey water Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 238000006362 organocatalysis Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of method synthesizing aromatic primary amine in recirculated water phase system, the method is with aryl halides and ammonia as raw material, using water as solvent, with alkali metal or the carbonate of alkaline-earth metal, fluoride, phosphate and hydroxide or the compound of corresponding alkali can be converted in water as alkali, with polyamines yl carboxylic acid and salt compounds thereof as part, copper source catalyst, catalysis aryl halides and ammonia is used to form aromatic primary amine.The present invention is using water as solvent, without using any phase transfer catalyst, and catalyst, part and reaction dissolvent water can recycle, effectively improve the environment friendly of reaction, more conform to the requirement of green chemistry, especially its wide application range of substrates, prepares aspect at natural product, medicine and pesticide and has broad prospects.
Description
Technical field:
The present invention relates to technical field of chemistry, a kind of method particularly relating to synthesize aromatic primary amine in graywater phase system.
Background technology:
Aromatic primary amine is a kind of important organic synthesis intermediate, also it is the important intermediate in agricultural chemicals, dyestuff, medical and some other chemical materials manufacture process, it is widely used in ((a) K.Weissermel in pesticide, medicine and material science, H.J.Arpe, Industry Organic Chemistry, Wiley-VCH, Weinheim, 1997;(b)S.A.Lawrence,Amines:Synthesis Properties,and Application,Cambridge University Press,Cambridge,2004;(c)G.Evano,N.Blanchard,M.Toumi,Chem.Rev.,108(2008)3054-3131;(d) Y.Aubin, C.Fischmeister, C.M.Thomas, J.-L.Renaud, Chem.Soc.Rev., 39 (2010) 4130-4145.).Therefore, the most more convenient, prepare aromatic primary amine compounds efficiently and cause people and pay attention to widely.
Ammonia is a kind of nitrogen source ((a) D.M.Roundhill, Chem.Rev.1992,92,1 cheap and easy to get;(b)J.Kim,H.J.Kim,S.Chang,Eur.J.Org.Chem.,(2013)3201-3213;(c) J.L.Klinkenberg, J.F.Hartwig, Angew.Chem.Int.Ed., 50 (2011) 86-95.).Utilize fragrance halides and ammonia reaction can be directly synthesized and obtain aromatic primary amine compounds.In recent years, achievement in research ((a) Ley, the S.V. of the aromatic carbon-nitrogen coupling reaction of lot of documents or patent report palladium or copper catalysis are had;Thomas,A.W.Angew.Chem.Int.Ed.2003,42,5400;(b)D.S.Surry,S.L.Buchwald,
Angew.Chem.Int.Ed.2008,47,6338;(c)J.P.Corbet,Chem.Rev.,2006,106,2651;(d) J.F.Hartwig, Synlett, 2006, 1283.), but due in the C-N coupling reaction process of fragrance halides and ammonia, the aromatic primary amine that reaction generates can form competition with ammonia, substantial amounts of the secondary amine even generation of tertiary amine class by-product may be caused, thus reduce the productivity of aromatic primary amine, therefore, for being prepared the research of the method for aromatic primary amine by the reaction of fragrance halides with ammonia, there is also huge challenge ((a) F.Lang, D.Zewge, I.N.Houpis, R.P.Volante, Tetrahedron Letter.2001, 42, 3251;(b) M.C.Willis, Angew.Chem.Int.Ed.2007,46,3402.).In recent years, by adding suitable ligand compound, the coupling reaction of transition metal-catalyzed halogenated aryl hydrocarbon and ammonia is used to make some progress.
At present, increasing document reports method ((a) X.F.Wu, C.Darcel, Eur.J.Org.Chem.2009,4753 being prepared aromatic primary amine by fragrance halides of copper catalysis;(b)N.Xia,M.Taillefer,Angew.Chem.Int.Ed.2009,48,337;(c)H.Wu,C.Wolf,Chem.Commun.2009,3035;(d)D.Wang,Q.Cai,K.Ding,Adv.Synth.Catal.2009,351,1722;(e)C.T.Yang,Y.Fu,Y.B.Huang,J.Yi,Q.X.Guo,L.Liu,Angew.Chem.2009,121,7534,Angew.Chem.Int.Ed.2009,48,7398;(f)L.Jiang,X,Lu,H.Zhang,Y.Jiang,D.Ma,J.Org.Chem.2009,74,4546;(g)X.Zeng,W.Huang,Y.Qiu,S.Jiang,Org.Biomol.Chem.,9(2011)8224-8227;(h)K.G.Thakur,D.Ganapathy,G.Sekar,Chem.Commun.,47(2011)5076-5078;(i)C.Tao,W.Liu,A.Lv,M.Sun,Y.Tian,Q.Wang,J.Zhao,Synlett,(2010)
1355-1358(j)A.K.Jha,N.Jain,Tetrahedron Lett.,54(2013)4738-4741;(k)A.Srivastava,N.Jain,Tetrahedron,69(2013)5092-5097;(l)Y.Wang,J.Luo,T.Hou,Z.Liu,Aust.J.Chem.,66(2013)586-593;(m) A.S.Kumar, T.Ramani, B.Sreedhar, Synlett, 24 (2013) 938-942.).But these reactions are typically carried out in organic solvent, and the many table structures of part used are complicated, and price is higher, it is difficult to obtain.Along with the raising day by day of mankind's environmental consciousness, and the proposition of Green Chemistry concept, how reducing or even eliminating the harmful substance of discharge in chemical industry has become mankind's growing interest and problem demanding prompt solution.
Compared with organic solvent, water has the features such as inexpensive, safety, environmental friendliness.So being applied in organic synthesis using water as reaction medium, it is most to be hopeful to realize one of industrialized green synthesis method.Aqueous phase organic synthesis has become as the key areas of current Green Chemistry research, and existing more document reports metal or the organic reaction of organocatalysis in aqueous phase system.Starting from 2010, in aqueous phase system, the fragrant halides of copper catalysis also achieves certain progress ((a) Z.Wu, Z.Jiang with the coupling reaction of ammonia, D.Wu, H.Xiang, X.Zhou, Eur.J.Org.Chem., (2010) 1854-1857;(b)F.Meng,X.Zhu,Y.Li,J.Xie,B.Wang,J.Yao,Y.Wan,Eur.J.Org.Chem.,(2010)6149-6152;(c)H.-J.Xu,Y.-F.Liang,Z.-Y.Cai,H.-X.Qi,C.-Y.Yang,Y.-S.Feng,J.Org.Chem.,76(2011)2296-2300;(d)Y.Zhu,Y.Wei,Can.J.Chem.,89(2011)645-649;(e)Y.Li,X.Zhu,F.Meng,Y.Wan,Tetrahedron67(2011)5450-5454;(f)J.Chen,T.Yuan,W.Hao,M.Cai,Tetrahedron Lett.,
52(2011)3710-3713;(g)H.-J.Xu,Y.-F.Liang,Z.-Y.Cai,H.-X.Qi,C.-Y.Yang,Y.-S.Feng,J.Org.Chem.,76(2011)2296-2300;(h)M.Huang,L.Wang,X.Zhu,Z.Mao,D.Kuang,Y.Wan,Eur.J.Org.Chem.,(2012)4897-4901;(i) B.-S.Liao, S.-T.Liu, Catal.comnun., 32 (2013) 28-31.).But these the most due needs use the available catalyst of non-commercial and part, the catalyst system and catalyzing majority employed in substantial amounts of phase transfer catalyst, and these reactions that needs to use having the most does not has cyclicity.And use catalyst system and catalyzing capable of circulation inexpensive, commercially available, it is possible not only to reduce synthesis cost, and the pollution to environment can be reduced.
The present invention is under state natural sciences fund (No.21272282,20802095,20872182) is subsidized, the research carried out for providing a kind of economy, gentleness, the preparation method of eco-friendly aromatic primary amine.
Summary of the invention:
It is an object of the invention to overcome in prior art shortcoming present in the synthetic method of aromatic primary amine, a kind of catalyst, part and solvent reusable edible, simplicity, the method synthesizing aromatic primary amine of reaction condition gentleness, wide application range of substrates, environmental friendliness, process economy are provided.
The present invention is achieved by the following technical programs:
A kind of method synthesizing aromatic primary amine in recirculated water phase system, the method is with aryl halides and ammonia as raw material, using water as solvent, with alkali metal or the carbonate of alkaline-earth metal, fluoride, phosphate and hydroxide or the compound of corresponding alkali can be converted in water as alkali, with polyamines yl carboxylic acid or its esters compound as part, copper source catalyst, catalysis aryl halides and ammonia is used to form aromatic primary amine.
Described catalyst, part and reaction dissolvent water can recycle.
The concrete course of reaction of the present invention is: copper source catalyst, part, aryl halides, alkali, ammonia and water are sequentially added into reaction tube, seals, and uses common heating bath mode of heating 60-130 DEG C stirring reaction 2-36h；After reaction terminates, separating reaction mixed liquor purification, obtain aromatic primary amine product.
The reaction equation that the present invention relates to is as follows:
Wherein ArX is aryl halides, and X-is selected from iodine or bromine.
Aryl halides is preferably aryl iodide for thing or aryl bromo-derivative.
Ar is the aromatic rings that aryl or substituted aryl, preferably 2-or 3-or 4-bit strip has monosubstituted base, or with two replacements or the aromatic rings of multi-substituent, described aromatic rings includes phenyl ring and pyridine ring.
Described pyridine ring is 3-halo or 2-halo.
Described substituent group is selected from H ,-NO2, halogen, amide, acetyl group, alkyl, alkoxyl, amido or carboxyl, but be not limited to these substituent groups.
Described aryl halides is 1: 5-1: 20 with the mol ratio of ammonia.
Described polyamines yl carboxylic acid or its esters compound are selected from diethylene triamine pentacetic acid (DTPA) or ethylenediaminetetraacetic acid or ethylenediamine-N, N'-oxalic acid or triethylenetetramine hexaacetic acid or its sodium salt or potassium salt；The mol ratio of polyamines yl carboxylic acid or its esters compound and copper source catalyst is 1:1-4:1.
Copper source catalyst is selected from metallic copper, the oxide of copper and various monovalence or the mantoquita of bivalence, such as: copper powder, copper oxide, Red copper oxide, copper sulfate, copper nitrate, copper chloride, Cu-lyt., Hydro-Giene (Water Science)., Schweinfurt green etc.；Copper source catalyst is preferably 1:40-1:5 with the mol ratio of substrate aryl halides.
Described alkali is preferably one below: potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate, cesium fluoride, potassium phosphate；Alkali is preferably 1.5:1-3:1 with the mol ratio of substrate aryl halides.
There is advantages that
The present invention is using water as solvent, without using any phase transfer catalyst, and catalyst, part and reaction dissolvent water can recycle, with in document report compared with type reaction, effectively improve the environment friendly of reaction, more conform to the requirement of green chemistry, especially its wide application range of substrates, prepare aspect at natural product, medicine and pesticide and have broad prospects.Additionally, the present invention is simple to operate, process economy and environmental friendliness, wide application range of substrates, the catalyst used and part are commercially available and product inexpensive, that obtain to be easily isolated purification, productivity high.
Detailed description of the invention:
The following is and the present invention is further illustrated rather than limitation of the present invention.
The synthesis of embodiment 1:4-aminoanisole
By 187mg(1mmol) 4-bromoanisole, 1mL ammonia (25-28%, 13.3mmol), 8mg(0.1mmol) CuO, 58mg(0.2mmol) ethylenediaminetetraacetic acid, 112mg(2mmol) KOH, 1mL H2O adds in 10mL reaction tube, seals, and reacts 12h under the conditions of 100 DEG C.After reaction stops, being extracted with ethyl acetate, saturated common salt is washed, and anhydrous sodium sulfate is dried, filters, and filtrate decompression is distilled, and purifies through silicagel column column chromatography for separation, obtains 4-aminoanisole 98mg, yield 80%.
1H NMR(300MHz,CDCl3)δ6.75(d,J=7.8Hz,2H),6.65(d,J=8.2Hz,2H),3.75(s,3H),3.37(brs,2H).13C NMR(75MHz,CDCl3)δ:153.0,140.2,116.6,115.1,56.1.ESI-MS:m/z=124[M+H]+.
Embodiment 2: the synthesis of paranitroanilinum
By 202mg(1mmol) 4-Nitrobromobenzene, 1mL ammonia (25-28%, 13.3mmol), 6mg(0.1mmol) Cu, 79mg(0.2mmol) diethylene triamine pentacetic acid (DTPA), 80mg(2mmol) NaOH, 1mL H2O adds in 10mL reaction tube, seals, and reacts 2h under the conditions of 100 DEG C.After reaction stops, being extracted with ethyl acetate, saturated common salt is washed, and anhydrous sodium sulfate is dried, filters, and filtrate decompression is distilled, and purifies through silicagel column column chromatography for separation, obtains 4-aminoanisole 60mg, yield 44%.
1H NMR(300MHz,DMSO)δ8.05(d,J=8.9Hz,2H),6.62(d,J=8.9Hz,2H),4.39(s,2H).13CNMR(75MHz,CDCl3)δ:156.3,136.3,127.0,113.0.MS(EI+):m/z=138[M+].
The synthesis of embodiment 3:4-monomethylaniline.
By 170mg(1mmol) 4-toluene bromide, 1mL ammonia (25-28%, 13.3mmol), 28mg(0.2mmol) Cu2O, 67mg(0.2mmol) disodium EDTA, 112mg(2mmol) KOH, 1mL H2O adds in 10mL reaction tube, seals, and reacts 12h under the conditions of 130 DEG C.After reaction stops, being extracted with ethyl acetate, saturated common salt is washed, and anhydrous sodium sulfate is dried, filters, and filtrate decompression is distilled, and purifies through silicagel column column chromatography for separation, obtains 4-monomethylaniline. 80mg, yield 80%.
By 282mg(1mmol) 4-iodotoluene, 1mL ammonia (25-28%, 13.3mmol), 8mg(0.1mmol) CuO, 79mg(0.2mmol) diethylene triamine pentacetic acid (DTPA), 112mg(2mmol) KOH, 1mL H2O adds in 10mL reaction tube, seals, and reacts 6h under the conditions of 100 DEG C.After reaction stops, being extracted with ethyl acetate, saturated common salt is washed, and anhydrous sodium sulfate is dried, filters, and filtrate decompression is distilled, and purifies through silicagel column column chromatography for separation, obtains 4-monomethylaniline. 80mg, yield 80%.
1H NMR(300MHz,CDCl3)δ:7.00(d,J=7.6Hz,2H),6.63(d,J=7.5Hz,2H),3.41(br s,2H),2.29(s,3H).13C NMR(75MHz,CDCl3)δ:144.0,130.0,128.0,115.5,20.9.ESI-MS:m/z=108[M+H]+.
The synthesis of embodiment 4:3-aminoanisole
By 187mg(1mmol) 3-methoxybromobenzene, 1mL ammonia (25-28%, 13.3mmol), 19mg(0.1mmol) CuI, 79mg(0.2mmol) diethylene triamine pentacetic acid (DTPA), 112mg(2mmol) KOH, 1mL H2O adds in 10mL reaction tube, seals, and reacts 12h under the conditions of 100 DEG C.After reaction stops, being extracted with ethyl acetate, saturated common salt is washed, and anhydrous sodium sulfate is dried, filters, and filtrate decompression is distilled, and purifies through silicagel column column chromatography for separation, obtains 3-aminoanisole 111mg, yield 90%.
1H NMR(300MHz,CDCl3) δ 7.11 (t, J=10.3Hz, 1H), 6.52-6.09 (m, 3H), 3.79 (s, 3H).13CNMR(75MHz,CDCl3)δ:160.9,148.4,130.4,108.2,104.1,101.3,55.4.ESI-MS:m/z=124[M+H]+.
Embodiment 5: the synthesis of o-aminoanisole
By 187mg(1mmol) 2-methoxybromobenzene, 1mL ammonia (25-28%, 13.3mmol), 5mg(0.025mmol) Cu (NO3)2, 39.5mg(0.1mmol) and diethylene triamine pentacetic acid (DTPA), 112mg(2mmol) KOH, 1mL H2O adds in 10mL reaction tube, seals, and reacts 36h under the conditions of 100 DEG C.After reaction stops, being extracted with ethyl acetate, saturated common salt is washed, and anhydrous sodium sulfate is dried, filters, and filtrate decompression is distilled, and purifies through silicagel column column chromatography for separation, and the amount obtaining 2-aminoanisole is 31mg.Yield is 42%.
By 234mg(1mmol) 2-methoxyl group iodobenzene, 1mL ammonia (25-28%, 13.3mmol), 25mg(0.1mmol) CuSO4.5H2O, 79mg(0.2mmol) diethylene triamine pentacetic acid (DTPA), 112mg(2mmol) KOH, 1mL H2O adds in 10mL reaction tube, seals, and reacts 24h under the conditions of 100 DEG C.After reaction stops, being extracted with ethyl acetate, saturated common salt is washed, and anhydrous sodium sulfate is dried, filters, and filtrate decompression is distilled, and purifies through silicagel column column chromatography for separation, and the amount obtaining 2-aminoanisole is 91mg, and yield is 74%.
1H NMR(300MHz,CDCl3)δ6.77(m,4H),3.86(s,3H),3.79(br s,2H).13C NMR(75MHz,CDCl3)δ:147.5,136.3,121.3,118.7,115.3,110.7,55.8.ESI-MS:m/z=124[M+H]+.
The synthesis of embodiment 6:3,4,5-trimethoxy-aniline
By 261mg(1mmol) 3,4,5-trimethoxy-bromobenzenes, 0.35mL ammonia (25-28%, 4.655mmol), 8mg(0.1mmol) CuO, 70mg(0.4mmol) ethylenediamine-N, N'-oxalic acid, 112mg(2mmol) KOH, 1mL H2O adds in 10mL reaction tube, seals, and reacts 12h under the conditions of 130 DEG C.After reaction stops, being extracted with ethyl acetate, saturated common salt is washed, and anhydrous sodium sulfate is dried, filters, and filtrate decompression is distilled, and purifies through silicagel column column chromatography for separation, obtains 3,4,5-trimethoxy-aniline 110mg, yield 60%.
1H NMR(300MHz,CDCl3)δ5.92(s,2H),3.80(s,6H)3.76(s,3H),3.55(brs,2H).13C NMR(75MHz,CDCl3)δ:154.0,143.1,130.8,92.8,61.4,56.2.ESI-MS:m/z=184[M+H]+.
Embodiment 7: the synthesis of aniline
By 157mg(1mmol) bromobenzene, 1mL ammonia (25-28%, 13.3mmol), 8mg(0.1mmol) Cu (OAc)2, 40mg(0.1mmol) and ethylenediamine tetraacetic acid,dipotassium salt, 112mg(2mmol) KOH, 1mL H2O adds in 10mL reaction tube, seals, and reacts 24h under the conditions of 60 DEG C.After reaction stops, being extracted with ethyl acetate, saturated common salt is washed, and anhydrous sodium sulfate is dried, filters, and filtrate decompression is distilled, and purifies through silicagel column column chromatography for separation, obtains aniline 57mg, yield 61%.
1H NMR(300MHz,CDCl3)δ:7.23-7.12(m,2H),6.82-6.75(m,1H),6.74-6.66(m,2H),3.56(brs,2H).13C NMR(75MHz,CDCl3)δ:146.5,129.5,118.8,115.4.ESI-MS:m/z=94[M+H]+。
The synthesis of embodiment 8:4-chloroaniline
By 191mg(1mmol) 4-chloro-bromobenzene, 1mL ammonia (25-28%, 13.3mmol), 8mg(0.1mmol) CuO, 99mg(0.2mmol) triethylenetetramine hexaacetic acid, 112mg(2mmol) KOH, 1mL H2O adds in 10mL reaction tube, seals, and reacts 12h under the conditions of 100 DEG C.After reaction stops, being extracted with ethyl acetate, saturated common salt is washed, and anhydrous sodium sulfate is dried, filters, and filtrate decompression is distilled, and purifies through silicagel column column chromatography for separation, obtains 4-chloroaniline 78mg, yield 61%.
1H NMR(300MHz,CDCl3)δ7.09(d,J=8.8Hz,2H),6.60(d,J=8.8Hz,2H),3.68(br s,2H).13C NMR(75MHz,CDCl3)δ:145.2,129.3,123.3,116.5.MS(ESI+):m/z=127[M+H]+.
The synthesis of embodiment 9:3-chloroaniline
By 238mg(1mmol) 3-chloroiodobenzone, 1mL ammonia (25-28%, 13.3mmol), 10mg(0.1mmol) CuCl, 79mg(0.2mmol) diethylene triamine pentacetic acid (DTPA), 112mg(2mmol) KOH, 1mL H2O adds in 10mL reaction tube, seals, and reacts 6h under the conditions of 100 DEG C.After reaction stops, being extracted with ethyl acetate, saturated common salt is washed, and anhydrous sodium sulfate is dried, filters, and filtrate decompression is distilled, and purifies through silicagel column column chromatography for separation, obtains 3-chloroaniline and be respectively 101mg.Yield is 79%.
1H NMR(300MHz,CDCl3)δ7.05(t,J=7.9Hz,1H),6.75-6.64(m,2H),6.57-6.52(m,1H).13C NMR(75MHz,CDCl3)δ:147.8,135.0,130.5,118.7,115.2,113.5.ESI-MS:m/z=128[M+H]+.
The synthesis of embodiment 10:3,5-dimethylaniline
By 185mg(1mmol) 3,5-dimethyl iodobenzene, 1mL ammonia (25-28%, 13.3mmol), 8mg(0.1mmol) CuO, 134mg(0.4mmol) disodiumedetate, 112mg(2mmol) KOH, 1mL H2O adds in 10mL reaction tube, seals, reacts 6h under the conditions of 100 DEG C respectively.After reaction stops, being extracted with ethyl acetate, saturated common salt is washed, and anhydrous sodium sulfate is dried, filters, and filtrate decompression is distilled, and purifies through silicagel column column chromatography for separation, obtains 3, and 5-dimethylaniline is 89mg.Yield is 74%.
1H NMR(300MHz,CDCl3)δ6.46(s,1H),6.36(s,2H),3.42(br s,2H),2.27(s,6H).13C NMR(75MHz,CDCl3)δ:146.5,139.2,120.7,113.4,21.7.ESI-MS:m/z=122[M+H]+.
The synthesis of embodiment 11:2-nitroaniline
By 249mg(1mmol) 2-nitro iodobenzene, 1mL ammonia (25-28%, 13.3mmol), 8mg(0.1mmol) CuO, 79mg(0.2mmol) diethylene triamine pentacetic acid (DTPA), 636mg(3mmol) K3PO4, 1mL H2O adds in 10mL reaction tube, seals, and reacts 6h under the conditions of 100 DEG C.After reaction stops, being extracted with ethyl acetate, saturated common salt is washed, and anhydrous sodium sulfate is dried, filters, and filtrate decompression is distilled, and purifies through silicagel column column chromatography for separation, obtains 2-nitroaniline 100mg, yield 72%.
1H NMR(300MHz,CDCl3)δ:8.11(dd,J=8.5Hz,1.4Hz,1H),7.35(ddd,J=8.5Hz,7.0Hz,1.6Hz,1H),6.73(m,2H),6.03(s,2H).13C NMR(75MHz,DMSO)δ:146.8,136.3,131.0,126.0,119.8,116.1.ESI-MS:m/z=139[M+H]+.
The synthesis of embodiment 12:4-acetyl group aniline
By 199mg(1mmol) 4-acetyl group bromobenzene, 1mL ammonia (25-28%, 13.3mmol), 14mg(0.1mmol) CuCl2, 79mg(0.2mmol) and diethylene triamine pentacetic acid (DTPA), 489mg(1.5mmol) Cs2CO3, 1mL H2O adds in 10mL reaction tube, seals, and reacts 6h under the conditions of 100 DEG C.After reaction stops, being extracted with ethyl acetate, saturated common salt is washed, and anhydrous sodium sulfate is dried, filters, and filtrate decompression is distilled, and purifies through silicagel column column chromatography for separation, obtains 4-acetyl group aniline 90mg, yield 66%.
1H NMR(300MHz,CDCl3)δ7.77(d,J=5.4Hz,2H),6.62(d,J=5.7Hz,2H),4.23(br s,2H),2.48(s,3H).13C NMR(75MHz,CDCl3)δ:196.7,151.7,131.0,127.7,113.9,26.4.ESI-MS:m/z=136[M+H]+.
The synthesis of embodiment 13:3-aminopyridine
By 158mg(1mmol) 3-bromopyridine, 0.75mL ammonia (25-28%, 9.975mmol), 8mg(0.1mmol) CuO, 79mg(0.2mmol) diethylene triamine pentacetic acid (DTPA), 112mg(2mmol) KOH, 1mL H2O adds in 10mL reaction tube, seals, and reacts 12h under the conditions of 100 DEG C.After reaction stops, being extracted with ethyl acetate, saturated common salt is washed, and anhydrous sodium sulfate is dried, filters, and filtrate decompression is distilled, and purifies through silicagel column column chromatography for separation, obtains 3-aminopyridine 60mg, yield 64%.
1H NMR(300MHz,CDCl3)δ8.03-7.79(m,2H),6.99-6.78(m,2H),3.97(br s,2H).13C NMR(75MHz,CDCl3)δ:143.2,139.4,137.3,124.0,121.7.ESI-MS:m/z=95[M+H]+.
The synthesis of embodiment 14:4-fluoroaniline
By 175mg(1mmol) 4-bromofluorobenzene, 1.5mL ammonia (25-28%, 19.95mmol), 8mg(0.1mmol) CuO, 79mg(0.2mmol) diethylene triamine pentacetic acid (DTPA), 112mg(2mmol) NaOH, 1mL H2O adds in 10mL reaction tube, seals, and reacts 12h under the conditions of 100 DEG C.After reaction stops, being extracted with ethyl acetate, saturated common salt is washed, and anhydrous sodium sulfate is dried, filters, and filtrate decompression is distilled, and purifies through silicagel column column chromatography for separation, obtains 4-fluoroaniline 79mg, yield 71%.
1H NMR(300MHz,CDCl3)δ6.85(t,J=8.6Hz,2H),6.66–6.55(m,2H),3.31(br s,2H).13C NMR(75MHz,CDCl3)δ:158.1,155.0,142.6,116.4,116.3,115.7.ESI-MS:m/z=112[M+H]+.
The synthesis of embodiment 15:3,4-methylene dioxo group aniline
By 201mg(1mmol) 3,4-methylene-dioxy bromobenzene, 1mL ammonia (25-28%, 13.3mmol), 8mg(0.1mmol) CuO, 79mg(0.2mmol) diethylene triamine pentacetic acid (DTPA), 112mg(2mmol) KOH, 1mL H2O adds in 10mL reaction tube, seals, and reacts 12h under the conditions of 100 DEG C.After reaction stops, being extracted with ethyl acetate, saturated common salt is washed, and anhydrous sodium sulfate is dried, filters, and filtrate decompression is distilled, and purifies through silicagel column column chromatography for separation, obtains 3,4-methylene dioxo group aniline 100mg, and yield is 73%.
1H NMR(300MHz,CDCl3)δ6.61(d,J=8.1Hz,1H),6.28(s,1H),6.11(d,J=8.1Hz,1H),5.85(s,1H)13C NMR(75MHz,CDCl3)δ:148.s,141.6,140.5,108.8,107.1,100.9,98.3.MS(ESI+):m/z=138[M+H]+。
The synthesis of embodiment 16:4-aminobenzamide
By 200mg(1mmol) 4-brombenzamide, 1mL ammonia (25-28%, 13.3mmol), 8mg(0.1mmol) CuO, 79mg(0.2mmol) ethylenediaminetetraacetic acid, 276mg(2mmol) K2CO3, 1mL H2O adds in 10mL reaction tube, seals, and reacts 12h under the conditions of 100 DEG C.After reaction stops, being extracted with ethyl acetate, saturated common salt is washed, and anhydrous sodium sulfate is dried, filters, and filtrate decompression is distilled, and purifies through silicagel column column chromatography for separation, obtains 4-aminobenzamide 70mg, yield 59%.
1H NMR(300MHz,DMSO)δ7.50(d,J=8.5Hz,2H),6.44(d,J=8.5Hz,2H),5.53(br s,2H).13CNMR(101MHz,DMSO)δ168.0,151.6,129.0,121.0,112.4.MS(EI+):m/z=137[M+H]+.
The synthesis of embodiment 17:4-amino benzoic Acid
By 201mg(1mmol) 4-bromobenzoic acid, 1mL ammonia (25-28%, 13.3mmol), 8mg(0.1mmol) CuO, 79mg(0.2mmol) diethylene triamine pentacetic acid (DTPA), 112mg(2mmol) KOH, 1mL H2O adds in 10mL reaction tube, seals, and reacts 12h under the conditions of 100 DEG C.After reaction stops, regulating pH to 2-3 with dilute hydrochloric acid.Being extracted with ethyl acetate, saturated common salt is washed, and anhydrous sodium sulfate is dried, filters, and filtrate decompression is distilled, and purifies through silicagel column column chromatography for separation, obtains PABA 119mg, yield 87%.
1H NMR(300MHz,CDCl3)δ7.89(d,J=8.6Hz,2H),6.64(d,J=8.6Hz,2H),4.10(br s,2H).13CNMR(101MHz,DMSO)δ167.5,153.1,131.2,116.9,112.6.MS(EI+):m/z=136[M-H]-.
The synthesis of embodiment 18:2-aminopyridine
By 158mg(1mmol) 2-bromopyridine, 1mL ammonia (25-28%, 13.3mmol), 8mg(0.1mmol) CuO, 79mg(0.2mmol) diethylene triamine pentacetic acid (DTPA), 304mg(2mmol) CsF, 1mL H2O adds in 10mL reaction tube, seals, and reacts 12h under the conditions of 100 DEG C.After reaction stops, being extracted with ethyl acetate, saturated common salt is washed, and anhydrous sodium sulfate is dried, filters, and filtrate decompression is distilled, and purifies through silicagel column column chromatography for separation, obtains PA 80mg, yield 85%.
1H NMR(400MHz,CDCl3)δ:7.99(ddd,J=5.1,1.8,0.8Hz,1H),7.36-7.35(m,1H),6.59-6.56(m,1H),6.45-6.42(m,1H),4.63(s,2H).13C NMR(101MHz,CDCl3)δ159.9,149.2,139.1,115.2,110.1.ESI-MS:m/z=95[M+H]+.
Embodiment 19: the synthesis of p-phenylenediamine
By 172mg(1mmol) 4-bromaniline, 1mL ammonia (25-28%, 13.3mmol), 8mg(0.1mmol) CuO, 79mg(0.2mmol) diethylene triamine pentacetic acid (DTPA), 212mg(2mmol) Na2CO3, 1mL H2O adds in 10mL reaction tube, seals, and reacts 12h under the conditions of 100 DEG C.After reaction stops, being extracted with ethyl acetate, saturated common salt is washed, and anhydrous sodium sulfate is dried, filters, and filtrate decompression is distilled, and purifies through silicagel column column chromatography for separation, obtains p-phenylenediamine 68mg, yield 63%.
1H NMR(300MHz,CDCl3)δ:6.55,(s,4H),3.32(br s,4H).13C NMR(101MHz,CDCl3)δ140.0,118.1,78.7,78.4,78.1.ESI-MS:m/z=109[M+H]+。
Claims (7)
1. the method synthesizing aromatic primary amine in recirculated water phase system, with aryl halides and ammonia as raw material, using water as solvent, with alkali metal or
The carbonate of alkaline-earth metal, fluoride, phosphate and hydroxide are alkali, it is characterised in that with polyamines yl carboxylic acid or its esters compound for joining
Body, uses copper source catalyst, catalysis aryl halides and ammonia to form aromatic primary amine；Described aryl halides is selected from aryl iodide for thing or aryl
Bromo-derivative；Described aryl is the aromatic rings that 2-or 3-or 4-bit strip have monosubstituted base, or with two replacements or the aromatic rings of multi-substituent, described
Aromatic rings is selected from phenyl ring or pyridine ring；Described polyamines yl carboxylic acid or its esters compound selected from diethylene triamine pentacetic acid (DTPA) or ethylenediaminetetraacetic acid or
Ethylenediamine-N, N'-oxalic acid or triethylenetetramine hexaacetic acid or its sodium salt or potassium salt；Copper source catalyst is selected from metallic copper, the oxide of copper
And various monovalence or the mantoquita of bivalence；Catalyst, part and reaction dissolvent in described recirculated water phase system can recycle.
The method synthesizing aromatic primary amine in recirculated water phase system the most according to claim 1, it is characterised in that it specifically reacts and is: Jiang Tongyuan urges
Agent, part, aryl halides, alkali, ammonia and water are sequentially added into reaction tube, seal, 60-130 DEG C of stirring reaction 2-36h；Reaction
After end, separating reaction mixed liquor purification, obtain aromatic primary amine product.
The method synthesizing aromatic primary amine in recirculated water phase system the most according to claim 1 and 2, it is characterised in that polyamines yl carboxylic acid or its esters
Compound is 1:1-4:1 with the mol ratio of copper source catalyst.
The method synthesizing aromatic primary amine in recirculated water phase system the most according to claim 1 and 2, it is characterised in that described aryl halides and ammonia
The mol ratio of water is 1: 5-1: 20.
The method synthesizing aromatic primary amine in recirculated water phase system the most according to claim 1 and 2, it is characterised in that copper source catalyst and substrate virtue
The mol ratio of base halides is 1:40-1:5.
The method synthesizing aromatic primary amine in recirculated water phase system the most according to claim 1, it is characterised in that copper source catalyst selected from copper powder,
Any one in copper oxide, Red copper oxide, copper sulfate, copper nitrate, copper chloride, Cu-lyt., Hydro-Giene (Water Science)., Schweinfurt green.
The method synthesizing aromatic primary amine in recirculated water phase system the most according to claim 1 and 2, it is characterised in that described alkali is selected from one below:
Potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate, cesium fluoride, potassium phosphate；Alkali is 1.5:1-3:1 with the mol ratio of aryl halides.
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